JP2023038168A - Method of inspecting medical fluid, method of manufacturing medical fluid, method of managing medical fluid, method of manufacturing semiconductor device, method of inspecting resist composition, method of manufacturing resist composition, method of managing resist composition, and method of checking contamination state of semiconductor manufacturing device - Google Patents

Abstract

To provide a method of inspecting medical fluid, a method of manufacturing medical fluid, and a method of managing medical fluid that are capable of analyzing fine foreign matters in the medical fluid, to provide a method of manufacturing a semiconductor device, to provide a method of inspecting a resist composition, a method of manufacturing a resist composition, and a method of managing a resist composition that are capable of analyzing fine foreign matters in the resist composition, and to provide a method of checking a contamination state of a semiconductor manufacturing device capable of managing fine foreign matters in the semiconductor manufacturing device.SOLUTION: A method of inspecting medical fluid includes: a step 1X of preparing medical fluid; a step 2X of applying the medical fluid on a semiconductor substrate; and a step 3X of measuring presence or absence of surface defects of the semiconductor substrate, obtaining positional information on the semiconductor substrate of the surface defects of the semiconductor substrate, irradiating the surface defects of the semiconductor substrate with a laser beam on the basis of the positional information, and collecting analysis samples obtained by the irradiation by a carrier gas to carry out inductive coupling plasma mass analysis.SELECTED DRAWING: Figure 1

Description

The present invention provides a method for inspecting a chemical solution, a method for producing a chemical solution, a method for managing a chemical solution, a method for producing a semiconductor device, and a method for inspecting a resist composition using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). , a method for manufacturing a resist composition, a method for managing a resist composition, and a method for checking the state of contamination of semiconductor manufacturing equipment.

Currently, various semiconductor devices are manufactured using semiconductor substrates such as silicon substrates. Defects such as foreign matter on the surface of the semiconductor substrate may result in insufficient formation of transistor gates, disconnection of wiring, etc., resulting in defective semiconductor devices. can be. Defects such as foreign matter on the surface of the semiconductor substrate affect the yield of semiconductor devices.

Defects in a semiconductor substrate can be evaluated using, for example, the technique of evaluating residual metal impurities inside a silicon crystal of a silicon wafer described in Patent Document 1. The method of evaluating residual metal impurities inside the silicon crystal of the silicon wafer of Patent Document 1 is to perform heat treatment, collect the metal impurities inside the silicon crystal on the silicon wafer surface, and then perform vapor phase decomposition inductively coupled plasma mass spectrometry (VPD). -ICP-MS) to measure the concentration of metal impurities collected on the surface of the silicon wafer. The number of surface defects on a silicon wafer is measured using SurfScan SP5 manufactured by KLA Corporation.

JP 2019-195020 A Japanese Patent Application Laid-Open No. 2020-027920

The gas-phase decomposition method inductively coupled plasma mass spectrometry disclosed in Patent Document 1 described above melts the silicon wafer and cannot non-destructively evaluate defects in the semiconductor substrate. As a method for non-destructively evaluating defects in a semiconductor substrate, there is a method for evaluating metal contamination on a wafer disclosed in Patent Document 2.

In the method for evaluating metal contamination on a wafer in Patent Document 2, a particle counter of a light scattering type is used as a foreign matter inspection device, which detects foreign matter by scanning the wafer surface with a laser beam and measuring the light scattering intensity from the foreign matter. (for example, SurfScan SP5 manufactured by KLA Corporation), and the use of a laser microscope with a confocal optical system (for example, MAGICS manufactured by Lasertec Co., Ltd.) that detects foreign matter by detecting the difference in reflected light from the wafer surface. ing. SEM (Scanning Electron Microscope) observation of bright spots based on the coordinates obtained in the first step, and EDX (Energy dispersive X-ray spectroscopy) analysis based on characteristic X-rays generated by electron beam irradiation. is described.

Here, as described above, when there is a defect such as a foreign substance on the surface of the semiconductor substrate, defects on the surface of the semiconductor substrate become more likely as semiconductor devices become finer and more highly integrated. , the influence of producing defective semiconductor devices and degrading the yield increases. Therefore, it is important to measure the defects on the surface of the semiconductor substrate, and among the defects of the semiconductor substrate, the measurement of minute particles becomes more important. However, when the evaluation method for metal contamination of a wafer described in Patent Document 2 is used for analysis of minute particles of about 20 nm on the surface of a semiconductor substrate, there is a high possibility that elemental analysis cannot be performed by EDX.
As in the case of the semiconductor substrate described above, it is desired that the chemicals and resist compositions be free from defects such as foreign matter from the viewpoint of quality control and manufacturing. Measurement of minute foreign matter and its elemental analysis are desired.
Also, in semiconductor manufacturing equipment, it is desired to control minute foreign matter because the contamination status affects the performance, quality, etc. of manufactured products. In order to manage minute foreign matter in semiconductor manufacturing equipment, there is a demand for measurement and elemental analysis of minute foreign matter that causes defective products in semiconductor devices that are particularly miniaturized and highly integrated.

An object of the present invention is to provide a method for inspecting a chemical solution, a method for manufacturing a chemical solution, and a chemical solution capable of quality control of the chemical solution even when the amount of minute foreign substances contained in the chemical solution is very small. management method, semiconductor device manufacturing method, resist composition inspection method capable of analyzing minute foreign matter in the resist composition, resist composition manufacturing method, minute amount of minute foreign matter contained in the resist composition Provided are a method for controlling a resist composition, a method for manufacturing a semiconductor device, and a method for checking the state of contamination in a semiconductor manufacturing apparatus, capable of controlling the quality of the resist composition even in the presence of microscopic particles in the semiconductor manufacturing apparatus. to do.

To achieve the above object, the invention [1] includes a step 1X of preparing a chemical solution, a step 2X of applying the chemical solution on a semiconductor substrate, measuring the presence or absence of defects on the surface of the semiconductor substrate, Obtain positional information on the semiconductor substrate of the defects on the surface of the semiconductor substrate, irradiate the defects on the surface of the semiconductor substrate with laser light based on the positional information, and recover the analysis sample obtained by irradiation with a carrier gas. and a step 3X of inductively coupled plasma mass spectrometry.
Invention [2] is the chemical liquid inspection method according to Invention [1], which has a step 4X of determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in step 3X.
Invention [3] is the chemical liquid inspection method according to Invention [2], further comprising a step 5X of measuring the number of defects containing a metal element after step 4X.
Invention [4] is the chemical solution according to Invention [1], which has a step 5X of measuring the number of defects containing a metal element in the defects based on the mass spectrometry data in the defects obtained in step 3X. Inspection method.

In invention [5], the chemical contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, The method for inspecting a chemical solution according to any one of inventions [1] to [4], wherein the total content of metal elements is 10 mass ppb or less with respect to the total mass of the chemical solution.
Invention [6] is the method for testing a chemical solution according to any one of inventions [1] to [5], wherein the carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less.

Invention [7] is a method for producing a chemical solution, including the method for inspecting a chemical solution according to any one of Inventions [1] to [6].
The invention [8] includes a step 1X of preparing a chemical solution, a step 2X of applying the chemical solution on a semiconductor substrate, measuring the presence or absence of defects on the surface of the semiconductor substrate, and detecting defects on the surface of the semiconductor substrate. A step of obtaining the positional information of, irradiating the defect on the surface of the semiconductor substrate with laser light based on the positional information, recovering the analysis sample obtained by irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry. 3X, a step 4X of determining the presence or absence of the metal element in the defect from the mass spectrometry data in the defect obtained in the step 3X, and a step 5X of measuring the number of defects containing the metal element, or Based on the mass spectrometry data in the defects obtained in step 3X, it has a step 5X of measuring the number of defects containing a metal element in the defects, and the number of defects obtained in step 5X is within the allowable range. and a step 6X of determining whether or not.

In invention [9], the chemical contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, The method for managing a chemical solution according to Invention [8], wherein the total content of metal elements is 10 mass ppb or less with respect to the total mass of the chemical solution.
Invention [10] is the chemical management method according to Invention [8] or [9], wherein the carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less.

The invention [11] includes a step 1X of preparing a chemical solution, a step 2X of applying the chemical solution on a semiconductor substrate, measuring the presence or absence of defects on the surface of the semiconductor substrate, and detecting defects on the surface of the semiconductor substrate. A step of obtaining positional information, irradiating a defect on the surface of a semiconductor substrate with a laser beam based on the positional information, recovering an analysis sample obtained by irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry. 3X, a step 4X of determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in the step 3X, and a step 5X of measuring the number of defects containing the metal element, or Based on the mass spectrometry data in the defects obtained in step 3X, it has a step 5X of measuring the number of defects containing a metal element in the defects, and the number of defects obtained in step 5X is within the allowable range. and a step 7X of manufacturing a semiconductor device using the chemical solution determined to be within the allowable range in the step 6X.

