Method for inspecting chemical solution, method for producing chemical solution, method for controlling chemical solution, method for producing semiconductor device, method for inspecting resist composition, method for producing resist composition, method for controlling resist composition, and method for checking contamination status of semiconductor manufacturing apparatus

Abstract

This invention provides a method for inspecting a pharmaceutical solution capable of analyzing minute foreign matter in a pharmaceutical solution, a method for manufacturing a pharmaceutical solution, a method for managing a pharmaceutical solution, a method for manufacturing a semiconductor device, a method for inspecting a photoresist composition capable of analyzing minute foreign matter in a photoresist composition, a method for manufacturing a photoresist composition, a method for managing a photoresist composition, and a method for confirming the contamination status of a semiconductor manufacturing apparatus capable of managing minute foreign matter in a semiconductor manufacturing apparatus. The method for inspecting the pharmaceutical solution includes: a process for preparing the pharmaceutical solution (1X); a process for coating the pharmaceutical solution onto a semiconductor substrate (2X); and a process (3X) for determining whether there are defects on the surface of the semiconductor substrate, obtaining location information of the defects on the semiconductor substrate surface, irradiating the defects on the semiconductor substrate surface with laser light based on the location information, recovering the analytical sample obtained by irradiation using a carrier gas, and performing inductively coupled plasma mass spectrometry analysis.

Description

Technical Field

[0001] This invention relates to a method for inspecting reagents using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), a method for manufacturing reagents, a method for managing reagents, a method for manufacturing semiconductor devices, a method for inspecting photoresist components, a method for manufacturing photoresist components, a method for managing photoresist components, and a method for confirming the contamination status of a semiconductor manufacturing apparatus. Prior Technology

[0002] Currently, silicon substrates and other semiconductor substrates are used to manufacture various semiconductor devices. When defects such as foreign objects exist on the surface of the semiconductor substrate, sometimes the gate of the transistor cannot be fully formed during the manufacturing process, or wiring breaks occur, resulting in defective semiconductor devices. Such defects on the surface of the semiconductor substrate affect the yield of semiconductor devices.

[0003] Regarding defects in semiconductor substrates, for example, the method for evaluating residual metal impurities within the silicon crystal of a silicon wafer described in Patent Document 1 can be used. The method in Patent Document 1 for evaluating residual metal impurities within the silicon crystal of a silicon wafer involves heat treatment to cause the metal impurities within the silicon crystal to accumulate on the surface of the silicon wafer, followed by vapor phase decomposition inductively coupled plasma mass spectrometry (VPD-ICP-MS) to determine the concentration of metal impurities accumulated on the surface of the silicon wafer. The number of surface defects on the silicon wafer is determined using a SurfScan SP5 manufactured by KLA Corporation. [Previous Technical Documents] [Patent Literature]

[0004] Patent Document 1: Japanese Patent Application Publication No. 2019-195020 Patent Document 2: Japanese Patent Application Publication No. 2020-027920 Summary of the Invention

[0005] [The problem that the invention aims to solve]

[0006] The inductively coupled plasma mass spectrometry (ICP-MS) method described in Patent Document 1 dissolves the silicon wafer, making it impossible to non-destructively evaluate defects in the semiconductor substrate. Patent Document 2 describes a method for evaluating metal contamination in a wafer as a non-destructive method for evaluating defects in a semiconductor substrate.

[0007] In the evaluation method for metal contamination of a wafer described in Patent Document 2, a particle counter (e.g., KLA Corporation's SurfScanSP5) is used as a foreign object inspection device, employing a confocal optical system laser microscope (e.g., Lasertec Corporation's MAGICS) that detects foreign objects by scanning the wafer surface with laser light and measuring the intensity of light scattering from them, and a confocal optical system that detects foreign objects by detecting the difference in reflected light from the wafer surface. The method also includes SEM (Scanning Electron Microscope) observation of bright spots based on coordinates obtained in the first process, and EDX (Energy Dispersive X-ray Spectroscopy) analysis based on characteristic X-rays generated by electron beam irradiation.

[0008] As mentioned above, when defects such as foreign matter exist on the surface of a semiconductor substrate, especially with the miniaturization and high integration of semiconductor devices, the impact of surface defects on the semiconductor substrate on the production of defective semiconductor devices and the resulting decrease in yield is becoming increasingly significant. Therefore, it is important to measure the surface defects of the semiconductor substrate, and it is even more important to measure the minute foreign matter within the semiconductor substrate defects. However, when the method for evaluating metal contamination of wafers described in Patent Document 2 is used to analyze minute foreign matter of about 20 nm on the surface of a semiconductor substrate, there is a high possibility that elemental analysis cannot be performed using EDX. Similar to the semiconductor substrates mentioned above, from the perspective of quality management and manufacturing, it is also desirable to be free of defects such as foreign matter in the pharmaceutical solution and photoresist composition. Therefore, it is desirable to measure foreign matter, and in particular, it is desirable to measure and analyze the elements of minute foreign matter. Furthermore, in semiconductor manufacturing facilities, contamination can affect the performance and quality of manufactured products, thus requiring the management of minute foreign matter. To manage minute foreign matter in semiconductor manufacturing facilities, it is particularly desirable to measure and perform elemental analysis on minute foreign matter that contributes to the miniaturization and high integration of semiconductor components, thereby preventing defects.

[0009] The purpose of this invention is to provide a method for inspecting a pharmaceutical solution capable of analyzing minute foreign matter in the solution, a method for manufacturing a pharmaceutical solution, a method for managing a pharmaceutical solution that enables quality control even when the solution contains trace amounts of minute foreign matter, a method for manufacturing a semiconductor element, a method for inspecting a photoresist composition capable of analyzing minute foreign matter in the photoresist composition, a method for manufacturing a photoresist composition, a method for managing a photoresist composition that enables quality control even when the photoresist composition contains trace amounts of minute foreign matter, a method for manufacturing a semiconductor element, and a method for confirming the contamination status of a semiconductor manufacturing apparatus capable of managing minute foreign matter in a semiconductor manufacturing apparatus. [Methods for solving problems]

[0010] To achieve the above objectives, one aspect of the present invention provides a method for inspecting a pharmaceutical solution, comprising: a process 1X of preparing the pharmaceutical solution; a process 2X of coating the pharmaceutical solution onto a semiconductor substrate; and a process 3X of determining whether there are defects on the surface of the semiconductor substrate, obtaining position information of the defects on the surface of the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the position information, recovering the analytical sample obtained by irradiation using a carrier gas, and performing inductively coupled plasma mass spectrometry analysis. Preferably, the process includes a process 4X that determines whether a defect contains a metal element based on mass spectrometry data of the defect obtained in process 3X. Preferably, after process 4X, there is a process 5X that determines the number of defects containing a metal element. Preferably, the process 5X includes a process 5X that determines the number of defects containing a metal element based on mass spectrometry data of the defect obtained in process 3X.

[0011] Preferably, the solution contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total content of the metallic elements is less than 10 ppb by mass relative to the total mass of the solution. Preferably, the water content of the carrier gas is above 0.00001 ppm by volume and below 0.1 ppm by volume.

[0012] One aspect of the present invention provides a method for manufacturing a pharmaceutical solution, which includes a method for inspecting the pharmaceutical solution. One embodiment of the present invention provides a method for managing a pharmaceutical solution, comprising: a process 1X of preparing the pharmaceutical solution; a process 2X of coating the pharmaceutical solution onto a semiconductor substrate; a process 3X of determining whether there are defects on the surface of the semiconductor substrate, obtaining position information of the defects on the surface of the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the position information, recovering the analytical sample obtained by irradiation using a carrier gas and performing inductively coupled plasma mass spectrometry analysis; a process 4X of determining whether there are metal elements in the defects based on the mass spectrometry data of the defects obtained in process 3X and a process 5X of determining the number of defects containing metal elements, or a process 5X of determining the number of defects containing metal elements based on the mass spectrometry data of the defects obtained in process 3X; and a process 6X of determining whether the number of defects obtained in process 5X is within an acceptable range.

[0013] Preferably, the solution contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total content of the metallic elements is less than 10 ppb by mass relative to the total mass of the solution. Preferably, the water content of the carrier gas is above 0.00001 ppm by volume and below 0.1 ppm by volume.

[0014] One aspect of the present invention provides a method for manufacturing a semiconductor device, comprising: a process 1X of preparing a reagent solution; a process 2X of coating the reagent solution onto a semiconductor substrate; a process 3X of determining whether there are defects on the surface of the semiconductor substrate, obtaining position information of the defects on the surface of the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the position information, recovering the analytical sample obtained by irradiation using a carrier gas and performing inductively coupled plasma mass spectrometry analysis; a process 4X of determining whether there are metal elements in the defects based on the mass spectrometry data of the defects obtained in process 3X and a process 5X of determining the number of defects containing metal elements, or a process 5X of determining the number of defects containing metal elements based on the mass spectrometry data of the defects obtained in process 3X; a process 6X of determining whether the number of defects obtained in process 5X is within an acceptable range; and a process 7X of manufacturing a semiconductor device using a reagent solution determined to be within an acceptable range in process 6X.

[0015] Preferably, the solution is a pre-wetting solution, developing solution, rinsing solution, or cleaning solution. Preferably, the solution contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn, and the total content of the metallic elements is less than 10 ppb by mass relative to the total mass of the solution. Preferably, the water content of the carrier gas is more than 0.00001 ppm by volume and less than 0.1 ppm by volume.

[0016] One aspect of the present invention provides a method for inspecting a photoresist composition, comprising: a process 1Y for preparing the photoresist composition; a process 2Y for coating the photoresist composition onto a semiconductor substrate; and a process 3Y for determining whether there are defects in the coating of the photoresist composition, obtaining position information of the defects in the coating of the photoresist composition on the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the position information, recovering the analytical sample obtained by irradiation using a carrier gas, and performing inductively coupled plasma mass spectrometry analysis. Preferably, the process includes a process 4Y for determining whether a defect contains a metal element based on mass spectrometry data of the defect obtained in process 3Y. Preferably, after process 4Y, there is a process 5Y for determining the number of defects containing a metal element. Preferably, process 5Y includes a process for determining the number of defects containing a metal element based on mass spectrometry data of the defect obtained in process 3Y.

[0017] Preferably, the photoresist composition contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total content of the metallic elements is less than 10 ppb by mass relative to the total mass of the photoresist composition. Preferably, the water content of the carrier gas is above 0.00001 ppm by volume and below 0.1 ppm by volume.

[0018] One aspect of the present invention provides a method for manufacturing a photoresist composition, which includes a method for inspecting the photoresist composition. One aspect of the present invention provides a method for managing a photoresist composition, comprising: a process 1Y for preparing the photoresist composition; a process 2Y for coating the photoresist composition onto a semiconductor substrate; a process 3Y for determining whether there are defects in the coating of the photoresist composition, obtaining position information of the defects in the coating of the photoresist composition on the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the position information, recovering the analytical sample obtained by irradiation using a carrier gas and performing inductively coupled plasma mass spectrometry analysis; a process 4Y for determining whether there are metal elements in the defects based on the mass spectrometry data of the defects obtained in process 3Y and a process 5Y for determining the number of defects containing metal elements, or a process 5Y for determining the number of defects containing metal elements based on the mass spectrometry data of the defects obtained in process 3Y; and a process 6Y for determining whether the number of defects obtained in process 5Y is within an acceptable range.

[0019] Preferably, the photoresist composition contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total content of the metallic elements is less than 10 ppb by mass relative to the total mass of the photoresist composition. Preferably, the water content of the carrier gas is above 0.00001 ppm by volume and below 0.1 ppm by volume.

[0020] One aspect of the present invention provides a method for manufacturing a semiconductor device, comprising: a process 1Y for preparing a photoresist composition; a process 2Y for coating the photoresist composition onto a semiconductor substrate; a process 3Y for determining whether there are defects in the coating of the photoresist composition, obtaining position information of the defects in the coating of the photoresist composition on the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the position information, recovering the analytical sample obtained by irradiation using a carrier gas and performing inductively coupled plasma mass spectrometry analysis; a process 4Y for determining whether there are metal elements in the defects based on the mass spectrometry data of the defects obtained in process 3Y and a process 5Y for determining the number of defects containing metal elements, or a process 5Y for determining the number of defects containing metal elements based on the mass spectrometry data of the defects obtained in process 3Y; a process 6Y for determining whether the number of defects obtained in process 5Y is within an acceptable range; and a process 7Y for manufacturing a semiconductor device using the photoresist composition determined to be within the acceptable range in process 6Y.

[0021] Preferably, the photoresist composition contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total content of the metallic elements is less than 10 ppb by mass relative to the total mass of the photoresist composition. Preferably, the water content of the carrier gas is above 0.00001 ppm by volume and below 0.1 ppm by volume.

[0022] One aspect of the present invention provides a method for confirming the contamination status of a semiconductor manufacturing apparatus, comprising: a process 1Z of preparing a chemical solution; a process 2Z of cleaning the semiconductor manufacturing apparatus with the chemical solution; a process 3Z of coating the cleaned chemical solution from process 2Z onto a semiconductor substrate; a process 4Z of determining whether there are defects on the surface of the semiconductor substrate, obtaining position information of the defects on the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the position information, recovering the analytical sample obtained by irradiation using a carrier gas and performing inductively coupled plasma mass spectrometry analysis; and a process 5Z of determining whether there are metal elements in the defects based on the mass spectrometry data of the defects obtained in process 4Z. Preferably, process 6Z includes determining the number of defects containing metallic elements.

[0023] One aspect of the present invention provides a method for confirming the contamination status of a semiconductor manufacturing apparatus, comprising: a process 1Z of preparing a chemical solution; a process 2Z of cleaning the semiconductor manufacturing apparatus with the chemical solution; a process 3Z of coating the cleaned chemical solution from process 2Z onto a semiconductor substrate; a process 4Z of determining whether there are defects on the surface of the semiconductor substrate, obtaining position information of the defects on the surface of the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the position information, recovering the analytical sample obtained by irradiation using a carrier gas and performing inductively coupled plasma mass spectrometry analysis; and a process 6Z of determining the number of defects containing metal elements based on the mass spectrometry data of the defects obtained in process 4Z. Preferably, the water content of the carrier gas is above 0.00001 ppm by volume and below 0.1 ppm by volume. [Invention Effects]

[0024] According to the present invention, there are methods for inspecting a pharmaceutical solution capable of analyzing minute foreign matter in the solution, methods for manufacturing a pharmaceutical solution, methods for managing a pharmaceutical solution that can perform quality management even when the solution contains trace amounts of minute foreign matter, methods for manufacturing a semiconductor element, methods for inspecting a photoresist composition capable of analyzing minute foreign matter in the photoresist composition, methods for manufacturing a photoresist composition, methods for managing a photoresist composition that can perform quality management even when the photoresist composition contains trace amounts of minute foreign matter, methods for manufacturing a semiconductor element, and methods for confirming the contamination status of a semiconductor manufacturing apparatus capable of managing minute foreign matter in a semiconductor manufacturing apparatus. Simple Explanation of the Diagram

[0025] Figure 1 is a flowchart illustrating an example of a method for inspecting a pharmaceutical solution according to an embodiment of the present invention. Figure 2 is a flowchart illustrating an example of a method for managing a pharmaceutical solution according to an embodiment of the present invention. Figure 3 is a flowchart illustrating a first example of a method for manufacturing a semiconductor element according to an embodiment of the present invention. Figure 4 is a flowchart illustrating an example of a method for inspecting a photoresist composition according to an embodiment of the present invention. Figure 5 is a flowchart illustrating an example of a method for managing a photoresist composition according to an embodiment of the present invention. Figure 6 is a flowchart illustrating a second example of a method for manufacturing a semiconductor element according to an embodiment of the present invention. Figure 7 is a flowchart illustrating an example of a method for confirming the contamination state of a semiconductor manufacturing apparatus according to an embodiment of the present invention. Figure 8 is a schematic diagram illustrating a first example of an analytical apparatus according to an embodiment of the present invention. Figure 9 is a schematic diagram illustrating an example of an analytical unit of an analytical apparatus according to an embodiment of the present invention. Figure 10 is a schematic diagram illustrating a first example of an analytical method according to an embodiment of the present invention. Figure 11 is a schematic cross-sectional view illustrating a first example of an analytical method according to an embodiment of the present invention. Figure 12 is a schematic diagram illustrating a second example of an analytical apparatus according to an embodiment of the present invention. Figure 13 is a schematic diagram illustrating a third example of an analytical apparatus according to an embodiment of the present invention. Figure 14 is a schematic diagram showing a modified example of the analysis section of the analysis apparatus according to an embodiment of the present invention. Implementation

[0026] Hereinafter, based on the preferred embodiments shown in the accompanying drawings, the present invention describes in detail the method for inspecting a pharmaceutical solution, the method for manufacturing a pharmaceutical solution, the method for managing a pharmaceutical solution, the method for manufacturing a semiconductor element, the method for inspecting a photoresist composition, the method for manufacturing a photoresist composition, the method for managing a photoresist composition, and the method for confirming the contamination status of a semiconductor manufacturing apparatus. Furthermore, the figures described below are illustrative of the present invention, and the present invention is not limited to the figures shown below.

