Semiconductor substrate doping method and doping treatment device

Abstract

A method for doping a semiconductor substrate is provided which is a wet processing method and has excellent diffusibility of a dopant element in the semiconductor substrate. [Solution] This is a doping treatment method for semiconductor substrates, which includes a preparation step of preparing adjusted water with an adjusted concentration of dopant element and a pH of 2 or more, an application step of applying the adjusted water to a semiconductor substrate, and a heating step of heating the semiconductor substrate to which the adjusted water has been applied.The preparation step of adjusted water includes an addition step of adding a concentration adjuster containing a dopant component to the water to be treated while controlling the amount of addition, and a pH adjustment step of adjusting the pH of the water to be treated before or after the addition of the concentration adjuster.

Description

[Technical Field]

[0001] The present disclosure relates to a doping processing method and a doping processing apparatus for a semiconductor substrate. [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 more applicable to semiconductor substrates having complex structures. The present inventors have found that in this case, the diffusibility of the dopant element in the semiconductor substrate may be insufficient.

[0005] An object of the present disclosure is to provide a method for doping a semiconductor substrate, which is a wet processing method and has excellent diffusibility of a dopant element in the semiconductor substrate. [Means for solving the problem]

[0006] One aspect of the doping treatment method for semiconductor substrates disclosed herein includes a preparation step of preparing adjusted water having an adjusted concentration of dopant elements and a pH of 2 or higher, an application step of applying the adjusted water to a semiconductor substrate, and a heating step of heating the semiconductor substrate to which the adjusted water has been applied.The preparation step of adjusted water includes an addition step of adding a concentration adjuster containing a dopant component to the water to be treated while controlling the amount of the agent added, and a pH adjustment step of adjusting the pH of the water to be treated before or after the addition of the concentration adjuster. [Effects of the Invention]

[0007] The doping method for a semiconductor substrate according to the present disclosure is a wet processing method and is excellent in diffusibility of dopant elements in a semiconductor substrate. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a block diagram that schematically illustrates one embodiment of a doping processing apparatus. [Figure 2] FIG. 2 is a block diagram that schematically illustrates one embodiment of a doping processing apparatus. [Figure 3] FIG. 3 is a block diagram that schematically illustrates one embodiment of a doping processing apparatus. [Figure 4] FIG. 4 is a block diagram that schematically illustrates one embodiment of a doping processing apparatus. 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] [Semiconductor substrate doping processing equipment] The doping treatment apparatus for a semiconductor substrate according to the present disclosure includes: an apparatus for producing adjusted water having a pH of 2 or more in which the concentration of a dopant element is adjusted; a coating device that coats the adjusted water on a semiconductor substrate; a heating device for heating the semiconductor substrate to which the adjusted water has been applied; Equipped with.

[0011] <Adjusted water manufacturing equipment> The manufacturing apparatus is an apparatus for manufacturing conditioned water in which the concentration of a dopant element is adjusted, and which is used to apply to a semiconductor substrate in a manufacturing process of a semiconductor or semiconductor device.

[0012] The manufacturing apparatus includes a dopant element concentration adjustment device that controls the amount of a concentration adjuster containing a dopant component added to the water to be treated, and a pH adjustment device that adjusts the pH of the water to be treated before or after the addition of the concentration adjuster. The manufacturing apparatus 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.

[0013] The manufacturing apparatus may be equipped with an impurity component removal device that selectively removes at least a portion of undesired impurity components, which are different from the desired dopant components, from the water to be treated or the concentration adjuster to which the concentration adjuster may be added.

[0014] The manufacturing apparatus 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 aqueous solutions obtained by adding a concentration adjuster, etc., to raw water are collectively referred to as "water to be treated."

[0015] The manufacturing apparatus 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 in a semiconductor or semiconductor device manufacturing process. By using such adjusted water, a 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 to appropriate locations on the semiconductor substrate surface in 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.

[0017] 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.

[0018] The conditioned water produced using the manufacturing apparatus is transported to a point of use (UP), such as an application apparatus for applying the conditioned water to a semiconductor substrate in a semiconductor or semiconductor device manufacturing process, or a heating apparatus for heating the semiconductor substrate to which the conditioned water has been applied.