Invention [12] is the method for manufacturing a semiconductor device according to Invention [11], wherein the chemical is a prewet liquid, a developer, a rinse liquid, or a cleaning liquid.
In invention [13], the chemical contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, The method for manufacturing a semiconductor device according to invention [11] or [12], wherein the total content of the metal elements is 10 mass ppb or less with respect to the total mass of the chemical solution.
Invention [14] is the method for manufacturing a semiconductor device according to any one of Inventions [11] to [13], wherein the carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less.

The invention [15] comprises a step 1Y of preparing a resist composition, a step 2Y of applying the resist composition on a semiconductor substrate, measuring the presence or absence of defects in the coating film of the resist composition, and applying the resist composition. Obtaining the positional information of the defects in the film on the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with a laser beam based on the positional information, and recovering the analysis sample obtained by the irradiation with a carrier gas. and a step 3Y of inductively coupled plasma mass spectrometry.
Invention [16] is the method for inspecting a resist composition according to Invention [15], comprising Step 4Y of determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in Step 3Y.
Invention [17] is the method for inspecting a resist composition according to Invention [16], comprising Step 5Y of measuring the number of defects containing a metal element after Step 4Y.
Invention [18] is the resist composition according to Invention [15], which has a step 5Y of measuring the number of defects containing a metal element in the defects based on the mass spectrometry data in the defects obtained in step 3Y. A method of inspecting objects.

In invention [19], the resist composition contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn. The method for inspecting a resist composition according to any one of Inventions [15] to [18], wherein the total content of the metal elements is 10 mass ppb or less with respect to the total mass of the resist composition.
Invention [20] is the method for inspecting a resist composition according to any one of Inventions [15] to [19], wherein the carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less. .

Invention [21] is a method for producing a resist composition, comprising the method for inspecting the resist composition according to any one of Inventions [15] to [20].
The invention [22] comprises a step 1Y of preparing a resist composition, a step 2Y of applying the resist composition on a semiconductor substrate, measuring the presence or absence of defects in the coating film of the resist composition, and applying the resist composition. Obtaining the positional information of the defects in the film on the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with a laser beam based on the positional information, and recovering the analysis sample obtained by the irradiation with a carrier gas. Step 3Y for inductively coupled plasma mass spectrometry, Step 4Y for determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in Step 3Y, and measuring the number of defects containing the metal element Step 5Y, or Step 5Y of measuring the number of defects containing a metal element in the defects based on the mass spectrometry data in the defects obtained in Step 3Y, the defects obtained in Step 5Y and a step 6Y of determining whether the number of is within the allowable range.

Invention [23] provides that the resist composition contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn. The method for managing a resist composition according to Invention [22], wherein the total content of the metal elements is 10 mass ppb or less with respect to the total mass of the resist composition.
Invention [24] is the method for managing a resist composition according to Invention [22] or [23], wherein the carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less.

Invention [25] comprises Step 1Y of preparing a resist composition, Step 2Y of coating the resist composition on a semiconductor substrate, measuring the presence or absence of defects in the coating film of the resist composition, and applying the resist composition. Obtaining the positional information of the defects in the film on the semiconductor substrate, irradiating the defects on the surface of the semiconductor substrate with a laser beam based on the positional information, and recovering the analysis sample obtained by the irradiation with a carrier gas. Step 3Y for inductively coupled plasma mass spectrometry, Step 4Y for determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in Step 3Y, and measuring the number of defects containing the metal element Step 5Y, or Step 5Y of measuring the number of defects containing a metal element in the defects based on the mass spectrometry data in the defects obtained in Step 3Y, the defects obtained in Step 5Y Step 6Y of determining whether the number of is within the allowable range, and Step 7Y of manufacturing a semiconductor device using the resist composition determined to be within the allowable range in Step 6Y. Method.

In invention [26], the resist composition contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn. The method for manufacturing a semiconductor device according to the invention [25], wherein the total content of the metal elements is 10 mass ppb or less with respect to the total mass of the resist composition.
Invention [27] is the method for manufacturing a semiconductor device according to Invention [25] or [26], wherein the carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less.

The invention [28] comprises a step 1Z of preparing a chemical solution, a step 2Z of cleaning a semiconductor manufacturing apparatus using the chemical solution, a step 3Z of applying the chemical solution after cleaning in the step 2Z onto a semiconductor substrate, and a surface of the semiconductor substrate. measuring the presence or absence of defects on the surface of the semiconductor substrate, obtaining positional information on the semiconductor substrate 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 positional information, A step 4Z of recovering the analysis sample obtained by irradiation with a carrier gas and performing inductively coupled plasma mass spectrometry, and a step 5Z of determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in the step 4Z. A method for checking a contamination state of a semiconductor manufacturing apparatus, comprising:
Invention [29] is the method for checking the state of contamination of a semiconductor manufacturing apparatus according to Invention [28], including the step 6Z of measuring the number of defects containing a metal element.

The invention [30] comprises a step 1Z of preparing a chemical solution, a step 2Z of cleaning a semiconductor manufacturing apparatus using the chemical solution, a step 3Z of applying the chemical solution after cleaning in the step 2Z onto a semiconductor substrate, and a surface of the semiconductor substrate. measuring the presence or absence of defects on the surface of the semiconductor substrate, obtaining positional information on the semiconductor substrate 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 positional information, Step 4Z of recovering the analysis sample obtained by irradiation with a carrier gas and performing inductively coupled plasma mass spectrometry, and the number of defects containing a metal element based on the mass spectrometry data in defects obtained in Step 4Z and a step 6Z of measuring the contamination state of semiconductor manufacturing equipment.
Invention [31] is the contamination state of the semiconductor manufacturing apparatus according to any one of Inventions [28] to [30], wherein the carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less. Confirmation method.

INDUSTRIAL APPLICABILITY According to the present invention, there are provided a method for inspecting a chemical solution, a method for manufacturing a chemical solution, and a chemical solution capable of quality control even when the amount of minute foreign substances contained in the chemical solution is very small. management method, semiconductor device manufacturing method, resist composition inspection method capable of analyzing minute foreign matter in the resist composition, resist composition manufacturing method, minute amount of minute foreign matter contained in the resist composition Provided are a method for controlling a resist composition, a method for manufacturing a semiconductor device, and a method for checking the state of contamination in a semiconductor manufacturing apparatus, capable of controlling the quality of the resist composition even in the presence of microscopic particles in the semiconductor manufacturing apparatus. can.

It is a flow chart which shows an example of the inspection method of the medical fluid of the embodiment of the present invention. 4 is a flow chart showing an example of a method for managing a chemical solution according to an embodiment of the present invention; 1 is a flow chart showing a first example of a method for manufacturing a semiconductor device according to an embodiment of the present invention; 1 is a flow chart showing an example of a resist composition inspection method according to an embodiment of the present invention. 1 is a flow chart showing an example of a resist composition management method according to an embodiment of the present invention. 4 is a flow chart showing a second example of a method for manufacturing a semiconductor device according to an embodiment of the invention; 4 is a flow chart showing an example of a method for checking the contamination state of the semiconductor manufacturing equipment according to the embodiment of the present invention; 1 is a schematic diagram showing a first example of an analyzer according to an embodiment of the present invention; FIG. It is a schematic diagram showing an example of an analysis unit of the first example of the analysis device of the embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram explaining the 1st example of the analysis method of embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section explaining the 1st example of the analysis method of embodiment of this invention. It is a schematic diagram which shows the 2nd example of the analyzer of embodiment of this invention. FIG. 4 is a schematic diagram showing a third example of the analysis device according to the embodiment of the present invention; It is a schematic diagram which shows the modification of the analysis part of the analysis apparatus of embodiment of this invention.

Hereinafter, based on the preferred embodiments shown in the accompanying drawings, the method of inspecting a chemical solution, the method of producing a chemical solution, the method of managing a chemical solution, the method of producing a semiconductor device, the method of inspecting a resist composition, and the resist composition of the present invention. A manufacturing method, a resist composition control method, and a method for confirming the state of contamination of semiconductor manufacturing equipment will be described in detail.
It should be noted that the drawings described below are examples for explaining the present invention, and the present invention is not limited to the drawings shown below.