[0027] Furthermore, the "~" sign indicating a range of values ​​includes the values ​​written on both sides. For example, ε is the range of values ​​εa to εb, where ε is the range that includes both values ​​εa and εb. If represented by numerical symbols, it would be εa≦ε≦εb. Unless otherwise specified, angles such as "angle expressed in specific numerical values," "parallel," "perpendicular," and "orthogonal" include the error range generally permissible in the corresponding technical field. Furthermore, "same" includes the error range generally permissible in the corresponding technical field. Additionally, "the entire surface," etc., includes the error range generally permissible in the corresponding technical field. "Preparation" refers not only to preparing specific materials through synthesis or formulation, but also to preparing prescribed items through purchase. Furthermore, "ppm" means "parts-per-million (10⁻⁶)," "ppb" means "parts-per-billion (10⁻⁹)," "ppt" means "parts-per-trillion (10⁻¹²)," and "ppq" means "parts-per-quadrillion (10⁻¹⁵)." The composition of the reagent and photoresist will be explained later. Although inductively coupled plasma mass spectrometry (ICP-MS) analysis is performed as described below, the specific apparatus structure used for performing ICP-MS analysis will be described later. The semiconductor manufacturing apparatus described below is not particularly limited. Examples of semiconductor manufacturing apparatus include coating and developing machines, spin coaters, semiconductor wafer cleaning equipment, and developing equipment.

[0028] In the manufacturing process of semiconductor devices, various chemicals used, such as developing solutions, rinsing solutions, pre-wetting solutions, and stripping solutions, require high purity. Therefore, the inspection and management of these chemicals are crucial, aiming to analyze for minute foreign matter. The following describes the inspection and management methods for these chemicals.

[0029] [Methods for testing the drug solution] Figure 1 is a flowchart illustrating an example of a method for inspecting a pharmaceutical solution according to an embodiment of the present invention. In the method for inspecting a pharmaceutical solution, firstly, a pharmaceutical solution to be inspected is prepared (process 1X, step S10). Next, the pharmaceutical solution is coated onto a semiconductor substrate (not shown) (process 2X, step S12). The coating of the pharmaceutical solution onto the semiconductor substrate is not particularly limited; for example, a coating and developing machine can be used. Furthermore, the semiconductor substrate is not particularly limited; for example, a silicon substrate can be used. Also, the size of the semiconductor substrate is not particularly limited and can be appropriately determined based on the specifications of the coating apparatus used to coat the pharmaceutical solution onto the semiconductor substrate and the specifications of the apparatus used for performing inductively coupled plasma mass spectrometry analysis, as well as the amount of pharmaceutical solution to be measured.

[0030] Next, the presence of defects on the surface of the semiconductor substrate is determined, and the location information of the defects on the semiconductor substrate is obtained (step S14). Based on the location information, laser light is irradiated onto the defects on the surface of the semiconductor substrate, and the irradiated sample is recovered using a carrier gas and subjected to inductively coupled plasma mass spectrometry (Chemical 3X, step S16). Through the inductively coupled plasma mass spectrometry analysis in step S16 (Chemical 3X), the elemental composition of specific micro-defects is determined. Also, the size of specific micro-defects is determined. Through inductively coupled plasma mass spectrometry analysis, mass spectrometry data of defects in the pharmaceutical solution is obtained. The mass spectrometry data of the pharmaceutical solution includes elemental information and size information of specific defects analyzed by inductively coupled plasma mass spectrometry. This operation enables the inspection of pharmaceutical solutions, and in the pharmaceutical solution inspection method, it is possible to analyze micro-foreign matter in the pharmaceutical solution.

[0031] The series of processes (process 3X, steps S14 and S16) for performing inductively coupled plasma mass spectrometry analysis after coating the semiconductor substrate with the solution will be described in detail later. Furthermore, in the method for inspecting the chemical solution, it is preferable to have a process that measures the presence of defects on the surface of the semiconductor substrate before applying the chemical solution to the semiconductor substrate. At this time, the location and size of the defects are measured. Therefore, the measured defects can be distinguished as defects originating from the semiconductor substrate and defects originating from the chemical solution.

[0032] By using inductively coupled plasma mass spectrometry (process 3X, steps S14 and S16), the elements of specific minute defects can be identified, thereby enabling the determination of minute foreign matter and the inspection of the drug solution. To perform inductively coupled plasma mass spectrometry (ICP-MS), a drug solution can be coated onto a semiconductor substrate to analyze minute foreign matter within the solution. ICP-MS can be performed with the drug solution on the semiconductor substrate, or after coating the substrate, the solvent in the drug solution can be evaporated or volatilized, leaving no solvent on the substrate.

[0033] The method for inspecting the solution can also include a process 4X (step S18) that determines whether there are metal elements in the defects based on mass spectrometry data obtained in process 3X. The solution can be inspected based on the presence or absence of metal elements. Furthermore, after process 4X (step S18), process 5X (step S20) can be performed to determine the number of defects containing metal elements. The number of defects containing metal elements can be used to inspect the solution. In the solution inspection method, specific defect elements are identified by inductively coupled plasma mass spectrometry analysis (process 3X, step S16). In step S18, an attempt is made to select the metal element from the mass spectrometry data containing information about the element of the specific defect. If no metal element is selected from the mass spectrometry data, it is determined that there is no metal element. On the other hand, if a metal element is selected from the mass spectrometry data, it is determined that there is a metal element. In step S20, when it is determined that there is a metal element in step S18, the number of defects containing metal elements is measured. For example, the number of defects containing metal elements is determined by counting the number of defects containing metal elements.

[0034] Alternatively, process 4X (step S18), which determines the presence or absence of metal elements, can be omitted. Instead, the number of defects containing metal elements can be determined based on mass spectrometry data of the defects obtained in process 3X (step S16) (process 5X, step S20). In this case, in step S20, metal elements are selected from the mass spectrometry data containing information about the elements in the specific defects, and the number of selected metal elements is counted to determine the number of defects containing metal elements. Thus, the number of defects containing metal elements can also be used to inspect the pharmaceutical solution.

[0035] [Method for manufacturing the medicinal solution] The above-described inspection method for the pharmaceutical solution can be applied to the manufacturing method of the pharmaceutical solution. The results of inductively coupled plasma mass spectrometry analysis are utilized in the manufacturing method. Furthermore, for example, in the manufacturing method, a threshold or permissible range for the number of defects in the pharmaceutical solution is preset. For the manufactured pharmaceutical solution, the number of defects is determined using the above-described inspection method. The determined number of defects is compared with the threshold or permissible range; if the number of defects is below the threshold or within the permissible range, it is considered acceptable and is treated as a product. Conversely, if the number of defects exceeds the threshold or is outside the permissible range, it is considered unacceptable and is not treated as a product. The permissible range for the number of defects in the pharmaceutical solution is, for example, 0.07 defects / cm² or less. Preferably, the permissible range for the number of defects in the pharmaceutical solution is 0.0001 to 10 defects / cm², more preferably 0.0002 to 1 defect / cm², and even more preferably 0.0005 to 0.5 defects / cm².

[0036] [Management methods for liquid medicine] Figure 2 is a flowchart illustrating an example of a pharmaceutical liquid management method according to an embodiment of the present invention. Furthermore, in the pharmaceutical liquid management method, detailed descriptions of processes identical to those in the pharmaceutical liquid inspection method described above are omitted. Compared to the pharmaceutical liquid inspection method, the pharmaceutical liquid management method shown in Figure 2 has the same processes as the pharmaceutical liquid inspection method, except that it involves preparing the pharmaceutical liquid to be managed (process 1X, step S10) and has a process 6X (step S22) for determining whether the number of defects obtained in process 5X (step S20) is within the acceptable range. The process for preparing the pharmaceutical liquid (process 1X, step S10) differs in whether it is an inspection target or a managed target, but in practice, the pharmaceutical liquid is the same. Therefore, process 6X (step S22) for determining whether the number of defects is within the acceptable range will be described.

[0037] In the method for managing the pharmaceutical solution, a threshold or allowable range for the number of defects in the solution is preset. The threshold for the number of defects in the solution is set, for example, based on the number of defects in the previous manufacturing batch of the solution being studied, but is not limited to this; it can be a target value, a set value, or the average of multiple manufacturing batches. The allowable range for the number of defects in the solution is, for example, 0.07 defects / cm² or less. Preferably, the allowable range for the number of defects in the solution is 0.0001 to 10 defects / cm², more preferably 0.0002 to 1 defect / cm², and even more preferably 0.0005 to 0.5 defects / cm². Step S22 (Process 6X) compares the number of defects containing metal elements obtained in step S20 with a threshold or allowable range for the number of defects in the solution. For example, if the measured number of defects in the solution is below the threshold or within the allowable range, the solution is considered a qualified product (step S23). On the other hand, if the number of defects exceeds the threshold or is outside the allowable range, the solution is considered a non-qualified product (step S24). In this way, the quality of the solution can be managed based on the number of defects in the solution. In this solution management method, even when the solution contains trace amounts of minute foreign matter, the quality of the solution can be managed.

[0038] [Example 1 of a semiconductor device manufacturing method] Figure 3 is a flowchart illustrating a first example of a semiconductor device manufacturing method according to an embodiment of the present invention. Furthermore, in this first example of the semiconductor device manufacturing method, detailed descriptions of processes identical to those in the chemical solution inspection method are omitted. Compared to the chemical solution inspection method, the first example of the semiconductor device manufacturing method shown in Figure 3 has the same processes as the chemical solution inspection method, except for the preparation of the chemical solution for manufacturing the semiconductor device (process 1X, step S10), process 6X (step S26) which includes determining whether the number of defects obtained in process 5X (step S20) is within the acceptable range, and process 7X (step S27) which uses the chemical solution determined to be within the acceptable range in process 6X to manufacture the semiconductor device. The process of preparing the chemical solution (process 1X, step S10) differs depending on whether it is for inspection or for manufacturing a semiconductor device, but the chemical solution itself is the same. Therefore, process 6X (step S22) which determines whether the number of defects is within the acceptable range will be described.

[0039] In a semiconductor device manufacturing method, a threshold or allowable range for the number of defects in the chemical solution is predetermined. This threshold or allowable range is set, for example, based on the number of defects in a previous manufacturing batch of the chemical solution being tested, but is not limited to this; it can be a target value, a set value, or the average of multiple manufacturing batches. The allowable range for the number of defects in the chemical solution is, for example, 0.07 defects / cm² or less. Preferably, the allowable range for the number of defects in the chemical solution is 0.0001 to 10 defects / cm², more preferably 0.0002 to 1 defect / cm², and even more preferably 0.0005 to 0.5 defects / cm². Step S26 compares the number of defects containing metal elements obtained in step S20 with a threshold or allowable range of the number of defects in the solution. For example, if the measured number of defects in the solution is below the threshold or within the allowable range, it is used in the semiconductor device manufacturing method (step S27). Furthermore, in step S26 (process 6X), solutions where the measured number of defects exceeds the threshold, i.e., solutions where the measured number of defects is outside the allowable range, are not used in the semiconductor device manufacturing process (step S28). Thus, in the semiconductor device manufacturing method, the selected solutions are used in the semiconductor device manufacturing process to manufacture semiconductor devices. The semiconductor device manufacturing process corresponds to the type of solution; for example, if the solution is a developer, it is used in a photolithography process. In the semiconductor device manufacturing method, the solution is not particularly limited as long as it is related to the manufacturing of the semiconductor device; for example, it can be a pre-wetting solution, developer, rinsing solution, or cleaning solution.

[0040] Photoresist components used in the manufacturing process of semiconductor devices must be free of defects such as foreign matter. Therefore, inspection and management of photoresist components are crucial, and the ability to analyze minute foreign objects within them is desirable. The following describes methods for inspecting and managing photoresist components.

[0041] [Methods for inspecting photoresist composition] Figure 4 is a flowchart illustrating an example of a photoresist composition inspection method according to an embodiment of the present invention. The photoresist composition inspection method differs from the above-described solution inspection method in that the object of inspection is a photoresist composition; otherwise, the process is essentially the same as the solution inspection method. The photoresist composition inspection method prepares the photoresist composition to be inspected (process 1Y, step S30). Next, the photoresist composition is coated onto a semiconductor substrate (process 2Y, step S32). After coating the photoresist composition onto the semiconductor substrate (not shown), a film is formed, creating a photoresist composition coating film on the semiconductor substrate. The coating of the photoresist composition onto the semiconductor substrate is not particularly limited; for example, a coating and developing machine can be used. Furthermore, the semiconductor substrate is not particularly limited; the semiconductor substrate used in the above-described solution inspection method can be used. Furthermore, the size of the semiconductor substrate is not particularly limited, similar to the inspection method for the aforementioned solution. It can be appropriately determined based on the specifications of the coating apparatus for coating the photoresist composition on the semiconductor substrate and the specifications of the apparatus for performing inductively coupled plasma mass spectrometry analysis, as well as the amount of photoresist composition measured.

[0042] Next, the presence of defects in the photoresist coating is determined, and the location information of the defects in the photoresist coating on the semiconductor substrate is obtained (step S34). Based on the location information, laser light is irradiated onto the defects in the photoresist coating on the semiconductor substrate surface. The sample obtained by irradiation is recovered using a carrier gas and subjected to inductively coupled plasma mass spectrometry (ICP-MS) analysis (process 3Y, step S36). Through the ICP-MS analysis in step S36, the elements of specific micro-defects are identified. Furthermore, the size of the micro-defects is also identified. Mass spectrometric data of the defects in the photoresist composition is obtained through ICP-MS analysis. The mass spectrometric data of the photoresist composition includes elemental information and size information of the specific defects identified by ICP-MS analysis. This operation enables the inspection of photoresist compositions. In the photoresist composition inspection method, it is possible to analyze micro-defects in the photoresist composition.

[0043] The series of processes (process 3Y, steps S34 and S36) for performing inductively coupled plasma mass spectrometry analysis after the photoresist composition is coated onto the semiconductor substrate will be described in detail later. Furthermore, in the method for inspecting photoresist components, it is preferable to have a process that measures the presence of defects on the surface of the semiconductor substrate before coating the photoresist component onto the semiconductor substrate. At this time, the location and size of the defects are measured. Thus, the measured defects can be distinguished as defects originating from the semiconductor substrate and defects originating from the photoresist component.

[0044] By using inductively coupled plasma mass spectrometry (process 3Y, steps S34 and S36), the elements of specific minute defects can be identified, thereby enabling the determination of minute foreign matter and the inspection of photoresist composition. To perform inductively coupled plasma mass spectrometry (ICP-MS), photoresist compositions can be coated onto a semiconductor substrate to analyze minute foreign matter within the photoresist composition. For example, ICP-MS can be performed when the photoresist composition is a coating on the semiconductor substrate. Defects in the photoresist composition coating are measured. Furthermore, defects in the photoresist composition coating refer to defects arising from unintentionally present trace amounts of foreign matter within the photoresist composition; the meaning of defects in the photoresist composition coating is the same as that of defects in the photoresist composition itself.

[0045] The method for inspecting photoresist composition can also include a process 4Y (step S38) that determines the presence or absence of metal elements in defects based on mass spectrometry data obtained in process 3Y. The photoresist composition can be inspected based on the presence or absence of metal elements. Furthermore, after process 4Y (step S38), process 5Y (step S40) can also be performed to determine the number of defects containing metal elements. The number of defects containing metal elements can be used to inspect the photoresist composition. In the photoresist composition inspection method, specific defect elements are identified by inductively coupled plasma mass spectrometry analysis (process 3Y, step S36). In step S38, an attempt is made to select the metal element from the mass spectrometry data containing information about the element of the specific defect. If no metal element is selected from the mass spectrometry data, it is determined that there is no metal element. On the other hand, if a metal element is selected from the mass spectrometry data, it is determined that there is a metal element. In step S40, if it is determined that there is a metal element in step S38, the number of defects containing metal elements is measured. For example, the number of defects containing metal elements is determined by counting the number of defects containing metal elements.