[0019] <Dopant element concentration adjustment device> The manufacturing apparatus includes a device for adjusting the concentration of the dopant element. 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] Examples of arsenic compounds include arsenic trioxide-sodium sulfate, arsenic acid, arsenous acid, and trialkyl arsenates such as triethoxyarsenic and tri-n-butoxyarsenic.

[0025] Boron compounds include boric acid, metaboric acid, boronic acid, perboric acid, hypoboric acid, diboron trioxide, trialkyl borates, tetrahydroxydiborane, monoalkoxytrihydroxydiborane, dialkoxydihydroxydiborane, trialkoxymonohydroxydiborane, and tetraalkoxydiborane.

[0026] The concentration of the dopant element in the adjusted water obtained by the above-mentioned production apparatus is appropriately set depending on the 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 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-mentioned range.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] <Impurity component removal device> In one embodiment, the manufacturing apparatus 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.

[0031] 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.

[0032] 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.

[0033] 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).

[0034] The ion exchange resin may be, for example, a gel-type resin.

[0035] The removal device may include an ion exchange resin tower. The ion exchange resin tower may be one stage or two or more stages.

[0036] The above-mentioned removal device is, for example, a device that removes impurity components so that the concentration of 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.

[0037] In one embodiment, the removal device is located upstream or downstream, preferably downstream, of the dopant element concentration adjustment device on the transfer line for the water to be treated, thereby reducing the concentration of impurity components (e.g., metal elements and ions) in the water to be treated.

[0038] In one embodiment, the removal device is included in the dopant element concentration adjustment device. That is, in one embodiment, the concentration adjustment device may further include the removal device. This makes it possible, for example, to remove impurity components or reduce their concentrations in a concentration adjuster containing a dopant component that is added to the water to be treated, thereby making it possible to remove impurity components or reduce their concentrations in the water to be treated.

[0039] <pH adjuster and oxidation-reduction potential adjuster> The manufacturing apparatus further includes a pH adjuster that adjusts the pH of water to be treated, such as ultrapure water. The pH adjuster 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.

[0040] In one embodiment, the pH adjuster adjusts the pH of the water to be treated so that the pH of the adjusted water is 2 or higher, preferably 3 to 11, more preferably 5 to 10, and even more preferably 7 to 10. In one embodiment, the pH adjuster adjusts the pH of the water to be treated to 2 or higher, preferably 3 to 11, more preferably 5 to 10, and even more preferably 7 to 10. Adjusted water adjusted to such a pH has excellent diffusibility of dopant elements in semiconductor substrates, and by using this adjusted water, semiconductors or semiconductor devices having appropriate conductivity can be manufactured.

[0041] The manufacturing apparatus may further include an oxidation-reduction potential adjusting device (hereinafter also referred to as "ORP adjusting device") that adjusts the oxidation-reduction potential (hereinafter also referred to as "ORP adjusting device") of the water to be treated, such as ultrapure water. The ORP adjusting device is preferably located downstream of the pH adjusting 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 adjusting device.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] In one embodiment, the pH adjuster adjusts the pH of the water to be treated to preferably 8 to 11. A pH of 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 and the like included in degassing devices or gas dissolved membrane devices.

[0050] 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.

[0051] The pH adjuster is preferably a liquid, more preferably an aqueous solution of an alkaline compound, and even more preferably an aqueous ammonia solution.

[0052] 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. The ORP is a value measured at 23°C using a known ORP meter.

[0053] <Hydrogen peroxide removal device> The production apparatus 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 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 pressurization. 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 production apparatus 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, 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 may further include a gas dissolved film type device. 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 preferably further includes a water quality monitor for the water to be treated or the adjusted water. The water quality monitor measures the water quality (e.g., the concentration of the dopant element, the concentration of the active ingredient of the pH adjuster, and the pH) 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 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, for example, and monitors whether the concentration of the dopant element is at a desired value and / or measures the concentration or pH of the active ingredient of the pH adjuster and monitors whether these are 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, oxidation-reduction potential (ORP), and the concentration of an inert gas in the water to be treated or the conditioned water, 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 preferably further comprises 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 to the control device, for example, electrically or wirelessly. The control device may be connected to at least one device selected from the group consisting of the concentration adjusting device, pH adjusting device, ORP adjusting device, and gas dissolved film type device, for example, electrically or wirelessly.