In the following, "~" indicating a numerical range includes the numerical values described on both sides. For example, when ε is numerical value ε _a to numerical value ε _b , the range of ε is a range including numerical value ε _a and numerical value ε _b , and represented by mathematical symbols, ε _a ≤ ε ≤ ε _b .
Angles such as “specified numerical angle,” “parallel,” “perpendicular,” and “perpendicular,” unless otherwise specified, include the generally accepted error ranges in the relevant technical fields.
In addition, "same" includes the margin of error that is generally allowed in the relevant technical field. Also, "whole surface" and the like include an error range that is generally allowed in the relevant technical field.
The term "preparation" includes not only preparation by synthesizing or preparing a specific material, but also procurement of a predetermined item by purchase or the like.
In addition, “ppm” means “parts-per-million (10 ⁻⁶ )”, “ppb” means “parts-per-billion (10 ⁻⁹ )”, and “ppt” means “parts-per -trillion (10 ⁻¹² )” and “ppq” means “parts-per-quadrillion (10 ⁻¹⁵ )”.
The chemical solution and resist composition will be described later. In addition, inductively coupled plasma mass spectrometry is performed as described later, and the specific apparatus configuration for performing inductively coupled plasma mass spectrometry will be described later.
The semiconductor manufacturing equipment described later is not particularly limited, but examples of the semiconductor manufacturing equipment include a coater/developer, a spin coater, a cleaning device for semiconductor wafers, a developing device, and the like.

2. Description of the Related Art Various chemical solutions such as developer, rinse, prewet, and remover used in the manufacturing process of semiconductor devices are required to be of high purity. For this reason, inspection and management of various chemical solutions have become important, and it is desired to be able to analyze minute foreign substances in chemical solutions. A method for inspecting a chemical solution and a method for managing the chemical solution will be described below.

[Method for inspecting chemical solution]
FIG. 1 is a flow chart showing an example of a chemical liquid inspection method according to an embodiment of the present invention.
In the method for inspecting a chemical solution, first, a chemical solution to be inspected is prepared (step 1X, step S10).
Next, a chemical solution is applied onto a semiconductor substrate (not shown) (step 2X, step S12).
Although the application of the chemical solution to the semiconductor substrate is not particularly limited, for example, a coater/developer is used.
Also, the semiconductor substrate is not particularly limited, but for example, a silicon substrate is used. In addition, although the size of the semiconductor substrate is not particularly limited, it depends on the amount of the chemical solution to be measured, such as the specifications of the coating device that applies the chemical solution to the semiconductor substrate and the specifications of the device that performs inductively coupled plasma mass spectrometry. determined as appropriate.

Next, the presence or absence of defects on the surface of the semiconductor substrate is measured to obtain positional information on the semiconductor substrate of defects on the surface of the semiconductor substrate (step S14). Based on the positional information, defects on the surface of the semiconductor substrate are irradiated with a laser beam, and an analysis sample obtained by the irradiation is collected with a carrier gas and subjected to inductively coupled plasma mass spectrometry (step 3X, step S16). . Elements of minute defects are identified by inductively coupled plasma mass spectrometry in step S16 (step 3X). Also, the size of minute defects is specified. Inductively coupled plasma mass spectrometry provides mass spectrometry data in defects in chemical solutions. The chemical liquid mass spectrometry data includes information on the element of the defect identified by the inductively coupled plasma mass spectrometry and information on the size of the defect. In this manner, the chemical liquid can be inspected, and the method for inspecting the chemical liquid enables the analysis of minute foreign substances in the chemical liquid.

A series of steps (step 3X, steps S14 and S16) of performing the above-described inductively coupled plasma mass spectrometry after applying the chemical solution to the semiconductor substrate will be described later in detail.
It is preferable that the method for inspecting the chemical liquid includes a step of measuring the presence or absence of defects on the surface of the semiconductor substrate to be used before applying the chemical liquid to the semiconductor substrate. In this case, the position information and size of the defect are measured. Thereby, the measured defects can be distinguished into those originating from the semiconductor substrate and those originating from the chemical solution.

By inductively coupled plasma mass spectrometry (step 3X, steps S14 and S16), the element of the minute defect can be specified, so that the minute foreign matter can be measured and the chemical liquid can be inspected.
For inductively coupled plasma mass spectrometry, a chemical solution can be applied to a semiconductor substrate to analyze minute foreign substances in the chemical solution. In inductively coupled plasma mass spectrometry, the chemical solution may be in a state on the semiconductor substrate, and after the chemical solution is applied to the semiconductor substrate, the solvent contained in the chemical solution is volatilized or evaporated to remove the solvent contained in the chemical solution from the semiconductor substrate. Inductively coupled plasma mass spectrometry may be performed in the state.

The chemical liquid inspection method may further include a step 4X (step S18) of determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in step 3X. A chemical solution can be inspected based on the presence or absence of a metal element.
Furthermore, after the step 4X (step S18), a step 5X (step S20) of measuring the number of defects containing a metal element may be provided. The number of defects containing metallic elements can be used to test the chemical solution.
In the chemical liquid inspection method, the defective element is specified by inductively coupled plasma mass spectrometry (step 3X, step S16). In step S18, an attempt is made to select a metal element from the mass spectrometry data containing information on the identified defect element. If no metal element is singled out from the mass spectrometry data, it is determined that there is no metal element. On the other hand, if the metal element is selected from the mass spectrometry data, it is determined that the metal element is present.
In step S20, if it is determined in step S18 that there is a metal element, the number of defects containing the metal element is measured. For example, the number of defects containing a metal element is measured by counting the number of defects containing a metal element.

In addition, without performing the step 4X (step S18) for determining the presence or absence of the metal element, based on the mass spectrometry data in the defect obtained in the step 3X (step S16), the defect containing the metal element in the defect may be measured (step 5X, step S20). In this case, in step S20, a metal element is selected from the mass spectrometry data containing information on the identified defect element, and the number of defects containing the metal element is counted by counting the number of selected metal elements. to measure. This also makes it possible to inspect the chemical solution using the number of defects containing a metal element.

[Method for producing chemical solution]
The method for inspecting the chemical solution described above can be used in the method for manufacturing the chemical solution. The results of inductively coupled plasma mass spectrometry are used in the chemical manufacturing method.
Further, for example, in a method for manufacturing a chemical solution, a threshold value or an allowable range for the number of defects in the chemical solution is set in advance. The number of defects in the manufactured chemical solution is measured by the above-described inspection method for the chemical solution. The measured number of defects in the chemical liquid is compared with the threshold value or the allowable range, and the product whose number of defects is equal to or less than the threshold value or within the allowable range is accepted as a product. On the other hand, if the number of defects exceeds the threshold or is out of the allowable range, the product is rejected. The allowable range for the number of defects in the chemical solution is, for example, 0.07/cm ² or less. The allowable range for the number of defects in the chemical solution is preferably 0.0001 to 10/cm ² , more preferably 0.0002 to 1/cm ² , and even more preferably 0.0005 to 0.5/cm ² . .

[Method of managing chemicals]
FIG. 2 is a flow chart showing an example of a method for managing a chemical liquid according to an embodiment of the present invention. In the chemical management method, the detailed description of the same steps as in the above-described chemical inspection method will be omitted.
Compared to the chemical inspection method, the chemical liquid management method shown in FIG. It has the same steps as the chemical liquid inspection method, except that it has a step 6X (step S22) of determining whether or not is within the allowable range.
The step of preparing the chemical solution (step 1X, step S10) is practically the same as the chemical solution, although there is a difference in whether it is an object to be inspected or an object to be managed. Therefore, the step 6X (step S22) of determining whether or not the number of defects is within the allowable range will be described.

In the chemical liquid management method, a threshold value or an allowable range for the number of defects in the chemical liquid is set in advance. The threshold value for the number of chemical liquid defects is set based on, for example, the number of chemical liquid defects in the previous production lot of the target chemical liquid, but is not limited to this, and may be a target value or a set value. , may be the average value of a plurality of production lots. The allowable range for the number of defects in the chemical solution is, for example, 0.07/cm ² or less. The allowable range for the number of defects in the chemical solution is preferably 0.0001 to 10/cm ² , more preferably 0.0002 to 1/cm ² , and even more preferably 0.0005 to 0.5/cm ² . .
In step S22 (step 6X), the number of defects containing the metal element obtained in step S20 described above is compared with the threshold value or allowable range of the number of defects in the chemical solution. For example, if the measured number of defects in the chemical solution is equal to or less than the threshold value or within the allowable range, the chemical solution is accepted as an acceptable product (step S23). On the other hand, if the number of chemical liquid defects exceeds the threshold value or is out of the allowable range, the chemical liquid is rejected (step S24). Thus, the quality of the chemical can be controlled by the number of defects in the chemical. According to the method for controlling the chemical solution, quality control of the chemical solution is possible even when the amount of minute foreign matter contained in the chemical solution is very small.