[0046] Alternatively, process 4Y (step S38), which determines the presence or absence of metal elements, can be omitted. Instead, the number of defects containing metal elements can be determined based on mass spectrometry data obtained in process 3Y (step S36) (process 5Y, step S40). In this case, in step S40, metal elements are selected from the mass spectrometry data containing information about the elements in the specific defects, and the number of selected metal elements is counted to determine the number of defects containing metal elements. Therefore, the number of defects containing metal elements can also be used to inspect the photoresist composition.

[0047] [Manufacturing method of photoresist composition] The above-described inspection method for photoresist components can be applied to the manufacturing method of photoresist components. In the manufacturing method of photoresist components, the results of inductively coupled plasma mass spectrometry analysis are utilized. Furthermore, for example, in the manufacturing method of photoresist components, a threshold or permissible range for the number of defects in the photoresist components is predetermined. For the manufactured photoresist components, the number of defects in the photoresist components is determined using the above-described inspection method. The determined number of defects in the photoresist components is compared with the threshold or permissible range. Those with a number of defects below the threshold or within the permissible range are considered acceptable and are accepted as photoresist components. On the other hand, those with a number of defects exceeding the threshold or outside the permissible range are considered unacceptable and are not accepted as photoresist components. The permissible range for the number of defects in the photoresist components is, for example, 0.07 defects / cm² or less. Preferably, the permissible range for the number of defects in the photoresist components is 0.0001 to 10 defects / cm², more preferably 0.0005 to 5 defects / cm², and even more preferably 0.001 to 1 defect / cm².

[0048] [Management methods for photoresist components] Figure 5 is a flowchart illustrating an example of a photoresist composition management method according to an embodiment of the present invention. The photoresist composition management method differs from the above-described liquid management method in that the object of inspection is the photoresist composition, but it has the same process as the liquid management method. The photoresist composition management method shown in Figure 5, compared to the photoresist composition inspection method, has the same process as the photoresist composition inspection method, except that it involves preparing the photoresist composition to be managed (process 1Y, step S30) and has a process 6Y (step S42) for determining whether the number of defects obtained in the above-described process 5Y (step S40) is within an acceptable range. The process for preparing the photoresist composition (process 1Y, step S30) differs in whether it is an object of inspection or a managed object, but in reality, it is the same as the photoresist composition. Therefore, process 6Y (step S42), which determines whether the number of defects is within an acceptable range, will be explained.

[0049] In the method for managing photoresist components, a threshold or allowable range for the number of defects in the photoresist component is preset. The threshold for the number of defects in the photoresist component is set, for example, based on the number of defects in the previous manufacturing batch of the photoresist component being targeted, but is not limited to this; it can be a target value, a set value, or the average of multiple manufacturing batches. The allowable range for the number of defects in the photoresist component is, for example, 0.07 defects / cm² or less. Preferably, the allowable range for the number of defects in the photoresist component is 0.0001 to 10 defects / cm², more preferably 0.0005 to 5 defects / cm², and even more preferably 0.001 to 1 defect / cm². Step S42 (Process 6Y) compares the number of defects containing metal elements obtained in step S40 with a threshold or allowable range for the number of defects in the photoresist composition. For example, if the measured number of defects in the photoresist composition is below the threshold or within the allowable range, the photoresist composition is considered a qualified product (step S43). On the other hand, if the number of defects in the photoresist composition exceeds the threshold or is outside the allowable range, the photoresist composition is considered a non-qualified product (step S44). In this way, the quality of the photoresist composition can be managed by the number of defects in the photoresist composition.

[0050] [Example 2 of a semiconductor device manufacturing method] Figure 6 is a flowchart illustrating a second example of a semiconductor device manufacturing method according to an embodiment of the present invention. Furthermore, in this second example of the semiconductor device manufacturing method, detailed descriptions of processes identical to those used in the photoresist composition inspection method are omitted. Compared to the first example of the semiconductor device manufacturing method, this second example uses a photoresist composition instead of a chemical solution. Compared to the photoresist composition inspection method, the second example of the semiconductor device manufacturing method shown in Figure 6 has the same processes as the photoresist composition inspection method, except for the preparation of the photoresist composition for semiconductor device manufacturing (process 1Y, step S30), process 6Y (step S42) which includes determining whether the number of defects obtained in process 5Y (step S40) is within acceptable limits, and process 7Y (step S46) which uses the photoresist composition determined to be within acceptable limits in process 6Y to manufacture the semiconductor device. The process for preparing the photoresist composition (process 1Y, step S30) differs depending on whether it is for inspection or for manufacturing semiconductor devices, but in reality, the photoresist composition is the same. Therefore, process 6Y (step S42), which determines whether the number of defects is within the acceptable range, will be explained.

[0051] In a semiconductor device manufacturing method, a threshold or permissible range for the number of defects in the photoresist composition is predetermined. This threshold or permissible range is set, for example, based on the number of defects in a previous manufacturing batch of the photoresist composition being manufactured, but is not limited thereto; it can be a target value, a set value, or an average of multiple manufacturing batches. The permissible range for the number of defects in the photoresist composition is, for example, 0.07 defects / cm² or less. Preferably, the permissible range for the number of defects in the photoresist composition is 0.0001 to 10 defects / cm², more preferably 0.0005 to 5 defects / cm², and even more preferably 0.001 to 1 defect / cm². Step S44 compares the number of defects containing metal elements obtained in step S40 with a threshold or allowable range for the number of defects in the photoresist composition. For example, if the measured number of defects in the photoresist composition is below the threshold or within the allowable range, it is used in the semiconductor device manufacturing method (step S46). Furthermore, in process 6Y (step S44), photoresist compositions that are determined to have a measured number of defects exceeding the threshold, i.e., those whose measured number of defects is outside the allowable range, are not used in the semiconductor device manufacturing process (step S48). Thus, in the semiconductor device manufacturing method, the selected photoresist composition is used in the photolithography process of the semiconductor device to manufacture the semiconductor device.

[0052] [Method for Contamination Status Verification of Semiconductor Manufacturing Equipment] In semiconductor manufacturing equipment, contamination can affect the performance and quality of manufactured products, making it desirable to manage minute foreign matter. To manage minute foreign matter in semiconductor manufacturing equipment, it is particularly desirable to measure and analyze the elemental composition of minute foreign matter generated by defective semiconductor components that have advanced miniaturization and high integration. The following describes a method for confirming the contamination status of a semiconductor manufacturing equipment. Figure 7 is a flowchart illustrating an example of a method for confirming the contamination status of a semiconductor manufacturing equipment according to an embodiment of the present invention. The method for confirming the contamination status of a semiconductor manufacturing equipment shown in Figure 7 first prepares a cleaning solution (process 1Z, step S50). The cleaning solution is used for cleaning the semiconductor manufacturing equipment and is not particularly limited; examples include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), isopropanol (IPA), butyl acetate (nBA), cyclohexanone (CHN), ethyl lactate (EL), methyl ethyl ketone (MEK), γ-butyrolactone (GBL), 2-heptanone, or a mixture of these in any ratio.

[0053] Next, the semiconductor manufacturing apparatus is cleaned with a cleaning solution (process 2Z, step S52). The cleaning solution is then recovered. There are no particular limitations on the cleaning method for semiconductor manufacturing equipment. For example, methods such as passing the cleaning solution through the piping of the semiconductor equipment or spraying the cleaning solution into a container such as a chamber can be used. The cleaning solution from process 2Z (step S52) is coated onto the semiconductor substrate (process 3Z, step S54). There are no particular limitations on the coating of the cleaning solution onto the semiconductor substrate; for example, a coating and developing machine can be used. Furthermore, there are no particular limitations on the semiconductor substrate; for example, a silicon substrate can be used. Furthermore, there are no particular limitations on the size of the semiconductor substrate, and it can be appropriately determined based on the specifications of the coating apparatus used to coat the cleaning solution onto the semiconductor substrate and the specifications of the apparatus used for performing inductively coupled plasma mass spectrometry analysis, as well as the amount of cleaning solution measured.

[0054] Next, the presence of defects on the surface of the semiconductor substrate is determined, and the location information of the defects on the semiconductor substrate is obtained (step S56). Based on the location information, laser light is irradiated onto the defects on the surface of the semiconductor substrate, and the irradiated sample is analyzed by inductively coupled plasma mass spectrometry using carrier gas recovery (process 4Z, step S58). Through the inductively coupled plasma mass spectrometry analysis in step S58, the elemental composition of specific micro-defects is determined. Furthermore, the size of specific micro-defects is also determined. Therefore, the contamination status of the semiconductor manufacturing apparatus can be confirmed.

[0055] After the cleaning solution is coated onto the semiconductor substrate, the series of processes (process 4Z, steps S56 and S58) for inductively coupled plasma mass spectrometry analysis described above will be explained in detail later. Furthermore, in the method for confirming the contamination state of a semiconductor manufacturing apparatus, it is preferable to have a process that measures whether there are defects on the surface of the semiconductor substrate before applying the cleaning solution to the semiconductor substrate. At this time, the location and size of the defects are measured. Thus, the measured defects can be distinguished as defects originating from the semiconductor substrate and defects originating from the cleaning solution.

[0056] Next, a process 5Z (step S60) is performed to determine whether there are metal elements in the defect based on the mass spectrometry data of the defect obtained in process 4Z (step S58). The element of the defect is determined by inductively coupled plasma mass spectrometry (process 4Z, step S58). In step S58, an attempt is made to select the metal element from the mass spectrometry data containing information about the element of the specific defect. If no metal element is selected from the mass spectrometry data, it is determined that there is no metal element. On the other hand, if a metal element is selected from the mass spectrometry data, it is determined that there is a metal element. In step S60 (process 5Z), if it is determined that there is no metal element, the contamination of the semiconductor manufacturing apparatus is not serious, and the semiconductor manufacturing apparatus can be used (step S66). On the other hand, if it is determined that there is a metal element, the contamination of the semiconductor manufacturing apparatus is serious, and the semiconductor manufacturing apparatus is not used (step S68). Thus, the contamination status of the semiconductor manufacturing apparatus can be determined by the number of defects containing metal elements. In this way, in the method for confirming the contamination status of the semiconductor manufacturing apparatus, even if the amount of minute foreign matter contained in the cleaning solution is trace, minute foreign matter in the semiconductor manufacturing apparatus can be managed. In addition, when it is determined that there is a metal element, the number of defects containing metal elements can also be measured (process 6Z, step S62). For example, the number of defects containing metallic elements can be determined by counting the number of defects containing metallic elements.

[0057] Alternatively, the process 5Z (step S60) for determining the presence or absence of metal elements can be omitted, and the number of defects containing metal elements can be determined based on mass spectrometry data of defects obtained in process 4Z (step S58) (process 6Z, step S62). In this case, in step S62, metal elements are selected from the mass spectrometry data containing information about the elements of the specific defects, and the number of selected metal elements is counted to determine the number of defects containing metal elements. Therefore, the number of defects containing metal elements can also be used to determine the contamination status of the semiconductor manufacturing apparatus.

[0058] In methods for confirming the contamination status of semiconductor manufacturing equipment, a threshold or permissible range for the number of defects in the cleaning solution is pre-set, for example. The threshold or permissible range for the number of defects in the cleaning solution is appropriately determined based on the required cleanliness of the semiconductor manufacturing equipment, and a target value for the number of defects in the solution can be used. The permissible range for the number of defects in the solution is, for example, 0.07 defects / cm² or less. Preferably, the permissible range for the number of defects in the solution is 0.0001 to 10 defects / cm², more preferably 0.0002 to 1 defect / cm², and even more preferably 0.0005 to 0.5 defects / cm². Step S64 compares the number of defects containing metal elements obtained in step S62 with a threshold or permissible range for the number of defects in the cleaned solution. For example, if the measured number of defects in the cleaned solution is below the threshold or within the permissible range, the contamination of the semiconductor manufacturing apparatus is not severe, and the semiconductor manufacturing apparatus is used (step S66). Furthermore, in step S64, if the number of defects in the solution is determined to exceed the threshold, i.e., if the number of defects in the solution is determined to be outside the permissible range, the contamination of the semiconductor manufacturing apparatus is severe, and the semiconductor manufacturing apparatus is not used (step S68).

[0059] As described above, when it is determined that the semiconductor manufacturing apparatus will not be used, the semiconductor manufacturing apparatus can be cleaned again, and the semiconductor manufacturing apparatus can be repeatedly cleaned with the cleaning solution until it is determined that the semiconductor manufacturing apparatus will be used (step S66). Furthermore, in methods for confirming the contamination status of semiconductor manufacturing equipment, a preferred method is one that measures the presence or absence of defects in the cleaning solution before cleaning the semiconductor manufacturing equipment. In this process, the location and size of the defects are measured. This allows for the differentiation between defects in the cleaning solution and defects in the solution before cleaning.

[0060] In the above explanation, comparison and judgment involve inputting various numerical values ​​into a computer, comparing them with thresholds, and making a judgment based on the thresholds. Such comparison and judgment are performed, for example, using a computer. Furthermore, selecting a metal element from mass spectrometry data containing information about elements with specific defects means that, in a computer, for the element information in the stored mass spectrometry data, a specific metal element that matches the pre-stored metal element is selected from the mass spectrometry data.

[0061] The following describes a specific example of the analytical apparatus. [First Example of an Analytical Apparatus] FIG8 is a schematic diagram showing a first example of an analytical apparatus according to an embodiment of the present invention, and FIG9 is a schematic diagram showing an example of an analytical unit of the first example of an analytical apparatus according to an embodiment of the present invention. The analytical apparatus 10 shown in FIG8 has a surface defect measuring unit 20 and an analytical unit 30, which will be described in detail later. The analytical apparatus 10 takes a semiconductor substrate 50 as the measuring object and performs the measurement of whether there are defects on the surface of the semiconductor substrate and the analysis of defects on the surface of the semiconductor substrate. In addition, when performing the above-mentioned inspection of the solution or photoresist composition, the above-mentioned solution or photoresist composition is coated on the semiconductor substrate 50. The solution may also be in a state where the solvent contained in the solution evaporates or evaporates after being coated on the semiconductor substrate, so that the solvent contained in the solution is no longer on the semiconductor substrate. The photoresist composition forms a film after coating, and is in a state of coating film on the semiconductor substrate.

[0062] The analytical apparatus 10 has a first transport chamber 12a, a measuring chamber 12b, a second transport chamber 12c, and an analytical chamber 12d, arranged sequentially in the order of the first transport chamber 12a, the measuring chamber 12b, the second transport chamber 12c, and the analytical chamber 12d. The first transport chamber 12a, the measuring chamber 12b, the second transport chamber 12c, and the analytical chamber 12d are each divided by a wall 12h, but doors (not shown) may also be provided to allow the semiconductor substrate 50, which is the object of measurement, to move, and the doors are opened when the semiconductor substrate 50 passes through.

[0063] In the analysis apparatus 10, a semiconductor substrate 50 is conveyed from outside the analysis apparatus 10 to a first conveying chamber 12a, and then from the first conveying chamber 12a to a measuring chamber 12b, where surface defects of the semiconductor substrate 50 are measured. Next, the semiconductor substrate 50 with measured surface defects is conveyed from the measuring chamber 12b to a second conveying chamber 12c, and then to the analysis chamber 12d, where the analysis unit 30 analyzes the surface defects of the semiconductor substrate 50 based on the measurement results of whether or not defects exist on the surface 50a of the semiconductor substrate 50 in the surface defect measuring unit 20. In the analysis apparatus 10, to prevent the semiconductor substrate 50 from being exposed to external gases, the interiors of the first delivery chamber 12a, the measuring chamber 12b, the second delivery chamber 12c, and the analysis chamber 12d can be set to a specific atmosphere. For example, a vacuum pump can be installed to exhaust the gases inside the first delivery chamber 12a, the measuring chamber 12b, the second delivery chamber 12c, and the analysis chamber 12d to create a reduced-pressure atmosphere. Alternatively, an inert gas such as nitrogen can be supplied to the interiors of the first delivery chamber 12a, the measuring chamber 12b, the second delivery chamber 12c, and the analysis chamber 12d to create an inert gas atmosphere.

[0064] As described above, the first delivery chamber 12a delivers the semiconductor substrate 50, which is transported from outside the analytical apparatus 10, to the measuring chamber 12b. The first delivery chamber 12a has an inlet portion 12g on its side. A receiving container 13 is provided at the inlet portion 12g. To maintain an airtight seal between the inlet portion 12g and the receiving container 13, a sealing member (not shown) is provided at the inlet portion 12g. The receiving container 13, for example, houses a plurality of semiconductor substrates 50 arranged in a shelf-like configuration inside. The semiconductor substrates 50 are, for example, disc-shaped substrates. The receiving container 13 is, for example, a FOUP (Front Opening Unified Pod). By using the receiving container 13, the semiconductor substrates 50 can be transported to the analysis apparatus 10 in a sealed state without exposing them to external gases. This helps to suppress contamination of the semiconductor substrates 50.