[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 the amount of pH adjuster added or the supply rate in a pH adjustment device based on the water quality of the water to be treated or the adjusted water measured by a water quality monitoring device, or a device that controls at least one selected from the group consisting of the amount of ORP adjuster added or the supply rate in an ORP adjustment device, and the amount of inert gas added or the supply rate in a gas-dissolved membrane 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, a set ORP value, and a set concentration of the inert gas. The control of at least one selected from the group consisting of the concentration of the active ingredient, pH, ORP, and the concentration of the inert gas 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 may further include a temperature control device. The location of the temperature control device in the manufacturing apparatus is not particularly limited. Examples of the temperature control device include a heat exchanger.

[0081] <Flow path> In the manufacturing apparatus, 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 pipes, and may be provided with equipment such as tanks, pumps, joints, and valves.

[0082] 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.

[0083] <Coating equipment> The doping treatment apparatus further includes an application device for applying the prepared conditioned water to a semiconductor substrate at a point of use of the prepared conditioned water, the semiconductor substrate being used in a semiconductor or semiconductor device manufacturing process, for example. 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.

[0084] <Heating device> The doping treatment apparatus includes a heating device for heating the semiconductor substrate coated with the adjusted water, such as a hot plate, an oven, an infrared heater, an induction heating device, a dielectric heating device, a lamp annealing device, and a microwave heating device. The coating device and the heating device may be incorporated into one device or may be provided as independent devices. In the latter case, the semiconductor substrate coated with the adjusted water in the coating device is transferred to the heating device.

[0085] <Example of Doping Treatment Apparatus> Hereinafter, an embodiment of the doping processing apparatus will be described in detail with reference to the drawings. 1 to 4 are block diagrams each showing a schematic diagram of the doping treatment apparatus.

[0086] 1 includes a transfer line L1 for water W to be treated, such as ultrapure water, a dopant element concentration adjuster 10, a pH adjuster 50, an impurity component remover 20, and a water quality monitor 30. The transfer line L1 connects the concentration adjuster 10 and the pH adjuster 50, connects the pH adjuster 50 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, a pH adjuster 50, 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, a pH adjuster 50, and a monitoring device 30, in this order. The point of use (UP) is equipped with a conditioning water applicator and a semiconductor substrate heating device.

[0087] 2 includes a transfer line L1 for water W to be treated, such as ultrapure water, a dopant element concentration adjuster 10, a pH adjuster 50, a water quality monitor 30, and an impurity component remover 20. The transfer line L1 connects the concentration adjuster 10 and the pH adjuster 50, connects the pH adjuster 50 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, a pH adjuster 50, 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 a pH adjuster 50, in this order.

[0088] 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.

[0089] 3 includes a transfer line L1 for water W to be treated, such as ultrapure water, a concentration adjuster 10 for a dopant element, a pH adjuster 50, and a water quality monitor 30. The transfer line L1 connects the concentration adjuster 10 and the pH adjuster 50, and also connects the pH adjuster 50 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, a pH adjuster 50, and a water quality monitor 30. The adjusted water thus produced is sent to a point of use (UP) via a transfer line L2.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] The production apparatus 1 in FIG. 4 does not necessarily have to include at least one device selected from the group consisting of the hydrogen peroxide removal device 90, the ORP adjustment device 60, the degassing device 70, and the gas dissolved film type device 80.

[0094] 1 to 4 controls the amount or supply rate of the concentration adjuster in the concentration adjuster 10 and the amount or supply rate of the pH adjuster in the pH adjuster 50 based on the water quality (e.g., concentration of the dopant element, concentration of the active ingredient in the pH adjuster, pH) obtained by the water quality monitoring device 30. The control device 40 in FIG. 4 controls the amount or supply rate of the ORP adjuster in the ORP adjuster 60 and the inert gas in the gas dissolved film type device 80 based on the water quality obtained by the water quality monitoring device 30.