[First Example of Method for Manufacturing Semiconductor Device]
FIG. 3 is a flow chart showing a first example of a method for manufacturing a semiconductor device according to an embodiment of the present invention. In addition, in the first example of the semiconductor device manufacturing method, the detailed description of the same steps as the chemical liquid inspection method will be omitted.
The first example of the semiconductor device manufacturing method shown in FIG. A step 6X (step S26) of determining whether the number of defects obtained in S20) is within the allowable range, and a step 7X of manufacturing a semiconductor device using the chemical determined to be within the allowable range in the step 6X. (Step S27), it has the same steps as the chemical liquid inspection method.
The step of preparing the chemical solution (step 1X, step S10) is practically the same as the chemical solution, although there is a difference in whether it is used for the inspection object or in the manufacture of the semiconductor device. Therefore, the step 6X (step S22) of determining whether or not the number of defects is within the allowable range will be described.

In the semiconductor device manufacturing method, a threshold value or an allowable range for the number of chemical defects is set in advance. The threshold value or allowable range for the number of chemical defects is set based on, for example, the number of chemical defects in the previous production lot of the target chemical, but is not limited thereto, and is also set as a target value. It may be a value or an average value of a plurality of production lots. The allowable range for the number of defects in the chemical solution is, for example, 0.07/cm ² or less. The allowable range for the number of defects in the chemical solution is preferably 0.0001 to 10/cm ² , more preferably 0.0002 to 1/cm ² , and even more preferably 0.0005 to 0.5/cm ² . .
A step S26 compares the number of defects containing the metal element obtained in the above-described step S20 with the threshold value or allowable range of the number of chemical liquid defects. For example, if the measured number of defects in the chemical solution is below the threshold value or within the allowable range, it is used in the semiconductor device manufacturing method (step S27).
In step S26 (step 6X), the chemical solution for which the measured number of defects in the chemical solution is determined to exceed the threshold value, that is, the chemical solution for which the number of measured defects in the chemical solution is determined to be outside the allowable range is the semiconductor It is not used for manufacturing the device (step S28). As described above, in the semiconductor device manufacturing method, the selected chemical solution is used in the semiconductor device manufacturing process to manufacture the semiconductor device. The manufacturing process of semiconductor devices depends on the type of chemical solution. For example, if the chemical solution is a developer, it is used in the lithography process.
In the semiconductor device manufacturing method, the chemical liquid is not particularly limited as long as it relates to the manufacture of the semiconductor device, and is, for example, a prewet liquid, a developing liquid, a rinse liquid, or a cleaning liquid.

Resist compositions used in the manufacturing process of semiconductor devices are required to be free of defects such as foreign matter. For this reason, inspection and management of resist compositions have become important, and it is desired to be able to analyze minute foreign matter in resist compositions. A method for inspecting the resist composition and a method for managing the resist composition will be described below.

[Method for inspecting resist composition]
FIG. 4 is a flow chart showing an example of a resist composition inspection method according to an embodiment of the present invention. The method for inspecting a resist composition differs from the method for inspecting a chemical solution described above in that the object to be inspected is a resist composition, and the other steps are basically the same as those in the method for inspecting a chemical solution. .
In the resist composition inspection method, a resist composition to be inspected is prepared (step 1Y, step S30).
Next, a resist composition is applied onto a semiconductor substrate (not shown) (step 2Y, step S32). After applying the resist composition onto a semiconductor substrate (not shown), a film is formed to form a coating of the resist composition on the semiconductor substrate.
Coating of the resist composition onto the semiconductor substrate is not particularly limited, but for example, a coater/developer is used.
Moreover, the semiconductor substrate is not particularly limited, and the semiconductor substrate used in the above-described method for inspecting the chemical liquid can be used. Also, the size of the semiconductor substrate is not particularly limited in the same manner as in the above-described chemical liquid inspection method, but the specifications of the coating apparatus for coating the resist composition on the semiconductor substrate and the inductively coupled plasma mass spectrometry are performed. It is appropriately determined according to the amount of the resist composition to be measured, such as the specifications of the apparatus used for measurement.

Next, the presence or absence of defects in the coating film of the resist composition is measured to obtain positional information of the defects in the coating film of the resist composition on the semiconductor substrate (step S34). Based on the positional information, a laser beam is irradiated to defects in the coating film of the resist composition on the surface of the semiconductor substrate, and the analytical sample obtained by irradiation is collected with a carrier gas and subjected to inductively coupled plasma mass spectrometry. (step 3Y, step S36). Elements of minute defects are identified by inductively coupled plasma mass spectrometry in step S36. Also, the size of minute defects is specified. Inductively coupled plasma mass spectrometry provides mass spectrometry data in defects in resist compositions. The mass spectrometry data of the resist composition includes information on the elements of the defects identified by inductively coupled plasma mass spectrometry and information on the size of the defects. The resist composition can be inspected in this manner. In the resist composition inspection method, it is possible to analyze minute foreign matter in the resist composition.

A series of steps (step 3Y, steps S34 and S36) of performing the above-described inductively coupled plasma mass spectrometry after applying the resist composition to the semiconductor substrate will be described in detail later.
The method for inspecting the resist composition preferably includes a step of measuring the presence or absence of defects on the surface of the semiconductor substrate to be used before applying the resist composition to the semiconductor substrate. In this case, the position information and size of the defect are measured. Thereby, the measured defects can be distinguished into those originating from the semiconductor substrate and those originating from the resist composition.

By inductively coupled plasma mass spectrometry (Step 3Y, Steps S34 and S36), the element of minute defects can be specified, so that minute foreign matters can be measured and the resist composition can be inspected.
For inductively coupled plasma mass spectrometry, a resist composition can be applied to a semiconductor substrate and minute foreign matter in the resist composition can be analyzed. For example, inductively coupled plasma mass spectrometry is performed with the resist composition in the form of a coating film on a semiconductor substrate. Defects in the coating of the resist composition are measured. The defects in the coating film of the resist composition are derived from trace foreign matter unintentionally contained in the resist composition, and the defects in the coating film of the resist composition are considered to be defects of the resist composition. have the same meaning.

The resist composition inspection method may further include Step 4Y (Step S38) of determining the presence or absence of the metal element in the defect from the mass spectrometric data in the defect obtained in Step 3Y. A resist composition can be inspected based on the presence or absence of a metal element.
Furthermore, after step 4Y (step S38), step 5Y (step S40) of measuring the number of defects containing a metal element may be provided. The number of defects containing metallic elements can be used to inspect the resist composition.
In the resist composition inspection method, the defective element is specified by inductively coupled plasma mass spectrometry (step 3Y, step S36). In step S38, an attempt is made to select a metal element from the mass spectrometry data containing information on the identified defect element. If no metal element is singled out from the mass spectrometry data, it is determined that there is no metal element. On the other hand, if the metal element is selected from the mass spectrometry data, it is determined that the metal element is present.
In step S40, if it is determined in step S38 that there is a metal element, the number of defects containing the metal element is measured. For example, the number of defects containing a metal element is measured by counting the number of defects containing a metal element.

Based on the mass spectrometry data in the defects obtained in step 3Y (step S36) without performing step 4Y (step S38) for determining the presence or absence of the metal element, the number of defects containing a metal element in the defects may be measured (step 5Y, step S40). In this case, in step S40, a metal element is selected from the mass spectrometry data containing information on the identified defect element, and the number of defects containing the metal element is counted by counting the number of selected metal elements. to measure. This also allows the resist composition to be inspected using the number of defects containing a metal element.

[Method for producing resist composition]
The method for inspecting a resist composition described above can be used in a method for producing a resist composition. The results of inductively coupled plasma mass spectrometry are utilized in the method for producing the resist composition.
Further, for example, in the method of manufacturing a resist composition, the threshold value or allowable range for the number of defects in the resist composition is set in advance. The number of defects in the manufactured resist composition is measured by the resist composition inspection method described above. The measured number of defects in the resist composition is compared with the threshold value or the allowable range, and the resist composition having the number of defects below the threshold value or within the allowable range is accepted. On the other hand, if the number of defects exceeds the threshold value or is out of the allowable range, the resist composition is rejected. The allowable range for the number of defects in the resist composition is, for example, 0.07/cm ² or less. The allowable range for the number of defects in the resist composition is preferably 0.0001 to 10/cm ² , more preferably 0.0005 to 5/cm ² , and even more preferably 0.001 to 1/cm ² . .