[0065] A conveying device 14 is provided inside the first conveying chamber 12a. The conveying device 14 conveys the semiconductor substrate 50 in the receiving container 13 from the first conveying chamber 12a to the adjacent measuring chamber 12b. The transport device 14 is not particularly limited as long as it can remove the semiconductor substrate 50 from the receiving container 13 and transport it to the stage 22 of the testing chamber 12b. The transport device 14 shown in FIG8 has a transport arm 15 that holds the outer side of the semiconductor substrate 50 and a drive unit (not shown) that drives the transport arm 15. The transport arm 15 is mounted on the mounting part 14a and can rotate freely about the rotation axis C1. Furthermore, the structure of the transport arm 15 is not particularly limited to a structure that holds the outer side of the semiconductor substrate 50, as long as it can hold the semiconductor substrate 50 and transport it; a structure suitable for transporting semiconductor wafers between processes can be appropriately utilized. The mounting part 14a of the transport device 14 can move along the height direction V, and the transport arm 15 can move along the height direction V, which is parallel to the rotation axis C1. By moving the mounting part 14a along the height direction V, the position of the transport arm 15 in the height direction V can be changed.

[0066] (Surface Defect Measurement Department) Surface defects of the semiconductor substrate 50 are measured inside the measurement chamber 12b as described above. A surface defect measurement unit 20 is provided inside the measurement chamber 12b. The surface defect measurement unit 20 measures whether there are defects on the surface 50a of the semiconductor substrate 50, and obtains position information on the surface 50a of the semiconductor substrate 50 for defects on the surface 50a of the semiconductor substrate 50. The surface defect measurement unit 20 includes a stage 22 for placing the semiconductor substrate 50, an incident light Ls incident on the surface 50a of the semiconductor substrate 50 by means of an incident light Ls, and a focusing lens 24 for focusing the incident light Ls onto the surface 50a of the semiconductor substrate 50. The stage 22 for placing the semiconductor substrate 50 is rotatable about the rotation axis C2, allowing the position of the semiconductor substrate 50 in the height direction V to be changed, and also allowing the position in the direction H orthogonal to the height direction V to be changed. The stage 22 allows the illumination position of the incident light Ls on the surface 50a of the semiconductor substrate 50 to be changed. Therefore, by sequentially irradiating a specific area or the entire surface area of ​​the semiconductor substrate 50 with incident light Ls, defects such as foreign matter on the surface 50a of the semiconductor substrate 50 can be detected. Here, foreign matter on the surface 50a of the semiconductor substrate 50 refers to foreign matter originating from the aforementioned liquid or photoresist composition.

[0067] The wavelength of the incident light Ls irradiated by the incident section 23 is not particularly limited. The incident light Ls may be ultraviolet light, but it may also be visible light or other light. Here, ultraviolet light refers to light with a wavelength range of less than 400 nm, and visible light refers to light with a wavelength range of 400 to 800 nm. As the incident angle of the incident light Ls, all directions horizontal to the surface 50a of the semiconductor substrate 50 are set to 0°, and the direction perpendicular to the surface 50a of the semiconductor substrate 50 is set to 90°. At this time, if the incident angle of the incident light Ls is defined as a minimum of 0° to a maximum of 90°, then the incident angle of the incident light Ls is more than 0° and less than 90°, preferably more than 0° and less than 90°.

[0068] The surface defect measurement unit 20 has a light-receiving section that receives incident light Ls that is reflected or scattered by the surface 50a of the semiconductor substrate 50 and emitted as radiation. In the surface defect measurement unit 20 shown in FIG. 8, for example, two light-receiving sections 25 and 26 are provided. When either light-receiving section 25 or 26 receives radiation, it is considered that a defect exists on the surface 50a of the semiconductor substrate 50; when no radiation is generated, it is considered that there is no defect on the surface 50a of the semiconductor substrate 50. Thus, the presence or absence of defects on the surface 50a of the semiconductor substrate 50 is determined. A light-receiving portion 25 is disposed around the semiconductor substrate 50. A light-receiving portion 26 is disposed above the surface 50a of the semiconductor substrate 50. A condensing lens 27 is provided between the surface 50a of the semiconductor substrate 50 and the light-receiving portion 26. The emitted light generated by the incident light Ls is focused onto the light-receiving portion 26 by the condensing lens 27. By means of the condensing lens 27, the emitted light can be efficiently focused onto the light-receiving portion 26. Furthermore, the number of light-receiving portions is not particularly limited to two. In the surface defect measuring unit 20, it can be a structure of either the light-receiving portion 25 or the light-receiving portion 26, or it can be a structure with three or more light-receiving portions. The light-receiving portion 25 is a component that receives emitted light on the low-angle side. Receiving light on the low-angle side means receiving light in the range of 0° to 80° at the aforementioned incident angle. The light-receiving portion 26 is a component that receives emitted light on the high-angle side. Receiving light on the high-angle side means receiving light in the range of more than 80° and less than 90° at the aforementioned incident angle. The light-receiving parts 25 and 26 are, for example, composed of a photomultiplier tube or other light sensor. Furthermore, both the light-receiving parts 25 and 26 can accept unpolarized or polarized light.

[0069] The surface defect measurement unit 20 has a calculation unit 28 and a storage unit 29. The arithmetic unit 28 calculates the location information and size of the detected defects based on the information of the emitted light received by the light-receiving units 25 and 26. The location information of the defects refers to the information of the position coordinates of the defects on the surface 50a of the semiconductor substrate 50. The position coordinates are, for example, coordinates of a common reference position in the plurality of semiconductor substrates 50, and the origin of the reference position is set.

[0070] The incident light Ls irradiated by the incident light 23 is received by the light-receiving sections 25 and 26 and is emitted as radiation due to reflection or scattering caused by defects on the surface 50a of the semiconductor substrate 50. The emitted light is detected as a bright spot in the light-receiving sections 25 and 26. In the arithmetic unit 28, the size of the defect that generates the bright spot, i.e., the detection size, is calculated based on the size of a standard particle, according to the size of the bright spot in the light-receiving sections 25 and 26 containing information about the emitted light generated by the defect. The calculation of the detection size based on the size of the standard particle is performed using a commercially available surface inspection device or by employing a known arithmetic method. The arithmetic unit 28 obtains position information of the irradiation position of the incident light Ls from the control unit 42, and for example, obtains position information and size information of the defect on the surface 50a of the semiconductor substrate 50 based on information about the emitted light generated by the defect in the light-receiving sections 25 and 26. The obtained position information and size information of the defect on the surface 50a of the semiconductor substrate 50 are stored in the storage unit 29. The storage unit 29 is only required to store the location and size information of defects such as foreign objects on the surface 50a of the semiconductor substrate 50, and there are no particular limitations. For example, it can use various storage media such as volatile memory, nonvolatile memory, hard disk, or SSD (Solid State Drive).

[0071] Here, in the surface defect measuring unit 20, the stage 22 and the incident unit 23 are controlled by the control unit 42. Also, the calculation unit 28 is controlled by the control unit 42. The control unit 42 acquires position information of the incident light Ls irradiated by the incident unit 23 on the surface 50a of the semiconductor substrate 50. To irradiate the area of ​​the surface 50a of the semiconductor substrate 50 that is not irradiated with the incident light Ls, the control unit 42 drives the stage 22, changing the irradiation position of the surface 50a of the semiconductor substrate 50. In the surface defect measurement unit 20, the incident light Ls is irradiated over the entire area of ​​the surface 50a of the semiconductor substrate 50. For example, based on information from the emitted light received by the two light-receiving units 25 and 26, position information and size information of defects on the surface 50a of the semiconductor substrate 50 at each irradiation position are obtained. Thus, position information and size information of defects on the entire surface 50a of the semiconductor substrate 50 can be acquired. That is, position information and size information of two-dimensional defects on the surface 50a of the semiconductor substrate 50 can be acquired. When performing measurements using the surface defect measurement unit 20, the atmosphere of the measurement chamber 12b is not particularly limited; as described above, it can be a reduced pressure atmosphere or a nitrogen atmosphere. Furthermore, as the surface defect measuring unit 20, a surface inspection device (SurfScan SP5; manufactured by KLA Corporation) can be used, for example.

[0072] A conveying device 16 is provided inside the second conveying chamber 12c. The conveying device 16 is a device that conveys the semiconductor substrate 50, whose surface defects have been measured by the surface defect measuring unit 20 in the measuring chamber 12b, from the measuring chamber 12b to the analysis chamber 12d. The conveying device 16 can use a conveying device with the same structure as the conveying device 14 described above. The conveying device 16 has a conveying arm 15 that clamps the outer side of the semiconductor substrate 50 and a drive unit (not shown) that drives the conveying arm 15. The conveying arm 15 is mounted on a mounting portion 16a and can rotate freely about a rotation axis C1. The mounting portion 16a of the conveying device 16 can move along the height direction V and can also move along the height direction V in a direction parallel to the rotation axis C1. By moving the mounting portion 16a, on which the conveying arm 15 is mounted, along the height direction V, the conveying arm 15 can change its position in the height direction V.

[0073] (Analysis Department) The analysis chamber 12d contains an analysis unit 30. The analysis unit 30 uses LA-ICP-MS (Laser Ablation-Inductively Coupled Plasma Mass Spectrometer) for analysis. ICP-MS (Inductively Coupled Plasma Mass Spectrometer) is a device that uses plasma of argon gas at approximately 10,000°C generated through inductive coupling to ionize elements in a liquid sample and perform mass spectrometry analysis. LA-ICP-MS involves irradiating defects 51 on the surface 50a of a semiconductor substrate 50 with laser light in the laser ablation section (LA section), using a carrier gas to introduce the sample obtained by irradiation into the ICP-MS section (Inductively Coupled Plasma Mass Spectrometer) for quantitative analysis of the elements contained in the sample.

[0074] The analysis unit 30 has a mounting stage 32 for placing a semiconductor substrate 50 and a container 33 for receiving the semiconductor substrate 50 placed on the mounting stage 32. An analysis unit 36 ​​is connected to the container section 33 via a pipe 39. The semiconductor substrate 50 is analyzed while it is entirely housed within the container section 33. The stage 32 on which the semiconductor substrate 50 is placed is rotatable about the rotation axis C3, allowing the position of the semiconductor substrate 50 in the height direction V to be changed, and also its position in the direction orthogonal to the height direction V. The stage 32 is controlled by a control unit 42. The control unit 42 drives the stage 32 to irradiate the defects 51 on the surface 50a of the semiconductor substrate 50 with laser light La, thus changing the irradiation position on the surface 50a of the semiconductor substrate 50. Here, if no material is coated or formed on the surface 50a of the semiconductor substrate 50, the defects 51 on the surface 50a of the semiconductor substrate 50 are defects 51 inherent to the semiconductor substrate 50 itself, originating from the semiconductor substrate 50. However, as described above, when performing inspections of the solution or photoresist composition, if the solution or photoresist composition is coated on the semiconductor substrate 50, the defect 51 originates from the solution or from the photoresist composition.

[0075] The analysis unit 30 includes a light source 34 that irradiates laser light La onto defects 51 on the surface 50a of the semiconductor substrate 50 as measured by the surface defect measurement unit 20. A focusing lens 35 is provided between the light source 34 and the surface 50a of the semiconductor substrate 50 to focus the laser light La onto the defects 51 on the surface 50a of the semiconductor substrate 50. The light source unit 34 and the focusing lens 35 are disposed outside the container unit 33. A window (not shown) through which the laser light La can pass is provided on the container unit 33 to allow the laser light La to pass through the interior. The light source unit 34 uses femtosecond laser light, nanosecond laser light, picosecond laser light, or attosecond laser light, etc. For example, a Ti:Sapphire laser light can be used as a femtosecond laser light.

[0076] The analysis unit 30 has a carrier gas supply unit 38 that supplies carrier gas to the container unit 33. The carrier gas supply unit 38 includes a gas supply source (not shown), such as a gas cylinder for storing carrier gas, a regulator (pressure regulator) connected to the gas supply source, and a regulating valve (not shown) for controlling the amount of carrier gas supplied. For example, the regulator and the regulating valve are connected via a tube, and the regulating valve is connected to the container unit 33 via a pipe. Helium or argon can be used as the carrier gas, for example. Furthermore, the analysis unit 30 includes a clean gas supply unit 40 for supplying clean gas to the container unit 33. The clean gas supply unit 40 includes: a gas supply source (such as a gas cylinder for storing clean gas); a regulator (pressure regulator) connected to the gas supply source; and a regulating valve (not shown) for controlling the amount of clean gas supplied. For example, the regulator and the regulating valve are connected via a tube, and the regulating valve is connected to the container unit 33 via a tube. Helium or argon can be used as the clean gas, for example.

[0077] Furthermore, an outlet 41 is provided on the container section 33 to allow the cleaning gas to flow out from inside the container section 33 to the outside. The outlet 41 is, for example, composed of a pipe and a valve. By opening the valve, the cleaning gas can flow out from inside the container section 33 to the outside. For rinsing, a heater (not shown) can be installed in the container section 33. By heating the container section 33 with cleaning gas supplied to it, foreign matter such as ablated deposits or adsorbed gases are removed. This improves the cleanliness of the container section 33 and reduces contamination of the semiconductor substrate 50. Furthermore, the heater can be, for example, an infrared lamp or a xenon flash lamp. In addition to cleaning gas, a carrier gas can also be used for rinsing.

[0078] <Analysis Unit> The analysis unit 36 ​​utilizes the aforementioned ICP-MS unit to irradiate defects 51 on the surface 50a of the semiconductor substrate 50 with laser light La. The sample obtained from the irradiation is recovered using a carrier gas and subjected to inductively coupled plasma mass spectrometry analysis. Furthermore, ICP stands for Inductively Coupled Plasma. In the analysis unit 36, the analyte is ionized using a high-temperature plasma maintained by high-frequency electromagnetic induction. The ions are detected using a mass spectrometer, thereby determining the atomic species and their concentration. For example, as shown in FIG9, the analysis unit 36 ​​includes: a plasma torch 44 that generates plasma ionizing the analyte sample introduced from the piping 39 along with a carrier gas; and a mass spectrometry analysis unit 46 having an ion introduction section located near the front end of the plasma torch 44.

[0079] The plasma torch 44 is, for example, a triple-tube structure, through which carrier gas is introduced from the piping 39. Furthermore, a plasma gas for plasma formation is introduced into the plasma torch 44. Argon is used as an example of the plasma gas. A high-frequency coil (not shown) connected to a high-frequency power supply (not shown) is provided on the plasma torch 44. By applying a high-frequency current of about 1~2KW, such as 27.12MHz or 40.68MHz, to the high-frequency coil, plasma is formed inside the plasma torch 44.

[0080] In the mass spectrometry analysis unit 46, ions generated by the plasma torch 44 are introduced into the ion lens unit 46a and the mass spectrometer unit 46b via the ion introduction unit. The ion lens unit 46a and the mass spectrometer unit 46b are depressurized by a vacuum pump (not shown), so that the ion lens unit 46a on the plasma torch 44 side becomes a low vacuum and the mass spectrometer unit 46b becomes a high vacuum.

[0081] The ion lens section 46a is provided with a plurality of ion lenses 47, for example, three ion lenses 47. The ion lenses 47 are components for separating ions in the mass spectrometer section 46b. Within the ion lens section 46a of the mass spectrometry analysis section 46, the light and ions of the plasma are separated by the ion lens 47, allowing only the ions to pass through.

[0082] The mass spectrometer section 46b is a component that separates ions according to their mass-to-charge ratio and detects them using a detector 49. The mass spectrometer section 46b includes a reflector 48 that reflects ions that have passed through the ion lens section 46a to the detector 49, and a detector 49 that detects the ions. The reflector 48, also known as an ion mirror, is a device that uses an electrostatic field to reverse the flight direction of charged particles. By using the reflector 48, charged particles with the same mass-to-charge ratio but different kinetic energies can be converged on the time axis and arrive at the detector 49 at approximately the same time. The reflector 48 can compensate for errors and improve the mass separation energy. The reflector 48 can be a known reflector used in time-of-flight mass spectrometers (TOF-MS).

[0083] Detector 49 is not particularly limited as long as it can detect ions and specific elements, and can use known detectors used in time-of-flight mass spectrometry (TOF-MS). The analysis unit 36 ​​can, for example, display the signal of the detected element ions as a graph (not shown) over time. The concentration of the detected element corresponds to the signal intensity.