[0095] The doping treatment device of the present disclosure has been described above based on the above embodiment with reference to the accompanying drawings, but the doping treatment device of the present disclosure is not limited to the above embodiment and can be modified in various ways.

[0096] [Method for doping semiconductor substrate] The doping treatment method for semiconductor substrates disclosed herein includes a step of preparing adjusted water having a pH of 2 or higher and an adjusted concentration of dopant elements (hereinafter also referred to as the "preparation step"), a step of applying the adjusted water to a semiconductor substrate (hereinafter also referred to as the "application step"), and a step of heating the semiconductor substrate to which the adjusted water has been applied (hereinafter also referred to as the "heating step").

[0097] <Preparation process> The preparation process 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"); a step of adjusting the pH of the water to be treated before or after the addition of the concentration adjuster (hereinafter also referred to as a "pH adjustment step"); It has.

[0098] In one embodiment, the preparation step further includes a step of measuring the concentration of the dopant element in the treatment target water or adjusted water to which the concentration adjuster has been added (hereinafter also referred to as a "water quality monitoring step").

[0099] In one embodiment, the preparation step further includes a step of selectively removing at least a portion of impurity components other than the dopant component from the treatment target water to which the concentration adjuster may be added (hereinafter also referred to as a "removal step"); or The adding step further includes a step (removing step) of selectively removing at least a part of impurity components different from the dopant component from the concentration adjusting agent.

[0100] The preparation step adjusts the concentration of the dopant element, and in one embodiment, produces adjusted water with a reduced content of impurity components. The adjusted water can be used to apply to semiconductor substrates in the manufacturing process of semiconductors or semiconductor devices.

[0101] In the addition step, a concentration adjuster containing a dopant component is added to water to be treated, such as ultrapure water, etc. 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, even more preferably 0.5 to 20,000 mg / L, and particularly preferably 1 to 13,000 mg / L.

[0102] In one embodiment of the pH adjustment step, the pH of the water to be treated is adjusted to 2 or higher, preferably 3 to 11, more preferably 5 to 10, and even more preferably 7 to 10. In one embodiment of the pH adjustment step, a pH adjuster is added to the water to be treated, for example, to adjust the pH of the water to be treated before or after the addition of the concentration adjuster to 2 or higher, preferably 3 to 11, more preferably 5 to 10, and even more preferably 7 to 10. Adjusted water adjusted to such a pH has excellent diffusibility of dopant elements in semiconductor substrates, and by using this adjusted water, semiconductors or semiconductor devices having appropriate conductivity can be manufactured.

[0103] 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.

[0104] In the water quality monitoring step, the water quality (e.g., the concentration of the dopant element, the concentration of the active ingredient of the pH adjuster, and pH) 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 at least one selected from the group consisting of the addition amount or supply rate of the concentration adjuster in the addition step and the addition amount or supply rate of the pH adjuster in the pH adjustment step so that the adjusted water has the desired water quality.

[0105] 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, an ORP adjustment step for adjusting the oxidation-reduction potential (ORP) of 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.

[0106] Regarding the details of the preparation process and the conditions for each process, the conditions described in the above section <Apparatus for producing adjusted water> can be applied, and description here will be omitted. The preparation step can be carried out using, for example, the production apparatus.

[0107] The adjusted water produced by the manufacturing apparatus or preparation process 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.

[0108] <Coating process> In the coating step, the adjusted water is coated onto the semiconductor substrate. Known coating methods can be used, including 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.

[0109] As the semiconductor substrate, various substrates that have conventionally been 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 thereof include Si, SiO2, SiCN, SiN, and SiC.

[0110] <Heating process> In the heating step, the semiconductor substrate coated with the adjusted water is heated, which allows the dopant element contained in the adjusted water to be diffused well into the semiconductor substrate.

[0111] From the viewpoints of the diffusibility of the dopant element, thermal budget, etc., the heating temperature in the heating step is preferably 200 to 1000°C, more preferably 300 to 900°C, even more preferably 400 to 800°C, and particularly preferably 400 to 700°C. From the above viewpoints, the heating time in the heating step is preferably 1 minute to 10 hours, more preferably 3 minutes to 5 hours, and even more preferably 5 minutes to 60 minutes.