[Method for managing resist composition]
FIG. 5 is a flow chart showing an example of a resist composition management method according to an embodiment of the present invention. The resist composition management method differs from the above-described chemical management method in that the inspection target is the resist composition, and has the same steps as the chemical management method.
Compared to the resist composition inspection method, the resist composition management method shown in FIG. 2. Except for having a step 6Y (step S42) of determining whether the number of defects obtained in 1. is within the allowable range, the steps are the same as those of the resist composition inspection method.
The process of preparing the resist composition (step 1Y, step S30) is practically the same as the resist composition, although there is a difference in whether it is an object of inspection or an object of management. Therefore, step 6Y (step S42) of determining whether or not the number of defects is within the allowable range will be described.

In the resist composition management method, a threshold or allowable range for the number of defects in the resist composition is set in advance. The threshold for the number of defects in the resist composition is set, for example, based on the number of defects in the resist composition of the previous production lot of the resist composition of interest, but is not limited thereto. It may be a value, a set value, or an average value of a plurality of production lots. The allowable range for the number of defects in the resist composition is, for example, 0.07/cm ² or less. The allowable range for the number of defects in the resist composition is preferably 0.0001 to 10/cm ² , more preferably 0.0005 to 5/cm ² , and even more preferably 0.001 to 1/cm ² . .
In step S42 (step 6Y), the number of defects containing the metal element obtained in step S40 described above is compared with the threshold or allowable range of the number of defects in the resist composition. For example, if the measured number of defects in the resist composition is equal to or less than the threshold value or within the allowable range, the resist composition is accepted as an acceptable product (step S43). On the other hand, if the number of defects in the resist composition exceeds the threshold or is out of the acceptable range, the resist composition is rejected (step S44). Thus, the quality of the resist composition can be controlled by the number of defects in the resist composition.

[Second Example of Method for Manufacturing Semiconductor Device]
FIG. 6 is a flow chart showing a second example of the semiconductor device manufacturing method according to the embodiment of the present invention. In the second example of the semiconductor device manufacturing method, the detailed description of the same steps as the resist composition inspection method will be omitted. A second example of the semiconductor device manufacturing method is a manufacturing method using a resist composition in place of the chemical solution in comparison with the first example of the semiconductor device manufacturing method.
The second example of the method for manufacturing a semiconductor device shown in FIG. Step 6Y (step S42) for determining whether the number of defects obtained in step 5Y (step S40) is within the allowable range, and using the resist composition determined to be within the allowable range in step 6Y, the semiconductor device It has the same steps as the inspection method of the resist composition except that it includes a step 7Y (step S46) of manufacturing.
The step of preparing the resist composition (step 1Y, step S30) is practically the same as the resist composition, although there is a difference in whether it is to be inspected or used in the manufacture of semiconductor devices. Therefore, step 6Y (step S42) of determining whether or not the number of defects is within the allowable range will be described.

In the method of manufacturing a semiconductor device, a threshold value or allowable range for the number of defects in the resist composition is set in advance. The threshold value or acceptable range of the number of defects in the resist composition is set based on, for example, the number of defects in the resist composition of the previous production lot of the target resist composition, but is not limited thereto. Instead, it may be a target value, a set value, or an average value of a plurality of production lots. The allowable range for the number of defects in the resist composition is, for example, 0.07/cm ² or less. The allowable range for the number of defects in the resist composition is preferably 0.0001 to 10/cm ² , more preferably 0.0005 to 5/cm ² , and even more preferably 0.001 to 1/cm ² . .
In step S42, the number of defects containing the metal element obtained in step S40 described above is compared with the threshold value or allowable range of the number of defects in the resist composition. For example, if the measured number of defects in the resist composition is below the threshold value or within the allowable range, it is used in the semiconductor device manufacturing method (step S46).
In step 6Y (step S42), it is determined that the measured number of defects in the resist composition exceeds the threshold value, that is, the resist composition determined that the measured number of defects in the resist composition is outside the allowable range. is not used for manufacturing semiconductor devices (step S48). Thus, in the semiconductor device manufacturing method, the selected resist composition is used in the lithography process of the semiconductor device to manufacture the semiconductor device.

[Method for confirming contamination state of semiconductor manufacturing equipment]
In semiconductor manufacturing equipment as well, contamination conditions affect the performance, quality, etc. of manufactured products, so it is desired to control minute foreign matter. In order to manage minute foreign matter in semiconductor manufacturing equipment, there is a demand for measurement and elemental analysis of minute foreign matter that causes defective products in semiconductor devices that are particularly miniaturized and highly integrated. A method for confirming the state of contamination of semiconductor manufacturing equipment will be described below.
FIG. 7 is a flow chart showing an example of the method for checking the contamination state of the semiconductor manufacturing equipment according to the embodiment of the present invention. In the method for confirming the state of contamination of semiconductor manufacturing equipment shown in FIG. 7, first, a chemical solution is prepared (step 1Z, step S50). The chemical solution is used for cleaning semiconductor manufacturing equipment, and is not particularly limited. (nBA), cyclohexanone (CHN), ethyl lactate (EL), methyl ethyl ketone (MEK), gamma-butyrolactone (GBL), 2-heptanone, or a mixture thereof at any ratio.

Next, the semiconductor manufacturing equipment is cleaned using a chemical solution (step 2Z, step S52). Collect the chemical solution after washing.
The method for cleaning the semiconductor manufacturing equipment is not particularly limited, but examples thereof include a method of passing a chemical solution through a pipe of the semiconductor device and a method of injecting the chemical solution into a container such as a chamber.
The chemical solution after cleaning in step 2Z (step S52) is applied onto the semiconductor substrate (step 3Z, step S54).
Although the application of the chemical solution to the semiconductor substrate after cleaning is not particularly limited, for example, a coater/developer is used.
Also, the semiconductor substrate is not particularly limited, but for example, a silicon substrate is used. In addition, the size of the semiconductor substrate is not particularly limited, but the specifications of the coating device that applies the chemical solution after cleaning to the semiconductor substrate, the specifications of the device that performs inductively coupled plasma mass spectrometry, etc. is appropriately determined according to the amount of the chemical solution.

Next, the presence or absence of defects on the surface of the semiconductor substrate is measured to obtain information on the positions of the defects on the surface of the semiconductor substrate (step S56). Based on the positional information, defects on the surface of the semiconductor substrate are irradiated with laser light, and an analysis sample obtained by irradiation is collected with a carrier gas and subjected to inductively coupled plasma mass spectrometry (step 4Z, step S58). Elements of minute defects are identified by inductively coupled plasma mass spectrometry in step S58. Also, the size of minute defects is specified. This makes it possible to check the contamination state of the semiconductor manufacturing equipment.

A series of steps (step 4Z, steps S56 and S58) of performing the above-described inductively coupled plasma mass spectrometry after applying the chemical solution after cleaning to the semiconductor substrate will be described later in detail.
The method for checking the contamination state of semiconductor manufacturing equipment preferably includes a step of measuring the presence or absence of defects on the surface of the semiconductor substrate to be used before applying the chemical solution after cleaning to the semiconductor substrate. In this case, the position information and size of the defect are measured. Thereby, the measured defects can be distinguished into those originating from the semiconductor substrate and those originating from the chemical solution after cleaning.

Next, there is a step 5Z (step S60) of determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in step 4Z (step S58).
Defective elements are identified by inductively coupled plasma mass spectrometry (step 4Z, step S58). At step S58, an attempt is made to select a metal element from the mass spectrometry data containing information on the identified defect element. If no metal element is singled out from the mass spectrometry data, it is determined that there is no metal element. On the other hand, if the metal element is selected from the mass spectrometry data, it is determined that the metal element is present.
If it is determined in step S60 (step 5Z) that there is no metal element, the semiconductor manufacturing equipment is less contaminated and can be used (step S66).
On the other hand, if it is determined that the metal element is present, it is determined that the semiconductor manufacturing equipment is badly contaminated and unused (step S68). As a result, the number of defects containing metal elements can be used to determine the contamination status of the semiconductor manufacturing equipment. As described above, in the method for checking the contamination state of semiconductor manufacturing equipment, it is possible to manage minute foreign substances in the semiconductor manufacturing equipment even when the amount of minute foreign substances contained in the chemical solution after cleaning is very small.
If it is determined that there is a metal element, the number of defects containing the metal element can also be measured (step 6Z, step S62). For example, the number of defects containing a metal element is measured by counting the number of defects containing a metal element.

Based on the mass spectrometry data in the defects obtained in step 4Z (step S58) without performing step 5Z (step S60) for determining the presence or absence of the metal element, the number of defects containing a metal element in the defect may be measured (step 6Z, step S62). In this case, in step S62, a metal element is selected from the mass spectrometry data containing information on the identified defect element, and the number of defects containing the metal element is counted by counting the number of selected metal elements. to measure. This also makes it possible to determine the contamination status of the semiconductor manufacturing equipment using the number of defects containing a metal element.