[0084] As shown in Figure 8, the analysis device 10 has a control unit 42. The control unit 42, based on the location and size information of foreign matter and other defects detected on the surface 50a of the semiconductor substrate 50 stored in the storage unit 29 of the surface defect measurement unit 20, drives the stage 32 of the analysis unit 30 or changes the irradiation position of the laser light La to irradiate the defects 51 on the surface 50a of the semiconductor substrate 50 with the laser light La. Thus, the defects 51 on the surface 50a of the semiconductor substrate 50 are analyzed. Furthermore, the analysis apparatus 10 is configured to perform inductively coupled plasma mass spectrometry analysis by the analysis unit 30 while the semiconductor substrate 50 is entirely housed within the container section 33, thereby suppressing contamination of the surface 50a of the semiconductor substrate 50.

[0085] In the analysis apparatus 10, the carrier gas and the cleaning gas are supplied by different systems, but it is not limited to this. Since the supply timing of the carrier gas and the cleaning gas is different, they can also be supplied to the container section 33 by sharing a single configuration. For example, it is also possible to configure a structure that does not provide a cleaning gas supply section 40 but only provides a carrier gas supply section 38. Furthermore, the water content of the carrier gas is preferably above 0.00001 ppm by volume and below 0.1 ppm by volume.

[0086] If the moisture content of the carrier gas is 0.00001 ppm or more and 0.1 ppm or less, contamination on the surface 50a of the semiconductor substrate 50 during analysis can be reduced within the container section 33. For example, when the moisture content of the carrier gas is high, impurities dissolve into trace amounts of moisture adhering to the surface of the carrier gas piping or the inner surface of the container section 33. Sometimes these impurities re-adhere to the semiconductor substrate 50, resulting in an increase in the number of defects. However, if the moisture content of the carrier gas is within the aforementioned range, such impurities can be suppressed. Furthermore, when the moisture content is low, the carrier gas passing near the semiconductor substrate 50 can easily cause the surface 50a of the semiconductor substrate 50 to become charged. As a result, charged particles suspended in the container section 33 are easily attracted to the surface 50a of the semiconductor substrate 50, or particles suspended nearby during transport in the delivery system are easily guided to the surface 50a of the semiconductor substrate 50. Also, it can easily cause re-adhesion of products resulting from laser ablation, but if the moisture content of the carrier gas is within the aforementioned range, these substances can be suppressed. The moisture content in the carrier gas can be determined using an atmospheric pressure ionization mass spectrometer (API-MS) (e.g., manufactured by NIPPON API CO., LTD.). There is no particular limitation on the method for preparing the moisture content; it can be achieved by performing a gas purification process to remove water (water vapor) contained in the raw material gas. In particular, the moisture content in the carrier gas can be adjusted by changing the number of purification cycles or the filter. In addition, the expected flow rate of the carrier gas is 1.69×10⁻³~1.69 Pa·m³ / sec (1~1000 sccm (standard cubic centimeter per minute)).

[0087] [Example of an analytical method] The analytical method includes: a process for determining whether there are defects on the surface of a semiconductor substrate and obtaining information on the location of defects on the semiconductor substrate; and a process for irradiating the defects on the surface of the semiconductor substrate with laser light based on the location information of the defects on the semiconductor substrate, recovering the analytical sample obtained by irradiation using a carrier gas, and performing inductively coupled plasma mass spectrometry analysis. The analytical method will be described in detail below. Figure 10 is a schematic diagram illustrating a first example of the analytical method according to an embodiment of the present invention, and Figure 11 is a schematic cross-sectional view illustrating a first example of the analytical method according to an embodiment of the present invention. Furthermore, in Figures 10 and 11, the same reference numerals are used to denote structures identical to those in the analytical apparatus 10 shown in Figure 8, and detailed descriptions thereof are omitted.

[0088] In the analysis method, for example, a storage container 13 containing a plurality of semiconductor substrates 50 is connected to an inlet portion 12g on the side of the first delivery chamber 12a of the analysis apparatus 10 shown in FIG8. The lid of the storage container 13 is opened, and the semiconductor substrates 50 are made available for removal from the storage container 13. Next, using the transport device 14 of the first transport chamber 12a, the semiconductor substrate 50 is removed from the storage container 13 and transported to the stage 22 of the measurement chamber 12b. By using this process of transporting the semiconductor substrate 50 from the storage container 13 to the stage 22 of the measurement chamber 12b, contamination of the semiconductor substrate 50 can be suppressed even when transported from outside the analysis apparatus 10. With contamination of the semiconductor substrate 50 suppressed, surface defects of the semiconductor substrate 50 can be measured using the surface defect measurement unit 20.

[0089] Next, within the measurement chamber 12b, surface defects of the semiconductor substrate 50 are measured using the surface defect measurement unit 20. This allows for the detection of the location and size of defects such as foreign objects on the surface 50a of the semiconductor substrate 50. For example, as shown in FIG10, a defect 51 can be represented on the surface 50a of the semiconductor substrate 50. The process of representing the defect 51 on the surface 50a of the semiconductor substrate 50 is called mapping. The location and size information of the defect 51 on the surface 50a of the semiconductor substrate 50 are stored in the storage unit 29. This location and size information of the defect 51 on the surface 50a of the semiconductor substrate 50 is called mapping information.

[0090] Next, using the conveying device 16 of the second conveying chamber 12c shown in FIG8, the semiconductor substrate 50 whose surface defects have been measured is conveyed from the measuring chamber 12b to the analysis chamber 12d. Next, within the analysis chamber 12d, analysis is performed using the analysis unit 30 based on the position and size information, i.e., mapping information, of the defect 51 on the surface 50a of the semiconductor substrate 50. As shown in FIG11, the analysis is performed with the semiconductor substrate 50 entirely housed within the container 33 and with carrier gas supplied to the container 33 from the carrier gas supply unit 38. During analysis, the position of the defect 51 is determined based on the mapping information, for example, by using the stage 32 to move the semiconductor substrate 50 to the position where the defect 51 is irradiated by laser light La. Next, as shown in FIG11, laser light La is irradiated onto the defect 51 on the surface 50a of the semiconductor substrate 50. The analysis sample 51a obtained by irradiating the defect 51 with laser light La is moved to the analysis unit 36 ​​using the carrier gas. The analysis sample 51a from the defect 51, moved by the carrier gas, is subjected to inductively coupled plasma mass spectrometry analysis in the analysis unit 36 ​​to determine the elements of the defect 51. Thus, mass spectrometry data of the defect 51 is obtained.

[0091] In the analytical method, it is preferable to have a process of cleaning the container section 33 with a cleaning gas before the analysis process. Specifically, the cleaning process involves supplying a cleaning gas into the container section 33 before the semiconductor substrate 50 is transported into the container section 33, heating the container section 33 with a heater, and performing a rinsing process. Through the cleaning process, foreign matter such as ablated deposits or adsorbed gases are removed from the container section 33.

[0092] Furthermore, in the analysis apparatus 10, the position information of the defects 51 on the surface 50a of the semiconductor substrate 50, obtained by measuring the defects 51 on the surface 50a of the semiconductor substrate 50 using a different device than the analysis apparatus 10, such as the surface defect measuring apparatus 70 (see FIG8), can be used. The position information of the defects 51 on the surface 50a of the semiconductor substrate 50 is, for example, the mapping information shown in FIG10. In this case, the mapping information obtained by the surface defect measuring apparatus 70 is supplied to the storage unit 29. Furthermore, in the surface defect measuring apparatus 70, the semiconductor substrate 50 on which the defects 51 on the surface 50a are measured is, for example, stored in the storage container 13 and transported to the analysis apparatus 10. The semiconductor substrate 50 is transported to the analysis chamber 12d through the first transport chamber 12a, the measuring chamber 12b, and the second transport chamber 12c. Next, the control unit 42 reads the mapping information from the storage unit 29 and determines the location of the defect 51 on the surface 50a of the semiconductor substrate 50 based on the mapping information. Then, the semiconductor substrate 50 is moved to the position where the defect 51 is irradiated by laser light La using the stage 32. Next, the defect 51 on the surface 50a of the semiconductor substrate 50 is irradiated with laser light La. The analytical sample 51a obtained by irradiating the defect 51 with laser light La is moved to the analysis unit 36 ​​using a carrier gas. The analytical sample 51a from the defect 51, moved by the carrier gas, is subjected to inductively coupled plasma mass spectrometry analysis in the analysis unit 36 ​​to determine the elements of the specific defect 51. Thus, mass spectrometry data of the defect 51 is obtained.

[0093] As described above, when analyzing defect 51 using the mapping information shown in FIG10 measured by the surface defect measuring device 70 (see FIG8), it is not necessary to measure the surface defects of the surface defect measuring unit 20 and the semiconductor substrate 50. Alternatively, the analysis device 10 may not include the surface defect measuring device 70 shown in FIG8. Furthermore, the location information of the defects 51 on the surface 50a of the semiconductor substrate 50 supplied to the storage unit 29 is not particularly limited to the information measured by the surface defect measuring device 70 (see Figure 8). The surface defect measuring device 70 may, for example, have a storage unit (not shown) for storing location information. Also, the surface defect measuring device 70 may have the same structure as the surface defect measuring unit 20. Therefore, the surface defect measuring device 70 may, for example, have: an incident section 23 that allows incident light Ls to be incident on the surface 50a of the semiconductor substrate 50; and a light receiving section 26 that receives the emitted light due to the incident light Ls being reflected or scattered by the defects 51 on the surface 50a of the semiconductor substrate 50.

[0094] [Example of an analytical apparatus] Figure 12 is a schematic diagram showing a second example of an analytical apparatus according to an embodiment of the present invention. Furthermore, in Figure 12, the same reference numerals are used for structures identical to those in the analytical apparatus 10 shown in Figure 8, and detailed descriptions thereof are omitted. The analytical apparatus 10a shown in Figure 12 differs from the analytical apparatus 10 shown in Figure 8 in that it lacks a second transport chamber 12c and a transport device 16, and that the surface defect measurement unit 20 and the analysis unit 30 are housed within a single processing chamber 12e. Otherwise, its structure is identical to that of the analytical apparatus 10 shown in Figure 8.

[0095] In the analysis apparatus 10a, surface defect measurement and analysis are performed while the semiconductor substrate 50 is entirely housed within the container section 33. In the analysis unit 30, the light source unit 34 is configured such that the optical axis of the laser light La is tilted relative to the surface 50a of the semiconductor substrate 50. In the analysis apparatus 10a, by placing the surface defect measurement unit 20 and the analysis unit 30 within a single processing chamber 12e, the apparatus can be miniaturized compared to the analysis apparatus 10 shown in FIG. 8. Furthermore, the structure allows for surface defect measurement performed by the surface defect measurement unit 20 and inductively coupled plasma mass spectrometry analysis performed by the analysis unit 30 while the semiconductor substrate 50 is entirely housed within the container unit 33. This reduces the transport of the semiconductor substrate 50, further suppressing contamination of the surface 50a of the semiconductor substrate 50. Consequently, the accuracy of defect measurement on the surface 50a of the semiconductor substrate 50 can be further improved, and contamination within the processing chamber 12e of the analysis apparatus 10a can also be suppressed.

[0096] [Example of an analytical method] The second example of the analytical method is basically the same as the first example of the analytical method described above. The second example differs from the first example in that the surface defect measurement performed by the surface defect measurement unit 20 is carried out while the semiconductor substrate 50 is entirely housed within the container section 33, and that the semiconductor substrate 50 with measured surface defects is not transported from the measurement chamber 12b to the analysis chamber 12d by the transport device 16 after the surface defect measurement. Otherwise, the process is the same as the first example of the analytical method. In the second example of the analytical method, the surface defect measurement performed by the surface defect measurement unit 20 and the inductively coupled plasma mass spectrometry analysis performed by the analysis unit 30 are carried out while the semiconductor substrate 50 is entirely housed within the container section 33. This further suppresses contamination of the surface 50a of the semiconductor substrate 50, thereby suppressing contamination within the processing chamber 12e of the analytical apparatus 10a. Furthermore, as described above, with the semiconductor substrate 50 entirely housed within the container section 33, surface defect measurement performed by the surface defect measurement section 20 and inductively coupled plasma mass spectrometry analysis performed by the analysis section 30 are performed. This eliminates the need for inter-process transport of the semiconductor substrate 50, thus shortening the analysis time compared to the first example of the analysis method. Moreover, as described above, contamination of the surface 50a of the semiconductor substrate 50 can be further suppressed.

[0097] Furthermore, in the analysis apparatus 10a, similarly to the analysis apparatus 10, mapping information, such as that shown in FIG10, can be obtained by measuring defects 51 on the surface 50a of the semiconductor substrate 50 using a different device than the analysis apparatus 10a, such as the surface defect measuring device 70 (see FIG12). In this case, the mapping information acquired by the surface defect measuring device 70 is supplied to the storage unit 29. Furthermore, in the surface defect measuring device 70, the semiconductor substrate 50 on which the defects 51 on the surface 50a are measured is, for example, stored in the storage container 13 and transported to the analysis apparatus 10a. In the analysis apparatus 10a, based on the mapping information, the elements of the defect 51 are determined by inductively coupled plasma mass spectrometry analysis of the analysis sample 51a from the defect 51 in the analysis unit 36d within the processing chamber 12e using the analysis unit 30, as described above. Thus, mass spectrometry data of the defect 51 is obtained. Even in this case, when using the mapping information measured by the surface defect measuring device 70 (see FIG. 12), it is not necessary to measure the surface defects of the surface defect measuring unit 20 and the semiconductor substrate 50. Furthermore, the analysis apparatus 10a can, of course, be structured similarly to the analysis apparatus 10 without the surface defect measuring device 70 shown in FIG. 12. Also, the location information of the defect 51 on the surface 50a of the semiconductor substrate 50 supplied to the storage unit 29 is not particularly limited to the information measured by the surface defect measuring device 70 (see FIG. 12).

[0098] [The third example of an analytical device] As described above, when using mapping information measured by a device other than the analysis apparatus, such as the surface defect measuring device 70, the surface defect measuring unit is not necessarily required in the analysis apparatus, and the analysis apparatus may be structured without a surface defect measuring unit. In this case, the analysis apparatus becomes a structure having only the analysis unit 30. FIG13 is a schematic diagram showing a third example of an analysis apparatus according to an embodiment of the present invention. Furthermore, in FIG13, the same reference numerals are used for the same structures as those in the analysis apparatus 10 shown in FIG8 and the analysis apparatus 10a shown in FIG12, and their detailed descriptions are omitted. Compared with the analysis apparatus 10 shown in FIG8, the analysis apparatus 10b shown in FIG13 is a structure without the first delivery chamber 12a, the delivery device 14, the measuring chamber 12b, the surface defect measuring unit 20, the second delivery chamber 12c, and the delivery device 16. Moreover, the analysis apparatus 10b uses the analysis unit 30 (refer to FIG8) as a mass spectrometry analysis device 72, and has the aforementioned surface defect measuring device 70 and mass spectrometry analysis device 72. The mass spectrometry analysis device 72 has the same structure as the analysis unit 30 described above (see Figure 8), therefore a detailed description of the mass spectrometry analysis device 72 is omitted.

[0099] In the analysis apparatus 10b, the surface defect measuring device 70 and the mass spectrometry analysis device 72 are independent devices, not a single unit. In this case, the mapping information acquired by the surface defect measuring device 70 is supplied to the storage unit 29. Furthermore, in the surface defect measuring device 70, the semiconductor substrate 50 on which defects 51 on the surface 50a have been measured is, for example, housed in the housing 13 and transported to the mass spectrometry analysis device 72. The semiconductor substrate 50 is transported to the analysis chamber 12d via the first transport chamber 12a. Next, in the mass spectrometry analysis apparatus 72, the control unit 42 reads the mapping information from the storage unit 29. Based on the mapping information, in the analysis chamber 12d, the analysis sample 51a from the defect 51 is analyzed by the analysis unit 36d using inductively coupled plasma mass spectrometry, as described above, to determine the elements of the specific defect 51. Thus, mass spectrometry data of the defect 51 is obtained. Furthermore, the position information of the defect 51 on the surface 50a of the semiconductor substrate 50 supplied to the storage unit 29 can also be position information other than that measured by the surface defect measuring apparatus 70 (see Figure 13).