[0112] [Method of manufacturing semiconductors or semiconductor devices] The doping method can be used to manufacture semiconductors or semiconductor devices by a manufacturing method including a step of doping a semiconductor substrate. Other known steps can be used as the doping step. Examples of semiconductor devices include transistors, diodes, and solar cells.

[0113] [Example of situation] The present disclosure relates to, for example, the following [1] to

[14] . [1] A doping treatment method for semiconductor substrates, comprising: a preparation step of preparing adjusted water having an adjusted concentration of a dopant element and a pH of 2 or more; an application step of applying the adjusted water to a semiconductor substrate; and a heating step of heating the semiconductor substrate to which the adjusted water has been applied, wherein the preparation step of the adjusted water comprises: an addition step of adding a concentration adjuster containing a dopant component to the water to be treated while controlling the amount of the agent added; and a pH adjustment step of adjusting the pH of the water to be treated before or after the addition of the concentration adjuster. [2] The doping treatment method for semiconductor substrates described in [1], wherein the preparation step 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. [3] The doping treatment method for a semiconductor substrate according to [2], wherein the concentration of the impurity component in the water to be treated or the concentration adjuster after the removal is 1 μg / L or less. [4] The method for doping a semiconductor substrate according to any one of [1] to [3] above, wherein the concentration of the dopant element in the adjusted water is 100,000 mg / L or less. [5] The method for doping a semiconductor substrate according to any one of [1] to [4] above, wherein the concentration adjusting agent is an aqueous solution containing the dopant component. [6] The doping treatment method for a semiconductor substrate according to [5], 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. [7] A method for manufacturing a semiconductor or a semiconductor device, comprising a step of doping a semiconductor substrate using the method for doping a semiconductor substrate according to any one of [1] to [6] above. [8] A doping treatment apparatus for semiconductor substrates, comprising: a manufacturing apparatus for adjusted water having a pH of 2 or more in which the concentration of a dopant element has been adjusted; an application apparatus for applying the adjusted water to a semiconductor substrate; and a heating apparatus for heating the semiconductor substrate to which the adjusted water has been applied; wherein the manufacturing apparatus comprises: a dopant element concentration adjustment apparatus for adding a concentration adjuster containing a dopant component to the water to be treated by controlling the amount of addition; and a pH adjustment apparatus for adjusting the pH of the water to be treated before or after the addition of the concentration adjuster. [9] The doping treatment device for semiconductor substrates described in [8], wherein the manufacturing apparatus is equipped with 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.

[10] The doping treatment device for a semiconductor substrate according to [9], 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.

[11] The doping treatment apparatus for semiconductor substrates described in [9] or

[10] , wherein the removal device is located upstream or downstream of the concentration adjustment device for the dopant element on the transfer line of the water to be treated.

[12] The doping treatment apparatus for a semiconductor substrate according to any one of [9] to

[11] , wherein the concentration adjustment device has the removal device.

[13] A doping treatment apparatus for semiconductor substrates according to any one of [8] to

[12] , wherein the manufacturing apparatus further comprises 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.

[14] The doping treatment apparatus for semiconductor substrates described in any one of [8] to

[13] , wherein the manufacturing apparatus further comprises an oxidation-reduction potential adjusting device that adjusts the oxidation-reduction potential of the water to be treated before or after the addition of the concentration adjuster. [Example]

[0114] The doping method for a semiconductor substrate according to the present disclosure will be described based on examples, but the doping method for a semiconductor substrate according to the present disclosure is not limited to the following examples.

[0115] 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, a doping treatment device equipped with the manufacturing apparatus 1 shown in FIG. 1 was used. The dopant element concentration adjustment 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 removal device 20 includes a cation exchange resin (product name KR-FC, manufactured by Kurita Water Industries Ltd.).

[0116] [Example 1] The following adjusted water was produced using the production apparatus 1 shown in FIG. 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 a concentration adjuster 10 so 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 a pH adjuster 50. Next, the mixed solution after pH adjustment was passed through a removal device 20 equipped with a cation exchange resin (product name KR-FC). In this way, adjusted water 1 was prepared, in which the concentrations of boric acid, arsenic acid, and phosphoric acid were each 1% by mass (10,000 ppm).