In the method for checking the contamination state of semiconductor manufacturing equipment, for example, a threshold value or an allowable range for the number of defects in chemical solutions after cleaning is set in advance. The threshold value or allowable range of the number of chemical defects after cleaning is appropriately determined according to the required cleanliness of the semiconductor manufacturing apparatus, and a target number of chemical liquid defects or the like is used. The allowable range for the number of defects in the chemical solution is, for example, 0.07/cm ² or less. The allowable range for the number of defects in the chemical solution is preferably 0.0001 to 10/cm ² , more preferably 0.0002 to 1/cm ² , and even more preferably 0.0005 to 0.5/cm ² . .
A step S64 compares the number of defects containing the metal element obtained in the above-described step S62 with the threshold or allowable range of the number of defects in the chemical solution after cleaning. For example, if the measured number of chemical defects after cleaning is equal to or less than the threshold value or within the allowable range, the semiconductor manufacturing equipment is low in contamination and can be used (step S66).
If it is determined in step S64 that the number of defects in the chemical solution exceeds the threshold value, that is, if it is determined that the number of defects in the chemical solution is out of the allowable range, the semiconductor manufacturing equipment is badly contaminated. is not used (step S68).

When it is determined not to use the semiconductor manufacturing equipment as described above, the semiconductor manufacturing equipment is cleaned again, and the chemical liquid after cleaning is used until it is determined that the semiconductor manufacturing equipment is to be used (step S66). The manufacturing equipment may be washed repeatedly.
The method for checking the contamination state of semiconductor manufacturing equipment preferably includes a step of measuring the presence or absence of defects in the chemical solution before cleaning the semiconductor manufacturing equipment. In this case, the position information and size of the defect are measured. As a result, defects in the chemical solution after cleaning can be distinguished from those before cleaning.

In the above description, the comparison and determination are performed by, for example, inputting various numerical values into a computer, comparing them with thresholds, etc., and making determinations based on the thresholds. Such comparisons and determinations are, for example, performed by a computer.
Further, selecting a metal element from the mass spectrometry data containing the information of the element of the identified defect means that the metal element stored in advance is compared with the information of the element of the mass spectrometry data stored in the computer. It is to identify those that match, and select those that are identified as metal elements from the mass spectrometry data.

A specific example of the analyzer will be described below.
[First example of analyzer]
FIG. 8 is a schematic diagram showing a first example of the analyzer of the embodiment of the present invention, and FIG. 9 is a schematic diagram showing an example of an analysis unit of the first example of the analyzer of the embodiment of the present invention. .
The analysis apparatus 10 shown in FIG. 8 has a surface defect measurement section 20 and an analysis section 30, which will be described later in detail. The analysis apparatus 10 measures the presence or absence of defects on the surface of the semiconductor substrate and analyzes the defects on the surface of the semiconductor substrate, using the semiconductor substrate 50 as a measurement target.
It should be noted that the above-described chemical solution or resist composition is applied onto the semiconductor substrate 50 when inspecting the above-described chemical solution or resist composition. After applying the chemical solution to the semiconductor substrate, the solvent contained in the chemical solution may be volatilized or evaporated so that the solvent contained in the chemical solution does not remain on the semiconductor substrate. After coating, the resist composition forms a film and is in the state of a coating film on the semiconductor substrate.

The analyzer 10 has a first transfer chamber 12a, a measurement chamber 12b, a second transfer chamber 12c, and an analysis chamber 12d. They are arranged consecutively in order. The first transfer chamber 12a, the measurement chamber 12b, the second transfer chamber 12c, and the analysis chamber 12d are each partitioned by a wall 12h. ) are provided, and the door may be opened when the semiconductor substrate 50 is passed through.

In the analyzer 10, the semiconductor substrate 50 is transported from the outside of the analyzer 10 to the first transport chamber 12a, transported from the first transport chamber 12a to the measurement chamber 12b, and the surface of the semiconductor substrate 50 is measured in the measurement chamber 12b. Defects are measured. Next, the semiconductor substrate 50 whose surface defects have been measured is transferred from the measurement chamber 12b to the second transfer chamber 12c and then to the analysis chamber 12d. Surface defects of the semiconductor substrate 50 are analyzed based on the results of measurement of the presence or absence of defects on the surface 50a of .
In the analyzer 10, the insides of the first transfer chamber 12a, the measurement chamber 12b, the second transfer chamber 12c, and the analysis chamber 12d can be made to have a specific atmosphere in order to prevent the semiconductor substrate 50 from being exposed to the outside air. . For example, a vacuum pump may be provided to evacuate the gas inside the first transfer chamber 12a, the measurement chamber 12b, the second transfer chamber 12c, and the analysis chamber 12d to create a reduced pressure atmosphere. Alternatively, an inert gas such as nitrogen gas may be supplied to the insides of the first transfer chamber 12a, the measurement chamber 12b, the second transfer chamber 12c, and the analysis chamber 12d to create an inert gas atmosphere.

As described above, the first transfer chamber 12a transfers the semiconductor substrate 50 transferred from the outside of the analysis device 10 to the measurement chamber 12b. An introduction portion 12g is provided on the side surface of the first transfer chamber 12a. A storage container 13 is installed in the introduction portion 12g. A seal member (not shown) is provided in the introduction portion 12g to keep the storage container 13 airtight.
The storage container 13 , for example, contains a plurality of semiconductor substrates 50 arranged in a shelf shape. The semiconductor substrate 50 is, for example, a disk-shaped substrate.
The storage container 13 is, for example, a FOUP (Front Opening Unified Pod). By using the storage container 13, the semiconductor substrate 50 can be transported to the analyzer 10 in a sealed state without being exposed to the outside air. As a result, contamination of the semiconductor substrate 50 can be suppressed.

A transport device 14 is provided inside the first transport chamber 12a. The transfer device 14 transfers the semiconductor substrate 50 in the storage container 13 from the first transfer chamber 12a to the adjacent measurement chamber 12b.
The transfer device 14 is not particularly limited as long as it can take out the semiconductor substrate 50 from the storage container 13 and transfer it to the stage 22 in the measurement chamber 12b.
The transfer device 14 shown in FIG. 8 has a transfer arm 15 that clamps the outside of the semiconductor substrate 50 and a drive unit (not shown) that drives the transfer arm 15 . The transfer arm 15 is attached to the attachment portion 14a and is rotatable around the rotation axis _C1 . The configuration of the transfer arm 15 is not particularly limited to one that clamps the outside of the semiconductor substrate 50 as long as the transfer arm 15 can hold and transfer the semiconductor substrate 50 . Any material used for transportation can be used as appropriate.
In the transport device 14, the mounting portion 14a can move in the height direction V, and the transport arm 15 can move in the height direction V parallel to the rotation axis _C1 . By moving the mounting portion 14a in the height direction V, the position of the transfer arm 15 in the height direction V can be changed.

(Surface defect measuring unit)
Surface defects of the semiconductor substrate 50 are measured in the measurement chamber 12b as described above. A surface defect measuring section 20 is provided inside the measuring chamber 12b.
The surface defect measurement unit 20 measures the presence or absence of defects on the surface 50a of the semiconductor substrate 50 and obtains positional 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 on which the semiconductor substrate 50 is placed, an incidence unit 23 that causes the incident light Ls to be incident on the surface 50a of the semiconductor substrate 50, and the incident light Ls that is focused on the surface 50a of the semiconductor substrate 50. and a condensing lens 24 that
The stage 22 on which the semiconductor substrate 50 is mounted is rotatable around the rotation axis _C2 , can change the position of the semiconductor substrate 50 in the height direction V, and can move in the direction H perpendicular to the height direction V. Can change position.
The stage 22 can change the irradiation position of the incident light Ls on the surface 50 a of the semiconductor substrate 50 . As a result, defects such as foreign matter on the surface 50a of the semiconductor substrate 50 can be detected by sequentially irradiating the incident light Ls onto a specific region or the entire surface of the surface 50a of the semiconductor substrate 50 .
Here, the foreign matter on the surface 50a of the semiconductor substrate 50 is derived from the chemical solution or resist composition described above.

The wavelength of the incident light Ls irradiated by the incident part 23 is not particularly limited. The incident light Ls is, for example, ultraviolet light, but may be visible light or other light. Here, the term "ultraviolet light" refers to light in the wavelength range of less than 400 nm, and the term "visible light" refers to light in the wavelength range of 400 to 800 nm.
The incident angle of the incident light Ls is 0° in all directions horizontal to the surface 50a of the semiconductor substrate 50 and 90° in the direction perpendicular to the surface 50a of the semiconductor substrate 50 . At this time, if the incident angle of the incident light Ls is specified from a minimum of 0° to a maximum of 90°, the incident angle of the incident light Ls is 0° or more and 90° or less, preferably more than 0° and less than 90°.