[0100] The analysis units 30 of the analysis apparatus 10, analysis apparatus 10a, and analysis apparatus 10b described above are not limited to the structures described above. Here, FIG14 is a schematic diagram showing a modified example of the analysis unit of the analysis apparatus according to an embodiment of the present invention. Furthermore, in FIG14, the same reference numerals are used to denote the same structures as those in the analysis apparatus 10 shown in FIG8, and their detailed descriptions are omitted. The analysis unit 30 may also include an imaging unit 60 for observing the surface 50a of the semiconductor substrate 50 and a display unit 62 for displaying the image obtained by the imaging unit 60. The imaging unit 60 allows observation of the location of the laser light La irradiation on the surface 50a of the semiconductor substrate 50, i.e., the location of the defect 51. Examples of imaging units 60 include CCD (Charge Coupled Device) sensors and CMOS (Complementary Metal Oxide Semiconductor) sensors. Examples of display units 62 include liquid crystal monitors and organic EL (Electro Luminescence) monitors. The light source unit 34 and the imaging unit 60 are configured, for example, to have their optical axes (not shown) orthogonal. The imaging unit 60 is positioned opposite the surface 50a of the semiconductor substrate 50. A semi-reflective mirror 64 is positioned at the intersection of the optical axis of the light source unit 34 and the optical axis of the imaging unit 60. The laser light La emitted from the light source 34 is reflected by the semi-reflective mirror 64 and, through the focusing lens 35, illuminates the surface 50a of the semiconductor substrate 50.

[0101] (Semiconductor substrate) There are no particular limitations on semiconductor substrates; various semiconductor substrates such as silicon (Si) substrates, sapphire substrates, SiC substrates, GaP substrates, GaAs substrates, InP substrates, or GaN substrates can be used. However, silicon semiconductor substrates are most commonly used as semiconductor substrates.

[0102] Furthermore, the following components can be exemplified as semiconductor elements. [Semiconductor Components] There are no particular limitations on semiconductor components. Examples include logic LSIs (Large Scale Integration) (e.g., ASICs (Application Specific Integrated Circuits), FPGAs (Field Programmable Gate Arrays), ASSPs (Application Specific Standard Products), etc.), microprocessors (e.g., CPUs (Central Processing Units), GPUs (Graphics Processing Units), etc.), memory (e.g., DRAMs (Dynamic Random Access Memory), HMCs (Hybrid Memory Cubes), MRAMs (Magnetic RAMs), PCMs (Phase-Change Memory), ReRAMs (Resistive RAMs), FeRAMs (Ferroelectric RAMs), NAND flash memory, etc.), and LEDs (Light Emitting Diodes). Diode (e.g., micro-flickers in mobile terminals, automotive applications, projector light sources, LCD backlights, general lighting, etc.), power components, analog ICs (integrated circuits) (e.g., DC-DC converters, insulated-gate bipolar transistors (IGBTs), etc.), MEMS (Micro Electro Mechanical Systems) (e.g., accelerometers, pressure sensors, oscillators, gyroscopes, etc.), wireless (e.g.,GPS (Global Positioning System), FM (Frequency Modulation), NFC (Nearfield Communication), RFEM (RF Expansion Module), MMIC (Monolithic Microwave Integrated Circuit), WLAN (Wireless Local Area Network), etc., Discrete Element, BSI (Back Side Illumination), CIS (Contact Image Sensor), Camera Module, CMOS (Complementary Metal Oxide Semiconductor), Passive Device, SAW (Surface Acoustic Wave) Filter, RF (Radio Frequency) Filter, RFIPD (Radio Frequency Integrated Passive Devices), BB (Broadband), etc.

[0103] The present invention is basically constructed as described above. The methods for inspecting the pharmaceutical solution, manufacturing the pharmaceutical solution, managing the pharmaceutical solution, manufacturing the semiconductor element, inspecting the photoresist composition, manufacturing the photoresist composition, managing the photoresist composition, and confirming the contamination status of the semiconductor manufacturing apparatus have been described in detail above. However, the present invention is not limited to the above embodiments, and various modifications or alterations can be made without departing from the spirit of the present invention.

[0104] [Medicine Solution] The solution contains an organic solvent as its main component. In this specification, "organic solvent" refers to a liquid organic compound present in an amount exceeding 10,000 ppm by mass relative to the total mass of the solution. That is, in this specification, a liquid organic compound present in an amount exceeding 10,000 ppm by mass relative to the total mass of the solution is equivalent to an organic solvent. Furthermore, in this specification, "liquid" means liquid at 25°C and atmospheric pressure.

[0105] The term "organic solvent as the main component" in a drug solution refers to an organic solvent content of 98.0% by mass or more, preferably 99.0% by mass or more, and even more preferably 99.90% by mass or more, relative to the total mass of the drug solution. The upper limit is less than 100% by mass. Organic solvents can be used alone or in combination. When using two or more organic solvents, it is preferable that their total content be within the range described above.

[0106] There is no particular limitation on the type of organic solvent used, and known organic solvents can be used. Examples of organic solvents include alkylene glycol monoalkyl ether carboxylic esters, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionic acid esters, cyclic lactones (preferably with 4 to 10 carbon atoms), monoketone compounds that may have rings (preferably with 4 to 10 carbon atoms), alkylene carbonate esters, alkyl alkoxyacetic acid esters, alkyl pyruvate esters, dialkyl alkylene, cyclic alkyl, dialkyl ethers, monohydric alcohols, dihydric alcohols, alkyl acetate esters, and N-alkylpyrrolidones, etc.

[0107] The organic solvent is preferably one or more selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), propylene carbonate (PC), isopropanol (IPA), 4-methyl-2-pentanol (MIBC), butyl acetate (nBA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisopentyl ether, isoamyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, cyclobutane, cycloheptanone, and 2-heptanone. Examples of using two or more organic solvents include the combined use of PGMEA and PGME, and the combined use of PGMEA and PC. Furthermore, the types and amounts of organic solvents in the drug solution can be determined using gas chromatography-mass spectrometry.

[0108] Sometimes, in addition to organic solvents, the liquid medicine may contain impurities. As impurities, metallic impurities can be cited as examples. Metallic impurities refer to metal ions and metallic impurities contained in the medicinal solution as solids (metallic elements, particulate metal-containing compounds, etc.). There are no particular limitations on the types of metallic elements contained in metallic impurities; for example, Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Al (aluminum), Cr (chromium), Ni (nickel), Ti (titanium), and Zn (zirconium). Metallic impurities can be components that are unavoidably present in the various components (raw materials) of the medicinal solution, components that are unavoidably present during the manufacture, storage, and / or transfer of the medicinal solution, or components that can be intentionally added.

[0109] The solution may also contain water. There are no particular restrictions on the type of water; for example, distilled water, ion-exchanged water, and pure water can be used. Water can be added to the drug solution, or it can be water that is inevitably mixed into the drug solution during the manufacturing process. Examples of unavoidable mixing during the manufacturing process of the drug solution include water being included in the raw materials used to manufacture the drug solution (e.g., organic solvents), and water being mixed (e.g., contamination) during the manufacturing process of the drug solution.

[0110] There is no particular limitation on the water content in the solution, but it is generally preferred to be less than 2.0% by mass, more preferably less than 1.0% by mass, and even more preferably less than 0.5% by mass relative to the total mass of the solution. Semiconductor chip manufacturing yields are superior when the water content in the solution is below 1.0% by mass. Furthermore, there is no specific lower limit, and it is often around 0.01% by mass. However, in manufacturing, it is difficult to set the water content below these values.

[0111] There are no particular limitations on the method for preparing the above-mentioned pharmaceutical solution. For example, methods such as purchasing organic solvents or obtaining organic solvents by reacting raw materials can be cited. Furthermore, it is preferable to prepare a pharmaceutical solution with a low content of the impurities already described (e.g., a pharmaceutical solution with an organic solvent content of 99% by mass or higher). Commercially available organic solvents include, for example, those referred to as "high-purity grade" organic solvents. In addition, the liquid medicine can be purified as needed. Examples of purification methods include distillation and filtration.

[0112] The solution preferably contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total content of the metallic elements is less than 10 ppb by mass relative to the total mass of the solution. If the value exceeds 10 ppb, correlation cannot be obtained between surface inspection devices (SurfScan SP5; manufactured by KLA Corporation) and indicators such as mass ppb based on ICP-MS, resulting in a smaller coefficient of determination. The contents of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn in the solution can be determined using the NexION 350 (trade name, manufactured by PerkinElmer) via ICP-MS (inductively coupled plasma mass spectrometry). Specific determination conditions using the ICP-MS method are as follows. Furthermore, the detection amount is determined by measuring the peak intensity relative to a standard solution of known concentration, converted to the mass of the metal component, and the content of the metal component in the treatment solution used in the determination (total metal content) is calculated. The content of the metal component is determined using a standard ICP-MS method. Specifically, ICP-MS software is used as the software for metal component analysis.

[0113] The determination of 0.01 ppq by mass is explained above. First, 1 mL of the reagent solution was applied as droplets onto a silicon wafer with a diameter of approximately 300 mm (12 inches). Then, it was dried without rotation. After determining the defect location of the silicon wafer using a surface inspection device (SurfScan SP7; manufactured by KLA Corporation), a cross-section near the defect location was cut out using FIB-SEM (HELIOS G4-EXL manufactured by Thermo Fisher Scientific), based on the coordinate file obtained using the surface inspection device (SurfScan SP7). While etching the cross-section using FIB (Focused Ion Beam)-SEM (Scanning Electron Microscope) or TEM (Transmission Electron Microscope), three-dimensional shape and elemental information was acquired using EDX. This process was performed on all defects. For example, if we consider the case where a spherical particle with Fe 13.5 nm (the limit of the surface inspection device (SurfScan SP7)) is found in 1 mL (concentration 1 g / cm 3) of drug solution, then in principle, it is possible to roughly determine 0.01 mass ppq by mass ratio conversion.

[0114] [Uses of the medicinal solution] Organic solvent-based solutions can be used in methods for manufacturing semiconductor devices and cleaning methods for semiconductor manufacturing equipment. Specifically, these solutions can be used in developing solutions, rinsing solutions, and pre-wetting solutions. In addition, they can be used in edge rinsing solutions, back rinsing solutions, photoresist stripping solutions, and diluents. Pre-wetting solutions are supplied to the semiconductor substrate before the formation of the photoresist film to facilitate the spread of the photoresist on the semiconductor substrate, thereby forming a uniform photoresist film with a smaller supply of photoresist. The aforementioned edge rinsing solution refers to a rinsing solution supplied to the periphery of the semiconductor substrate to remove the photoresist film from the periphery of the semiconductor substrate. For example, butyl acetate (nBA) can be used in developing solutions. Besides developing solutions, butyl acetate (nBA) can also be used for cleaning pipes or semiconductor wafers. Furthermore, 4-methyl-2-pentanol (MIBC) can be used in rinsing solutions. Propylene glycol monomethyl ether acetate (PGMEA) and isopropanol (IPA) can be used in cleaning solutions. Cyclohexanone (CHN) can be used in the pre-wetting solution.

[0115] [Photoresist composition] There is no particular limitation on the type of photoresist composition, and known photoresist compositions can be used. For example, as a photoresist composition, a photoresist composition containing a resin (hereinafter, also referred to as an "acid-degrading resin") having a group that generates a polar group due to the action of acid (hereinafter also referred to as an "acid-degrading group"), a photoacid generating agent, and a solvent can be used (hereinafter, also referred to as a "first photoresist composition"). The acid-degrading group is preferably a structure having a structure in which the polar group is removed by the action of acid and protected by a release group. That is, the acid-degrading resin has a repeating unit, and the repeating unit has an acid-degrading group. The resin having this repeating unit has increased polarity due to the action of acid, increased solubility in alkaline developing solution, and decreased solubility in organic solvent. As a polar group, it is preferably a base-soluble group, such as carboxyl, phenolic hydroxyl, fluorinated alcohol, sulfonic acid, phosphoric acid, sulfonamide, sulfonimide, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene, etc., as well as alcoholic hydroxyl groups.

[0116] Acid-degradable resins may contain repeating units other than repeating units with acid-degradable groups (e.g., repeating units with acid groups, repeating units with lactone groups, sulopentalide groups or carbonate groups, repeating units with fluorine atoms or iodine atoms, etc.). As an acid-degradable resin, a known acid-degradable resin can be used.

[0117] The photoacid generator is not particularly limited to any known type, but is preferably a compound that produces organic acids, such as sulfonic acids, bis(alkylsulfonyl)imines, and tri(alkylsulfonyl)methylates, by irradiation with photochemical rays or radiation, preferably electron beams or extreme ultraviolet light.

[0118] As solvents, water and organic solvents can be cited. There are no particular limitations on the types of organic solvents, and examples include alcohol solvents, ether solvents, ester solvents, ketone solvents, and hydrocarbon solvents.

[0119] The first photoresist composition may also contain materials other than acid-degradable resins, photoacid generators, and solvents. For example, the first photoresist composition may include an acid diffusion control agent. Examples of acid diffusion control agents include basic compounds and compounds having proton acceptor functional groups, which decompose upon exposure to photochemical rays or radiation, thereby producing compounds whose proton acceptor properties are reduced, disappear, or change from proton acceptor to acidic. Furthermore, the first photoresist composition may contain compounds selected from the group consisting of hydrophobic resins, surfactants, solubility inhibitors, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in the developer.

[0120] As a photoresist component, it can be a photoresist component containing a crosslinking agent having crosslinking groups, a compound having reactive groups that react with crosslinking groups, and a solvent (hereinafter, also referred to as "second photoresist component"). The combination of crosslinking groups and reactive groups is not particularly limited, and known combinations can be used. Furthermore, the crosslinking groups or reactive groups can be protected with protecting groups. For example, the second photoresist composition may further contain a photoacid generating agent, and the protecting group may be removed by the acid generated by the photoacid generating agent. Alternatively, the crosslinking agent and resin may undergo a condensation reaction to form a crosslinked structure by the acid generated by the photoacid generating agent. While the description has included both a crosslinking agent with crosslinking groups and a compound with reactive groups that react with the crosslinking groups in the second photoresist composition, a single compound containing both crosslinking groups and reactive groups may also be used.

[0121] As a photoresist composition, it can also be a photoresist composition containing a polymer with a main chain cleavage and a solvent. The term "main chain cleavage type" refers to a polymer whose main chain is cleaved when exposed to ionizing radiation, ultraviolet light, or other light. Examples of main chain cleavage type polymers include acrylic-based main chain cleavage type photoresists, such as polymethyl methacrylate (PMMA), ZEP (manufactured by Zeon Corporation of Japan), a copolymer of α-chloromethyl methacrylate and α-methylstyrene, and poly(2,2,2-trifluoroethyl α-chloroacrylate) (EBR-9, manufactured by Toray Industries, Inc.).

[0122] As a photoresist component, it can also be a so-called metallic photoresist component. Examples of the aforementioned metal photoresist compositions include photosensitive compositions capable of forming a coating containing a metal oxide-hydroxyl network, wherein the metal oxide-hydroxyl network has organic ligands via metal carbon bonds and / or metal carboxylate bonds. Examples of such metal photoresist compositions include those described in Japanese Patent Application Publication No. 2019-113855, the contents of which are incorporated herein by reference.

[0123] The photoresist composition preferably contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total content of the metallic element is less than 10 ppb by mass relative to the total mass of the photoresist composition. [Example]

[0124] The present invention will now be described in more detail based on embodiments. The materials, amounts, proportions, processing methods, and processing order shown in the following embodiments may be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the invention should not be limited by the embodiments shown below.

[0125] <Example A> [Preparation of the Solution] First, the solution (PGMEA (propylene glycol monomethyl ether acetate)) used in the examples described later was prepared. Specifically, first, a high-purity organic solvent reagent with a purity of 99% by mass or higher was purchased. Then, the purchased reagent was filtered using a suitable combination of the following filters to prepare the solution: • IEX-PTFE (15nm): 15nm IEX PTFE manufactured by Entegris • PTEE (12nm): 12nm PTFE manufactured by Entegris • UPE (3nm): 3nm PE filter manufactured by Entegris Furthermore, in order to adjust the amount of impurities in the solution, the source of the organic solvent reagent was appropriately changed, or the purity grade was changed, or distillation was performed before the above filtration process. The conditions were adjusted so that Fe became the main nanoparticle on the silicon substrate. Trace metals were measured in advance using an Agilent 8900 ICP-MS device manufactured by Agilent Technologies Inc. Hereinafter, Examples 1-13 and Comparative Examples 1-4 will be described. Furthermore, the results of Examples 1-13 and Comparative Examples 1-4 are shown in Table 1 below.