[0117] The pH was measured using a pH meter (Horiba). 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.

[0118] 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.

[0119] The resulting adjusted water was filled into a batch tank, and the silicon wafers were immersed in the adjusted water at 25°C for 10 minutes, after which they were removed from the adjusted water. The immersed silicon wafers were then annealed at 700°C for 20 minutes. To determine the amount of doped ions on the silicon wafers, the volume resistivity was calculated using a four-probe sheet resistance analyzer (SEMiLAb, FPP1000). The volume resistivity was evaluated according to the following criteria. The results are shown in Table 1.

[0120] Evaluation criteria for volume resistivity ◎: 1.0×10 -4 ~1.0×10 0 Ωcm ○:1.0×10 0 Ωcm super 1.0×10 5 Ωcm or less △:1.0×10 -4 Less than Ωcm ×:1.0×10 5 Ωcm super

[0121] 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 ◎:50nm or more 〇: 25nm or more, less than 50nm △: Over 5nm, under 25nm ×: 5nm or less

[0122] [Examples 2 to 5, Comparative Example 1] Adjusted waters 2 to 5 and 7 were prepared in the same manner as in Example 1, except that the types and amounts of the boric acid aqueous solution and pH adjuster were adjusted and the concentration or pH of each component was changed as shown in Table 1. Except for using these adjusted waters, the same procedures as in Example 1 were carried out.

[0123] [Example 6] The following adjusted water was produced using the production apparatus 1 shown in FIG. 1 (but without the removal apparatus 20) as follows. To ultrapure water, an aqueous phosphoric acid solution was added in a concentration adjuster 10 in an amount such that the phosphoric acid concentration in the adjusted water would be the value shown in Table 1, and then a pH adjuster (aqueous ammonia solution) was added in a pH adjuster 50 to adjust the pH to the value shown in Table 1, thereby preparing adjusted water 6. The same procedure as in Example 1 was carried out except that adjusted water 6 was used.

[0124] [Table 1] [Explanation of symbols]

[0125] 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 a pH of 2 or more in which the concentration of a dopant element is adjusted; a coating device that coats the adjusted water on a semiconductor substrate; a heating device for heating the semiconductor substrate to which the adjusted water has been applied; A doping treatment apparatus for a semiconductor substrate, comprising: 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; a pH adjusting device for adjusting the pH of the water to be treated before or after the addition of the concentration adjuster; 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; A doping treatment apparatus for a semiconductor substrate, comprising:

2. 2. The semiconductor substrate doping treatment device of claim 1, wherein the manufacturing apparatus is provided with 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.

3. The doping treatment apparatus for a semiconductor substrate according to claim 2 , 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.

4. 3. The doping treatment apparatus for semiconductor substrates according to claim 2, wherein the removal device is located on a transfer line for the water to be treated, upstream or downstream of the device for adjusting the concentration of the dopant element.

5. An apparatus for producing adjusted water having a pH of 2 or more in which the concentration of a dopant element is adjusted; a coating device that coats the adjusted water on a semiconductor substrate; a heating device for heating the semiconductor substrate to which the adjusted water has been applied; A doping treatment apparatus for a semiconductor substrate, comprising: 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; a pH adjusting device for adjusting the pH of the water to be treated before or after the addition of the concentration adjuster; Equipped with the concentration adjusting device has an impurity component removing device that selectively removes at least a part of an impurity component different from the dopant component from the concentration adjusting agent; Semiconductor substrate doping processing equipment.

6. The doping treatment apparatus for a semiconductor substrate according to claim 1 or 5, wherein the manufacturing apparatus further comprises an oxidation-reduction potential adjusting device that adjusts the oxidation-reduction potential of the water to be treated before or after the addition of the concentration adjusting agent.

7. 6. The doping treatment apparatus for a semiconductor substrate according to claim 1, wherein the concentration of the dopant element in the adjusted water is 100,000 mg / L or less.

8. 6. The doping treatment apparatus for a semiconductor substrate according to claim 1, wherein the concentration adjusting agent is an aqueous solution containing the dopant component.

9. 9. The doping treatment apparatus for a semiconductor substrate according to claim 8, 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.

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