The surface defect measurement unit 20 has a light receiving unit that receives radiation light emitted when the incident light Ls is reflected or scattered by the surface 50 a of the semiconductor substrate 50 . The surface defect measuring unit 20 shown in FIG. 8 has two light receiving units 25 and 26, for example. If radiation light is received by either of the light receiving portions 25 and 26, it is determined that there is a defect on the surface 50a of the semiconductor substrate 50. If radiation light is not generated, it is determined that there is no defect on the surface 50a of the semiconductor substrate 50. be done. Thus, the presence or absence of defects on the surface 50a of the semiconductor substrate 50 is measured.
The light receiving section 25 is arranged around the semiconductor substrate 50 . The light receiving section 26 is arranged above the surface 50 a of the semiconductor substrate 50 . A condenser lens 27 is provided between the surface 50 a of the semiconductor substrate 50 and the light receiving section 26 . Radiation light generated by the incident light Ls is condensed on the light receiving section 26 by the condensing lens 27 . The condensing lens 27 can efficiently condense the emitted light onto the light receiving section 26 . Note that the number of light receiving units is not particularly limited to two. The surface defect measuring section 20 may be configured with either one of the light receiving section 25 and the light receiving section 26, or may be configured with three or more light receiving sections.
The light receiving section 25 receives the emitted light on the low angle side. Light reception on the low angle side means light reception in the range of 0° or more and 80° or less in the incident angle described above.
The light receiving section 26 receives the emitted light on the high angle side. Light reception on the high angle side means light reception in the range of more than 80° and less than or equal to 90° in the incident angle described above.
The light receiving unit 25 and the light receiving unit 26 are composed of, for example, optical sensors such as photomultiplier tubes.
Both the light receiving section 25 and the light receiving section 26 can receive non-polarized light or polarized light.

The surface defect measurement section 20 has a calculation section 28 and a storage section 29 .
The calculation unit 28 calculates the position information of the detected defect and the size of the defect based on the information of the radiation light received by the light receiving units 25 and 26 . The defect position information is information on the position coordinates of the defect on the surface 50 a of the semiconductor substrate 50 . For example, a reference position common to a plurality of semiconductor substrates 50 is set in advance, and the position coordinates are set as the origin of the reference position.

The light receiving portions 25 and 26 receive radiation light emitted when the incident light Ls emitted by the incident portion 23 is reflected or scattered by defects on the surface 50 a of the semiconductor substrate 50 . The light receiving units 25 and 26 detect the emitted light as bright spots. In the calculation unit 28, the size of the defect that caused the bright spot, that is, the detection size, is calculated based on the size of the standard particle from the size of the bright spot including the information on the light emitted from the defect in the light receiving units 25 and 26. FIG. Calculation of the detection size based on the size of the standard particles is performed by a calculation device provided in a commercially available surface inspection device or by a known calculation method. The calculation unit 28 acquires the position information of the irradiation position of the incident light Ls from the control unit 42, and detects the defect on the surface 50a of the semiconductor substrate 50 based on the information of the light emitted by the defect at the light receiving units 25 and 26, for example. Obtain location information and defect size information. The obtained defect position information and defect size information on the surface 50 a of the semiconductor substrate 50 are stored in the storage unit 29 .
The storage unit 29 is not particularly limited as long as it can store position information and size information of defects such as foreign matter on the surface 50a of the semiconductor substrate 50. For example, a volatile memory, a nonvolatile memory, a hard disk , or SSD (Solid State Drive).

Here, in the surface defect measuring section 20 , the stage 22 and the incident section 23 are controlled by the control section 42 . The calculation unit 28 is also controlled by the control unit 42 .
The control unit 42 acquires positional information on the surface 50 a of the semiconductor substrate 50 of the incident light Ls irradiated by the incident unit 23 . The control unit 42 drives the stage 22 to irradiate a region of the surface 50a of the semiconductor substrate 50 that is not irradiated with the incident light Ls with the incident light Ls, thereby changing the irradiation position of the surface 50a of the semiconductor substrate 50.
The surface defect measurement unit 20 irradiates the entire region of the surface 50a of the semiconductor substrate 50 with the incident light Ls, and, for example, based on the information of the radiation light received by the two light receiving units 25 and 26, at each irradiation position. , to obtain defect position information and defect size information on the surface 50 a of the semiconductor substrate 50 . This makes it possible to obtain defect position information and defect size information on the entire surface 50 a of the semiconductor substrate 50 . That is, two-dimensional defect position information and defect size information on the surface 50a of the semiconductor substrate 50 are obtained.
The atmosphere in the measurement chamber 12b during measurement by the surface defect measurement unit 20 is not particularly limited, and may be a reduced pressure atmosphere or a nitrogen gas atmosphere as described above.
As the surface defect measuring unit 20, for example, a surface inspection device (SurfScan SP5; manufactured by KLA Corporation) can be used.

A transfer device 16 is provided inside the second transfer chamber 12c. The transport device 16 transports the semiconductor substrate 50 whose surface defects have been measured by the surface defect measuring section 20 in the measurement chamber 12b from the measurement chamber 12b to the analysis chamber 12d.
The conveying device 16 may have the same configuration as the conveying device 14 described above. The transport device 16 has a transport arm 15 that clamps the outside of the semiconductor substrate 50 and a drive unit (not shown) that drives the transport arm 15 . The transfer arm 15 is attached to the attachment portion 16a and is rotatable around the rotation axis _C1 .
The conveying device 16 can move the mounting portion 16a in the height direction V, and can move in the height direction V parallel to the rotation axis _C1 . The transfer arm 15 can change its position in the height direction V by moving the attachment portion 16 a to which the transfer arm 15 is attached in the height direction V. As shown in FIG.

(Analysis Department)
An analysis section 30 is provided inside the analysis chamber 12d. The analysis unit 30 performs analysis using LA-ICP-MS (Laser Ablation-Inductively Coupled Plasma Mass Spectrometer).
ICP-MS (Inductively Coupled Plasma Mass Spectrometer) ionizes elements in a liquid sample using plasma of argon gas at about 10000° C. generated by inductively coupling to perform mass spectrometry. LA-ICP-MS irradiates a defect 51 on the surface 50a of a semiconductor substrate 50 with a laser beam in a laser ablation section (LA section), and an analysis sample obtained by irradiation is subjected to an ICP-MS section (inductively coupled plasma (mass spectrometer) to perform quantitative analysis of the elements contained in the analysis sample.

The analysis unit 30 has a stage 32 on which the semiconductor substrate 50 is placed, and a container portion 33 that houses the semiconductor substrate 50 placed on the stage 32 .
An analysis unit 36 is connected to the container part 33 via a pipe 39 . The semiconductor substrate 50 is analyzed in a state in which the whole is accommodated in the container portion 33 . The stage 32 on which the semiconductor substrate 50 is placed is rotatable around the rotation axis _C3 , can change the position of the semiconductor substrate 50 in the height direction V, and can move in the direction H perpendicular to the height direction V. Can change position.
The stage 32 is controlled by the controller 42 . The control unit 42 drives the stage 32 to change the irradiation position on the surface 50a of the semiconductor substrate 50 in order to irradiate the defect 51 on the surface 50a of the semiconductor substrate 50 with the laser beam La.
Here, if nothing is applied or formed on the surface 50a of the semiconductor substrate 50, the defect 51 of the surface 50a of the semiconductor substrate 50 is the defect 51 of the semiconductor substrate 50 itself and the defect 51 derived from the semiconductor substrate 50. . However, as described above, when the chemical solution or the resist composition is applied to the semiconductor substrate 50 during the inspection of the chemical solution or the resist composition, the defects 51 are derived from the chemical solution or the resist composition.

The analysis unit 30 has a light source unit 34 that irradiates the defects 51 on the surface 50 a of the semiconductor substrate 50 measured by the surface defect measurement unit 20 with laser light La. Between the light source unit 34 and the surface 50 a of the semiconductor substrate 50 , a condenser lens 35 is provided for condensing the laser light La onto the defect 51 on the surface 50 a of the semiconductor substrate 50 .
The light source section 34 and the condenser lens 35 are provided outside the container section 33 . The container portion 33 is provided with a window portion (not shown) through which the laser beam La can pass so that the laser beam La can be transmitted through the container portion 33 .
A femtosecond laser, a nanosecond laser, a picosecond laser, an attosecond laser, or the like is used for the light source unit 34 . As a femtosecond laser, for example, a Ti:Sapphire laser can be used.