[0126] (Examples 1-13) In Examples 1-13, the chemical solution was adjusted on a 300mm diameter silicon substrate to achieve the particle count values ​​shown in the table. The adjusted chemical solution was applied to the 300mm diameter silicon substrate using a coating and developing apparatus. The coated silicon substrate was then placed in a storage container capable of holding the entire substrate and transported to a surface defect measurement unit. The surface defect measurement unit used a surface inspection device (SurfScan SP7; manufactured by KLA Corporation). In the surface inspection device, laser light was incident on the surface of the silicon substrate using optical defect inspection, and the scattered light was measured. This determined the position and size of defects on the silicon substrate, obtaining defect position and size information, which was then stored in a storage unit. Here, for the silicon substrate used in the chemical coating, the defect position and size were measured beforehand using the surface inspection device (SurfScan SP7). Based on the number of foreign particles after chemical coating, the difference between the number of foreign particles before and after chemical coating was calculated as the foreign particles originating from the chemical solution. Next, the silicon substrate, after surface defect measurement, is transported to the analysis unit. A laser ablation ICP-MS (LA-ICP-MS) instrument is used in the analysis unit. Furthermore, during the transport of the silicon substrate, it is loaded into a cell capable of housing the entire substrate, and carrier gas flows into the cell.

[0127] Based on the obtained defect location and size information (klarf file), elemental analysis of the defects based on laser ablation ICP mass spectrometry was performed using a laser ablation ICP mass spectrometry device, confirming that Fe could be detected at the specified locations after laser ablation. Laser ablation was performed with the silicon substrate housed in a container and with a carrier gas supplied. The analytical sample obtained from laser ablation was recovered using the carrier gas and analyzed by inductively coupled plasma mass spectrometry. A femtosecond laser was used in the laser ablation. Argon was used as the carrier gas. The carrier gas flow rate was set to 1.69 × 10⁻² Pa·m³ / sec (10 sccm). The moisture content in the carrier gas is shown in Table 1 below. A FOUP (Front Opening Unified Pod) was used as the container for housing the semiconductor substrate. Furthermore, prior to ablation, pre-cleaning was performed by circulating a cleaning gas at 1.69 × 10⁻¹ Pa·m³ / sec (100 sccm) within the cell for 1 minute.

[0128] (Comparative Examples 1-4) Comparative Examples 1-4 used a surface inspection apparatus (SurfScan SP7; manufactured by KLA Corporation) to incident laser light onto the surface of a silicon substrate. The location and size of defects on the silicon substrate were determined by measuring the scattered light, obtaining defect location and size information, which was then stored in a storage unit. Next, based on the obtained defect location and size information, Comparative Examples 1-4 attempted qualitative elemental analysis of defects on the silicon substrate after coating with the chemical solution using a defect detection apparatus (SEMVision G6 (manufactured by Applied Materials Corporation)). The qualitative elemental analysis of defects on the silicon substrate after coating with the chemical solution in Comparative Examples 1-4 was performed using SEM-EDS (Scanning Electron Microscope-Energy Dispersive X-ray Spectroscopy). Since SEM-EDS is performed under vacuum, no carrier gas is used. Therefore, for Comparative Examples 1-4, the "Moisture Content of Carrier Gas" column in Table 1 below is marked as "-".

[0129] Furthermore, in Examples 1-13 and Comparative Examples 1-4, after the coating solution was applied, the defect location information and size were measured using a surface inspection device (SurfScanSP7). The results are shown in the column "NP (SP7) on substrates below 20 nm after coating solution". In Examples 1-13 and Comparative Examples 1-4, after measuring defects in the pharmaceutical solution, the location and size of the defects were determined using a surface inspection device (SurfScan SP7). The results are shown in the column "NPs (SP7) on substrates below 20 nm after analysis". Furthermore, the "Detection Count of Fe in NPs below 20 nm" in Table 1 below represents the measurement results of defects in the pharmaceutical solutions of Examples 1-13 and Comparative Examples 1-4. In Table 1 below, nanoparticles are denoted as "NP".

[0130] [Table 1]

[0131] In Examples 1-13, Fe was detected even in tiny nanoparticle defects smaller than 20 nm, demonstrating the ability to inspect for minute metallic foreign matter in the manufactured pharmaceutical solution. In contrast, Fe below 20 nm was almost undetectable in Comparative Examples 1-4. Furthermore, Examples 1-13 yielded results comparable to those obtained with the surface inspection device (SurfScan SP7) in defect measurement. Also, in Examples 1-13, LA-ICP-MS was used. Therefore, by measuring defects, nanoparticles on the silicon substrate were ablated and disappeared, resulting in a reduction in nanoparticles after defect measurement. In Comparative Examples 1-4, SEM-EDX or SEM-EDS were used. Therefore, no reduction in nanoparticles was observed after defect measurement. Moreover, by setting the moisture content of the carrier gas to a range of 0.00001 ppm by volume and 0.1 ppm by volume, it was confirmed that the adhesion of nanoparticles caused by contamination on the silicon substrate surface during measurement could be suppressed, and contamination could be inhibited. The effectiveness of the present invention has been confirmed by the above.

[0132] <Example B> [Preparation of the Solution] Except for the type of solution, the same solution as in Example A was used. The following solutions were prepared: wafer cleaning solution (PGMEA (propylene glycol monomethyl ether acetate)), pre-wetting solution (CHN (cyclohexanone)), developer (nBA (butyl acetate)), and rinsing solution (MIBC (4-methyl-2-pentanol)). Furthermore, it was confirmed that the amount of any one of the trace metals was less than 10 ppb by mass. Examples 15-18 will be described below. The results of Examples 15-18 are shown in Table 2 below.

[0133] (Examples 15-18) In Examples 15-18, optical defect inspection was performed using a surface inspection device (SurfScan SP5; manufactured by KLA Corporation) in the same manner as in Examples 1-13, followed by inductively coupled plasma mass spectrometry analysis. The water content of the carrier gas was set to 0.1 ppm by volume.

[0134] (Medication solution management) The management tolerance value related to the number of metallic foreign matter on the silicon substrate during chemical coating is set to 150 or less [pieces / substrate] of metallic foreign matter smaller than 20 nm. Components that meet the management tolerance value are marked as "A" in the tolerance judgment column of Table 2 below, and components that do not meet the management tolerance value are marked as "B" in the tolerance judgment column of Table 2 below. In addition, nanoparticles are marked as "NP" in Table 2 below. The above management tolerance value is calculated by averaging the number of metallic foreign matter smaller than 20 nm obtained by LA-ICPMS in the manufacturing process using the above-mentioned chemical solution over past manufacturing practices. It can be seen that by using this management method, it is possible to manage metallic foreign matter smaller than 20 nm, i.e., nanoparticles, that become critical particles in advanced processes used to form patterns smaller than 20 nm in various chemical solutions such as wafer cleaning solutions, pre-wetting solutions, developing solutions, and rinsing solutions used for coating silicon substrates. Furthermore, the management method is also effective for drug solutions containing more than 10 ppb of any one of the various metal elements. However, since the dominant foreign matter is an ultra-small foreign matter smaller than 20 nm, the purity range is below 10 ppb. Therefore, such drug solutions cannot be managed in the existing technology. Thus, the above management method is a more effective management method.

[0135] (Component Manufacturing) The photolithography process described below was performed using a solution confirmed to be below the permissible limit. The number of defects was measured after the photolithography process. Clearly, when a solution confirmed to be within the permissible range was used, the number of defects after the photolithography process was low. Regarding the number of defects after the photolithography process, the photoresist after photolithography was ashed using an etching apparatus (TactrasVigus, manufactured by Tokyo Electron Limited) with oxygen plasma. Then, an optical defect inspection was performed using a surface inspection apparatus (SurfScanSP5; manufactured by KLA Corporation), thereby measuring the number of defects. The results are shown in the "Number of NPs after photolithography (≤20nm)" column of Table 2 below. Furthermore, in Table 2 below, ≤20nm indicates that the size of the nanoparticles is 20nm or less.

[0136] (Photolithography process) First, a silicon substrate with a diameter of approximately 300 mm (12 inches) was pre-wetted using cyclohexanone (CHN). Next, a photoresist resin composition was spin-coated onto the pre-wetted silicon substrate. Then, it was heated and dried on a hot plate at 150°C for 90 seconds to form a 90 nm thick photoresist film. For this photoresist film, a mask with a linewidth of 45 nm and a spacing of 45 nm, formed by reduced projection exposure and development, was patterned using an ArF excimer laser scanner (ASML, XT:1700i, wavelength 193 nm) under exposure conditions of NA=1.20, Dipole(oσ / iσ)=0.981 / 0.859, and gamma-polarized light. After irradiation, it was baked at 120°C for 60 seconds. Then, development and rinsing are performed, followed by baking at 110°C for 60 seconds to form a photoresist pattern with a linewidth of 45 nm and a spacing of 45 nm. The photoresist resin composition uses the substances shown below.

[0137] (Photoresist resin composition) The composition of the photoresist resin is described below. The photoresist resin composition is obtained by mixing the following components.

[0138] Acid-degradable resin (resin represented by the following formula (weight average molecular weight (Mw) 7500): the values ​​recorded in each repeating unit refer to moles): 100 parts by mass

[0139] [Chemical Formula 1]

[0140] The following photoacid generator: 8 parts by weight

[0141] [Chemical Formula 2]

[0142] The quencher described below: 5 parts by mass (mass ratio from left to right is 0.1:0.3:0.3:0.2). Furthermore, in the quencher described below, the weight-average molecular weight (Mw) of the polymeric substance is 5000. Also, the values ​​recorded in each repeating unit refer to molar ratios.

[0143] [Chemical Formula 3]

[0144] The hydrophobic resin shown below: 4 parts by weight (mass ratio set as (1):(2)=0.5:0.5). Furthermore, in the hydrophobic resins described below, the weight average molecular weight (Mw) of the hydrophobic resin of formula (1) is 7000, and the weight average molecular weight (Mw) of the hydrophobic resin of formula (2) is 8000. Additionally, in each hydrophobic resin, the values ​​recorded in each repeating unit refer to molar ratios.

[0145] [Chemical Formula 4]

[0146] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate): 3 parts by weight; Cyclohexanone: 600 parts by weight; γ-BL (γ-Butyrolactone): 100 parts by weight

[0147] [Table 2]

[0148] <Example C> [Preparation of the Photoresist Composition] The photoresist composition shown in Example B above was used. The photoresist composition was purified by filtration. It was then filled into a gallon bottle and connected to a coating and developing apparatus, LITHIUS PRO (registered trademark)-Z (manufactured by Tokyo Ginry Co., Ltd.). A silicon substrate with a diameter of approximately 300 mm (12 inches) was pre-wetted using cyclohexanone (CHN). Next, the photoresist resin composition was spin-coated onto the pre-wetted silicon substrate. Then, it was heated and dried on a hot plate at 150°C for 90 seconds to form a 45 nm thick photoresist film. Filtration conditions were adjusted to make Fe the dominant nanoparticle on the silicon substrate. Trace metals were pre-measured using an Agilent 8900 ICP-MS apparatus manufactured by Agilent Technologies.

[0149] Hereinafter, Examples 20-32 and Comparative Examples 20-23 will be described. Furthermore, the results of Examples 20-32 and Comparative Examples 20-23 are shown in Table 3 below. In Examples 20-32, the photoresist composition was adjusted on a silicon substrate with a diameter of 300 mm to achieve the particle values ​​shown in the table. Using a coating and developing apparatus, the adjusted photoresist composition was coated onto the 300 mm diameter silicon substrate. The silicon substrate coated with the photoresist composition was placed in a storage container capable of holding the entire substrate and transported to the surface defect measurement unit. A surface inspection device (SurfScan SP7; manufactured by KLA Corporation) was used in the surface defect measurement unit. In the surface inspection device, laser light was incident on the surface of the silicon substrate using optical defect inspection, and the scattered light was measured. This determined the position and size of defects on the silicon substrate, obtaining defect location information and defect size information, which were then stored in a storage unit. Here, for the silicon substrate used in photoresist coating, the defect location information and size are measured in advance using a surface inspection device (SurfScan SP7). Based on the number of foreign objects after photoresist coating, the difference between the number of foreign objects before and after photoresist coating is calculated as the foreign objects from the photoresist. Next, the silicon substrate with surface defect measurement is transported to the analysis unit. A laser ablation ICP mass spectrometry (LA-ICP-MS) device is used in the analysis unit. Furthermore, during the transport of the silicon substrate, it is loaded into a cell that can accommodate the entire silicon substrate, and a carrier gas flows into the cell.

[0150] Based on the obtained defect location and size information (klarf file), elemental analysis of the defects based on laser ablation ICP mass spectrometry was performed using a laser ablation ICP mass spectrometry device, confirming that Fe could be detected at the specified locations after laser ablation. Laser ablation was performed with the silicon substrate housed in a container and under a supplied carrier gas. The analytical sample obtained from laser ablation was recovered using the carrier gas and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). A femtosecond laser was used in the laser ablation. Argon was used as the carrier gas. The carrier gas flow rate was set to 1.69 × 10⁻² Pa·m³ / sec (10 sccm). The moisture content in the carrier gas is shown in Table 3 below. A FOUP (Front Opening Unified Pod) was used as the container for housing the semiconductor substrate. Furthermore, prior to ablation, pre-cleaning was performed by circulating a cleaning gas at 1.69 × 10⁻¹ Pa·m³ / sec (100 sccm) within the cell for 1 minute.

[0151] (Comparative Examples 20-23) Comparative Examples 20-23 used a surface inspection apparatus (SurfScan SP7; manufactured by KLA Corporation) to incident laser light onto the surface of a silicon substrate. The location and size of defects on the silicon substrate were determined by measuring the scattered light, and the location and size information of the defects were obtained and stored in the storage unit. Next, based on the obtained defect location and size information, Comparative Examples 20-23 attempted to perform qualitative elemental analysis of defects on the silicon substrate after photoresist coating using a defect detection apparatus (SEMVision G6 (manufactured by Applied Materials Corporation)). The qualitative elemental analysis of defects on the silicon substrate after photoresist coating in Comparative Examples 20-23 was performed using SEM-EDS (Scanning Electron Microscope-Energy Dispersive X-ray Spectroscopy). Since SEM-EDS is performed using an electron beam under vacuum, no carrier gas is used. Therefore, for Comparative Examples 20-23, the "Moisture Content of Carrier Gas" column in Table 3 below is marked as "-". Furthermore, in Table 3 below, nanoparticles are denoted as "NP".

[0152] Furthermore, in Examples 20-32 and Comparative Examples 20-23, after the photoresist composition was coated, the defect location information and size were measured using a surface inspection device (SurfScanSP7). The results are shown in the column "NP (SP7) on substrates below 20nm after photoresist composition coating". In Examples 20-32 and Comparative Examples 20-23, after measuring defects in the photoresist composition, the location and size of the defects were determined using a surface inspection device (SurfScan SP7). The results are shown in the column "NPs (SP7) on substrates below 20 nm after analysis". Furthermore, the "Detection Count of Fe in NPs below 20 nm" in Table 3 below represents the measurement results of defects in the photoresist composition of Examples 20-32 and Comparative Examples 20-23. In Table 3 below, nanoparticles are denoted as "NP".

[0153] [Table 3]

[0154] In Examples 20-32, Fe was detected even in tiny nanoparticle defects smaller than 20 nm, demonstrating the ability to inspect for minute metallic foreign matter in the manufactured pharmaceutical solution. In contrast, Fe below 20 nm was almost undetectable in Comparative Examples 20-23. Furthermore, Examples 20-32 obtained results in defect measurement comparable to those obtained with the surface inspection device (SurfScan SP7). Also, LA-ICPMS was used in Examples 20-32. Therefore, by measuring defects, nanoparticles on the silicon substrate were ablated and disappeared, resulting in a reduction in nanoparticles after defect measurement. In Comparative Examples 20-23, SEM-EDX or SEM-EDS were used. Therefore, no reduction in nanoparticles was observed after defect measurement. Moreover, by setting the moisture content of the carrier gas to a range of 0.00001 ppm by volume and 0.1 ppm by volume, it was confirmed that the adhesion of nanoparticles caused by contamination on the silicon substrate surface during measurement could be suppressed, and contamination could be inhibited. The effectiveness of the present invention has been confirmed by the above.

[0155] Example D [Manufacturing of the Photoresist Composition] The photoresist composition shown in Example B above was used. Furthermore, it was confirmed that the content of any one of the trace metal elements was less than 10 ppb by mass. Example 33 will be described below. The results of Example 33 are shown in Table 4 below.

[0156] (Example 33) In Example 33, similar to Examples 20-32 above, optical defect inspection was performed using a surface inspection device (SurfScan SP5; manufactured by KLA Corporation), followed by inductively coupled plasma mass spectrometry analysis. The water content of the carrier gas was set to 0.1 ppm by volume.

[0157] (Photoresist composition management) The management tolerance value related to the number of metallic foreign matter on the silicon substrate during photoresist coating is set to 500 or less [pieces / substrate] of metallic foreign matter smaller than 20 nm. Compositions that meet the management tolerance value are marked "A" in the tolerance judgment column of Table 4 below, and compositions that do not meet the management tolerance value are marked "B" in the tolerance judgment column of Table 4 below. Furthermore, nanoparticles are marked "NP" in Table 4 below. The above management tolerance value is calculated by averaging the number of metallic foreign matter smaller than 20 nm obtained from LA-ICPMS in the manufacturing of the above photoresist composition over past manufacturing practices. It can be seen that by using this management method, metallic foreign matter smaller than 20 nm, which becomes critical particles in advanced processes used to form patterns smaller than 20 nm in photoresist compositions, can be managed. Furthermore, the management method is also effective for photoresist compositions containing more than 10 ppb of any one of the various metal elements. However, since ultra-small foreign matter smaller than 20 nm becomes the dominant foreign matter in the purity range below 10 ppb, such photoresist compositions cannot be managed in the prior art. Therefore, the above management method is a more effective management method.

[0158] (Component Manufacturing) Using the photoresist composition confirmed to be below the allowable limit, the same photolithography process as in Example B was performed. The number of defects was measured after the photolithography process. Clearly, when a photoresist composition confirmed to be within the allowable range was used, the number of defects after the photolithography process was lower. Regarding the number of defects after the photolithography process, the photoresist after photolithography was ashed using an etching apparatus (TactrasVigus, manufactured by Tokyo Ginry Co., Ltd.) with oxygen plasma. Then, optical defect inspection was performed using a surface inspection apparatus (SurfScan SP5; manufactured by KLA Co., Ltd.), thereby measuring the number of defects. The results are shown in the "NP number after photolithography" column of Table 4 below. Also, in Table 4 below, ≤20nm indicates that the size of the nanoparticles is 20nm or less.

[0159] [Table 4]

[0160] <Example E> [Preparation of the Cleaning Solution] First, the cleaning solution (PGMEA (propylene glycol monomethyl ether acetate)) used in the example described later was prepared. Specifically, first, a high-purity organic solvent reagent with a purity of 99% by mass or higher was purchased. Then, the purchased reagent was filtered using a filter with the following appropriate combination to prepare the cleaning solution: • IEX-PTFE (15nm): 15nm IEX PTFE manufactured by Entegris • PTEE (12nm): 12nm PTFE manufactured by Entegris • UPE (3nm): 3nm PE filter manufactured by Entegris Furthermore, in order to adjust the amount of impurities in the cleaning solution described later, the source of the organic solvent reagent was appropriately changed, or the purity grade was changed, or distillation was performed before the above filtration process. Conditions were adjusted so that metal particles smaller than 20nm became the main nanoparticles on the silicon substrate.

[0161] (Performance confirmation of the cleaning solution) The cleaning solution was filled into a gallon bottle and connected to a thoroughly cleaned coating and developing apparatus, LITHIUS PRO (registered trademark)-Z (manufactured by Tokyo Yili Technology Co., Ltd.). After connection, the cleaning solution was applied to a silicon substrate with a diameter of approximately 300 mm (12 inches), and the silicon substrate was recovered. The recovered silicon substrate was measured as follows, and 50 nanoparticles of metal elements smaller than 20 nm were detected on the silicon substrate. The recovered silicon substrate was placed in a storage container capable of holding the entire silicon substrate and transported to the surface defect measurement unit. In the surface defect measurement unit, a surface inspection device (SurfScan SP5; manufactured by KLA Co., Ltd.) was used. In the surface inspection device, laser light was incident on the surface of the silicon substrate by optical defect inspection, and the scattered light was measured, thereby determining the position and size of defects on the silicon substrate, obtaining defect position information and defect size information, and storing them in the storage unit. Next, the silicon substrate that underwent surface defect measurement was transported to the analysis unit. A laser ablation ICP-MS (LA-ICP-MS) system was used in the analysis department. Furthermore, during silicon substrate transport, the silicon substrate was loaded into a cell capable of completely accommodating it, and a carrier gas was introduced into the cell. Based on the obtained defect location and size information (klarf file), elemental analysis of the defects based on laser ablation was performed using the LA-ICP-MS system. Laser ablation was performed with the silicon substrate housed within the container and with a carrier gas supplied. The analytical sample obtained from laser ablation was recovered using the carrier gas and subjected to inductively coupled plasma mass spectrometry (ICP-MS). A femtosecond laser was used in the laser ablation. Argon was used as the carrier gas. The carrier gas flow rate was set to 1.69 × 10⁻² Pa·m³ / sec (10 sccm). In addition, pre-cleaning is performed by circulating a cleaning gas within the unit for 1 minute at a rate of 1.69 × 10⁻¹ Pa·m³ / sec (100 sccm (standard cubic centimeter per minute)).

[0162] (Method for confirming contamination levels in semiconductor manufacturing equipment) Cleaning solution was filled into gallon bottles and connected to an unwashed LITHIUS PRO (registered trademark)-Z (manufactured by Tokyo Yili Technology Co., Ltd.). After connection, the cleaning solution was applied to a silicon substrate with a diameter of approximately 300 mm (12 inches). At this time, 10 mL was applied to the silicon substrate for every 1 L (1000 mL) of solution flowed. The silicon substrate was then recovered, and measurements were performed as described above to attempt the detection of nanoparticles of metallic elements. Furthermore, when the cleaning solution in the gallon bottle was used up, it was replaced with a new gallon bottle filled with cleaning solution. The detection counts of nanoparticles of metallic elements at each flow rate are shown in Table 5 below.

[0163] [Table 5]

[0164] As shown in Table 5, the more the liquid flow rate to the coating and developing unit increases, the fewer nanoparticles of metal elements are detected in the cleaning solution used for cleaning. This confirms that the contamination status of the coating and developing unit is improving.

[0165] 10, 10a, 10b: Analytical apparatus 12a: First transport chamber 12b: Measurement Chamber 12c: Second transport chamber 12d: Analytical Laboratory 12e: Processing Room 12g: Import section 12h: wall 13: Storage Containers 14: Conveying device 14a: Installation Department 15: Conveyor Arm 16: Conveying device 16a: Installation Department 20: Surface Defect Measurement Department 22, 32: Platform 23: Entrance section 24: Condensing Lens 25, 26: Light-receiving parts 27: Condensing Lens 28: Arithmetic Department 29: Storage Department 30: Analysis Department 33: Container Department 34: Light Source Section 35: Condensing Lens 36: Analysis Unit 38: Carrier Gas Supply Unit 39:Piping 40: Clean Gas Supply Department 41:Outflow department 42: Control Department 44: Plasma Torch 46: Mass Spectrometry Analysis Department 46a: Ion Lens Section 46b: Mass Spectrometer Section 47: Ion Lens 48: Reflector 49: Detector 50: Semiconductor substrate 50a: Surface 51: Defect 51a: Analytical Sample 70: Surface Defect Measurement Device 72: Mass spectrometry analysis device C1, C2, C3: Rotation axis H: Direction La: Laser light Ls: Incident light S10, S12, S14, S16, S18, S20: Steps S22, S23, S24, S26, S27, S28: Steps S30, S32, S34, S36, S38, S40: Steps S42, S43, S44, S46, S48, S50: Steps S52, S54, S56, S58, S60, S62: Steps S64, S66, S68: Steps V: Height direction

Claims

1. A method for testing a pharmaceutical solution, comprising: Preparation of the medicinal solution (1X); The process of coating the drug solution onto a semiconductor substrate (2X). The process (3X) involves determining whether there are defects on the surface of the semiconductor substrate, obtaining the location information of the defects on the surface of the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the location information, recovering the analytical sample obtained by irradiation using a carrier gas, and performing inductively coupled plasma mass spectrometry analysis, wherein the water content of the carrier gas is above 0.00001 ppm by volume and below 0.1 ppm by volume.

2. The method for testing the pharmaceutical solution as described in claim 1, wherein, A process (4X) is provided for determining whether a metal element is present in a defect based on mass spectrometry data obtained in the process (3X).

3. The method for testing the pharmaceutical solution as described in claim 2, wherein, After the process (4X), there is a process (5X) to determine the number of defects containing the metal element.

4. The method for testing the pharmaceutical solution as described in claim 1, wherein, A process (5X) is provided that determines the number of defects containing metallic elements in the defects based on mass spectrometry data obtained in the process (3X).

5. The method for testing the pharmaceutical solution as described in any one of claims 1 to 4, wherein, The drug solution contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total content of the metallic element is less than 10 ppb by mass relative to the total mass of the drug solution.

6. A method for manufacturing a medicinal liquid, comprising a method for testing the medicinal liquid as described in any one of claims 1 to 5.

7. A method for managing a medicinal liquid, comprising: The process of preparing the drug solution (1X); The process of coating the drug solution onto the semiconductor substrate (2X). Process (3X): determining whether there are defects on the surface of the semiconductor substrate, obtaining location information of the defects on the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the location information, recovering the analytical sample obtained by irradiation using a carrier gas, and performing inductively coupled plasma mass spectrometry analysis; Process (4X): determining whether there are metal elements in the defects based on the mass spectrometry data of the defects obtained in process (3X), and process (5X): determining the number of defects containing the metal elements, or determining the number of defects containing the metal elements based on the mass spectrometry data of the defects obtained in process (3X); and process (6X): determining whether the number of defects obtained in process (5X) is within the allowable range, wherein the water content of the carrier gas is 0.00001 ppm by volume or more and 0.1 ppm by volume or less.

8. The method for managing the liquid medicine as described in claim 7, wherein, The drug solution contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total content of the metallic element is less than 10 ppb by mass relative to the total mass of the drug solution.

9. A method for manufacturing a semiconductor device, comprising: The process of preparing the drug solution (1X); The process of coating the drug solution onto the semiconductor substrate (2X). Process (3X): determining whether there are defects on the surface of the semiconductor substrate, obtaining location information of the defects on the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the location information, recovering the analytical sample obtained by irradiation using a carrier gas, and performing inductively coupled plasma mass spectrometry analysis; Process (4X): determining whether there are metal elements in the defects based on the mass spectrometry data of the defects obtained in process (3X), and process (5X): determining the number of defects containing the metal elements based on the mass spectrometry data of the defects obtained in process (3X), or process (5X): determining whether the number of defects obtained in process (5X) is within the allowable range; Process (6X): manufacturing semiconductor devices using a solution determined to be within the allowable range in process (6X), wherein the water content of the carrier gas is 0.00001 ppm by volume or more and 0.1 ppm by volume or less.

10. A method for manufacturing a semiconductor device as described in claim 9, wherein, The solution is a pre-wetting solution, developing solution, rinsing solution, or cleaning solution.

11. A method for manufacturing a semiconductor device as described in claim 9, wherein, The drug solution contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total content of the metallic element is less than 10 ppb by mass relative to the total mass of the drug solution.

12. A method for inspecting photoresist components, comprising: The process includes: preparing a photoresist composition (1Y); coating the photoresist composition onto a semiconductor substrate (2Y); and a process (3Y) in which defects are measured in the coating of the photoresist composition, the location information of the defects in the coating of the photoresist composition on the semiconductor substrate is obtained, laser light is irradiated onto the defects on the surface of the semiconductor substrate based on the location information, and the analytical sample obtained by irradiation is recovered using a carrier gas and subjected to inductively coupled plasma mass spectrometry analysis, wherein the water content of the carrier gas is ≥0.00001 ppm by volume and ≤0.1 ppm by volume.

13. The method for inspecting photoresist components as described in claim 12, wherein, A process (4Y) is provided for determining whether a metal element is present in a defect based on mass spectrometry data obtained in the process (3Y).

14. The method for inspecting photoresist components as described in claim 13, wherein, Following the process (4Y), there is a process (5Y) for determining the number of defects containing the metal element.

15. The method for inspecting photoresist components as described in claim 12, wherein, A process (5Y) is provided that determines the number of defects containing metallic elements in the defects based on mass spectrometry data obtained in the process (3Y).

16. A method for inspecting a photoresist composition as described in any one of claims 12 to 15, wherein, The photoresist composition contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn, and the total content of the metallic element is less than 10 ppb by mass relative to the total mass of the photoresist composition.

17. A method for manufacturing a photoresist composition, comprising a method for inspecting the photoresist composition according to any one of claims 12 to 16.

18. A method for managing a photoresist composition, comprising: The process includes: a process for preparing a photoresist composition (1Y); a process for coating the photoresist composition onto a semiconductor substrate (2Y); a process (3Y) for determining whether there are defects in the coating of the photoresist composition, obtaining position information of the defects in the coating of the photoresist composition on the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the position information, recovering the analytical sample obtained by irradiation using a carrier gas, and performing inductively coupled plasma mass spectrometry analysis; a process (4Y) for determining whether there are metal elements in the defects based on the mass spectrometry data of the defects obtained in the process (3Y), and a process (5Y) for determining the number of defects containing the metal elements, or a process (5Y) for determining the number of defects containing the metal elements based on the mass spectrometry data of the defects obtained in the process (3Y); and a process (6Y) for determining whether the number of defects obtained in the process (5Y) is within the allowable range, wherein the water content of the carrier gas is 0.00001 ppm by volume or more and 0.1 ppm by volume or less.

19. A method for managing photoresist components as described in claim 18, wherein, The photoresist composition contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn, and the total content of the metallic element is less than 10 ppb by mass relative to the total mass of the photoresist composition.

20. A method for manufacturing a semiconductor device, comprising: The process includes: preparing a photoresist composition (1Y); coating the photoresist composition onto a semiconductor substrate (2Y); a process (3Y) measuring for defects in the photoresist composition coating, obtaining location information of the defects in the photoresist composition coating on the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the location information, recovering the analytical sample obtained by irradiation using a carrier gas, and performing inductively coupled plasma mass spectrometry analysis; a process (4Y) determining whether there are metal elements in the defects based on the mass spectrometry data obtained in the process (3Y) and a process (5Y) measuring the number of defects containing the metal elements, or a process (5Y) measuring the number of defects containing the metal elements based on the mass spectrometry data obtained in the process (3Y); a process (6Y) determining whether the number of defects obtained in the process (5Y) is within the allowable range; and a process (7Y) manufacturing a semiconductor device using a photoresist composition determined to be within the allowable range in the process (6Y). The water content of the carrier gas is above 0.00001 ppm by volume and below 0.1 ppm by volume.

21. A method for manufacturing a semiconductor device as described in claim 20, wherein, The photoresist composition contains at least one metallic element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn, and the total content of the metallic element is less than 10 ppb by mass relative to the total mass of the photoresist composition.

22. A method for confirming the contamination status of a semiconductor manufacturing apparatus, comprising: a process (1Z) of preparing a reagent solution; a process (2Z) of cleaning the semiconductor manufacturing apparatus using the reagent solution; a process (3Z) of coating the cleaned reagent solution from the process (2Z) onto a semiconductor substrate; a process (4Z) of determining whether there are defects on the surface of the semiconductor substrate, obtaining position information of the defects on the surface of the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the position information, recovering the analytical sample obtained by irradiation using a carrier gas and performing inductively coupled plasma mass spectrometry analysis; and a process (5Z) of determining whether there are metal elements in the defects based on the mass spectrometry data of the defects obtained in the process (4Z), wherein... The water content of the carrier gas is above 0.00001 ppm by volume and below 0.1 ppm by volume.

23. The method for confirming the contamination status of a semiconductor manufacturing apparatus as described in claim 22, wherein, This includes a process (6Z) for determining the number of defects containing the aforementioned metal element.

24. A method for confirming the contamination status of a semiconductor manufacturing apparatus, comprising: a process (1Z) of preparing a reagent solution; a process (2Z) of cleaning the semiconductor manufacturing apparatus using the reagent solution; a process (3Z) of coating the reagent solution after cleaning in the process (2Z) onto a semiconductor substrate; a process (4Z) of determining whether there are defects on the surface of the semiconductor substrate, obtaining position information of the defects on the surface of the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with laser light based on the position information, recovering the analytical sample obtained by irradiation using a carrier gas and performing inductively coupled plasma mass spectrometry analysis; and a process (6Z) of determining the number of defects containing metal elements in the defects based on the mass spectrometry data of the defects obtained in the process (4Z), wherein... The water content of the carrier gas is above 0.00001 ppm by volume and below 0.1 ppm by volume.

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