The analysis unit 30 has a carrier gas supply unit 38 that supplies carrier gas into the container unit 33 .
The carrier gas supply unit 38 includes a gas supply source (not shown) such as a cylinder in which carrier gas is stored, a regulator (pressure regulator) connected to the gas supply source, and an adjustment for controlling the supply amount of the carrier gas. valve (not shown). For example, the regulator and the regulating valve are connected by a tube, and the regulating valve and the container portion 33 are connected by a pipe. Carrier gas is, for example, helium gas or argon gas.
The analysis unit 30 also has a cleaning gas supply unit 40 that supplies cleaning gas into the container unit 33 . The cleaning gas supply unit 40 includes a gas supply source (not shown) such as a cylinder in which the cleaning gas is stored, a regulator (pressure regulator) connected to the gas supply source, and an adjustment for controlling the supply amount of the cleaning gas. valve (not shown). For example, the regulator and the regulating valve are connected by a tube, and the regulating valve and the container portion 33 are connected by a pipe. Helium gas or argon gas, for example, is used as the cleaning gas.

Further, the container portion 33 is provided with an outflow portion 41 for discharging the cleaning gas from the inside of the container portion 33 to the outside. The outflow part 41 is composed of, for example, a pipe and a valve. By opening the valve, the cleaning gas can flow out of the container portion 33 to the outside.
A heater (not shown) may be provided in the container part 33 to perform the flushing process. By heating the interior of the container 33 with the heater while the cleaning gas is being supplied into the container 33 , foreign matter such as ablated deposits or adsorbed gas is removed from the container 33 . As a result, the degree of cleanliness in the container portion 33 can be increased, and contamination of the semiconductor substrate 50 can be suppressed. For example, an infrared lamp or a xenon flash lamp is used as the heater.
In addition to the cleaning gas, a carrier gas can also be used for the flushing process.

<Analysis unit>
The analysis unit 36 uses the above-described ICP-MS, irradiates the defect 51 on the surface 50a of the semiconductor substrate 50 with the laser beam La, and collects and guides the analysis sample obtained by irradiation with a carrier gas. Coupled plasma mass spectrometry. Note that ICP is an abbreviation for inductively coupled plasma, and in the analysis unit 36, the object to be measured is ionized by high-temperature plasma maintained by high-frequency electromagnetic induction, and the ions are detected by a mass spectrometer to determine atomic species. , and the concentration of the detected atomic species.
For example, as shown in FIG. 9 , the analysis unit 36 includes a plasma torch 44 that generates plasma that ionizes the analysis sample introduced from the pipe 39 together with a carrier gas, and ion beams positioned near the tip of the plasma torch 44 . and a mass spectrometer 46 having an inlet.

The plasma torch 44 has, for example, a triple-pipe structure, and carrier gas is introduced from a pipe 39 . A plasma gas for forming plasma is introduced into the plasma torch 44 . Argon gas, for example, is used as the plasma gas.
The plasma torch 44 is provided with a high frequency coil (not shown) connected to a high frequency power supply (not shown). A plasma is formed inside the plasma torch 44 by applying a high frequency current of .

In the mass analysis section 46, ions generated by the plasma torch 44 are introduced into the ion lens section 46a and the mass spectrometer section 46b via the ion introduction section. The ion lens section 46a and the mass spectrometer section 46b are evacuated by a vacuum pump (not shown) so that the ion lens section 46a on the side of the plasma torch 44 becomes a low vacuum and the mass spectrometer section 46b becomes a high vacuum. is depressurized to

The ion lens portion 46a is provided with a plurality of ion lenses 47, for example, three. The ion lens 47 separates the ions into the mass spectrometer section 46b.
In the ion lens section 46a of the mass spectrometry section 46, the ion lens 47 separates the plasma light and the ions described above and allows only the ions to pass through.

The mass spectrometer unit 46b separates ions for each mass-to-charge ratio of the ions and detects them with the detector 49. FIG. The mass spectrometer section 46b has a reflectron 48 that reflects ions passing through the ion lens section 46a to a detector 49, and a detector 49 that detects ions. The reflectron 48 is also called an ion mirror, and is a device that uses an electrostatic field to reverse the flight direction of charged particles. By using the reflectron 48, charged particles having the same mass-to-charge ratio but different kinetic energies can be converged on the time axis and made to reach the detector 49 at approximately the same time. Reflectron 48 can compensate for errors and improve mass resolution. As the reflectron 48, a known one used for time-of-flight mass spectrometer (TOF-MS) can be used.

The detector 49 is not particularly limited as long as it can detect ions and identify elements, and a known detector used for a time-of-flight mass spectrometer (TOF-MS) can be used.
The analysis unit 36 allows, for example, the signals of the detected elemental ions (not shown) to be displayed as a chart over time (not shown). The concentration of the detected element corresponds with the signal intensity.

As shown in FIG. 8 , the analysis apparatus 10 has a control unit 42 . The control unit 42 causes the detected foreign matter on the surface 50 a of the semiconductor substrate 50 to be stored in the storage unit 29 of the surface defect measurement unit 20 . Based on the positional information and size information of the defect such as Irradiate. Thereby, the defects 51 on the surface 50a of the semiconductor substrate 50 are analyzed.
In addition, the analyzer 10 is configured so that inductively coupled plasma mass spectrometry can be performed by the analyzer 30 while the entire semiconductor substrate 50 is housed in the container 33, so that contamination of the surface 50a of the semiconductor substrate 50 can be suppressed. .

In the analyzer 10, the carrier gas and the cleaning gas are supplied through separate systems, but the present invention is not limited to this. 33. For example, the configuration may be such that only the carrier gas supply section 38 is provided without providing the cleaning gas supply section 40 .
Further, the carrier gas preferably has a water content of 0.00001 ppm by volume or more and 0.1 ppm by volume or less.

If the water content of the carrier gas is 0.00001 volume ppm or more and 0.1 volume ppm or less, contamination of the surface 50a of the semiconductor substrate 50 during analysis within the container part 33 can be reduced. For example, when the carrier gas contains a large amount of water, impurities are eluted into a small amount of water adhering to the surface of the carrier gas pipe or the inner surface of the container part 33, and these impurities redeposit on the semiconductor substrate 50, resulting in defects. Although the number may increase, if the water content of the carrier gas is within the above range, these are suppressed.
In addition, when the moisture content is small, the surface 50a of the semiconductor substrate 50 is likely to be charged when the carrier gas passes through the vicinity of the semiconductor substrate 50 . As a result, charged particles floating in the container 33 are easily attracted to the surface 50a of the semiconductor substrate 50, and particles floating nearby during transportation by the transportation system are easily attracted to the surface 50a of the semiconductor substrate 50. In addition, re-adhesion of products produced as a result of laser ablation is likely to occur, but if the water content of the carrier gas is within the above range, this is suppressed.
The amount of water contained in the carrier gas can be measured using an atmospheric pressure ionization mass spectrometer (API-MS) (eg, manufactured by Japan API Co., Ltd.).
A method for preparing the water content is not particularly limited, but it is realized by performing a gas refining step in which water (water vapor) contained in the raw material gas is removed to prepare the water content. In particular, the amount of water contained in the carrier gas can be adjusted by adjusting the number of times of purification or the filter.
The flow rate of the carrier gas is preferably 1.69×10 ⁻³ to 1.69 Pa·m ³ /sec (1 to 1000 sccm (standard cubic centimeter per minute)).

[First example of analysis method]
The analysis method includes a step of measuring the presence or absence of defects on the surface of the semiconductor substrate, obtaining positional information on the semiconductor substrate of the defects on the surface of the semiconductor substrate, and based on the positional information of the defects on the semiconductor substrate, the semiconductor substrate and a step of irradiating a laser beam to defects on the surface of the substrate, recovering an analysis sample obtained by the irradiation with a carrier gas, and subjecting the sample to inductively coupled plasma mass spectrometry. The analysis method will be specifically explained.
FIG. 10 is a schematic diagram illustrating the first example of the analysis method according to the embodiment of the present invention, and FIG. 11 is a schematic cross-sectional view illustrating the first example of the analysis method according to the embodiment of the present invention.
10 and 11, the same components as those of the analysis apparatus 10 shown in FIG. 8 are denoted by the same reference numerals, and detailed description thereof will be omitted.

In the analysis method, for example, the storage container 13 storing a plurality of semiconductor substrates 50 is connected to the introduction portion 12g on the side surface of the first transfer chamber 12a of the analysis apparatus 10 shown in FIG. The lid of the storage container 13 is opened to allow the semiconductor substrate 50 to be taken out from the storage container 13 .
Next, the semiconductor substrate 50 is taken out from the storage container 13 using the transfer device 14 in the first transfer chamber 12a, and transferred to the stage 22 in the measurement chamber 12b. Even if the semiconductor substrate 50 is transported from the outside of the analyzer 10, contamination of the semiconductor substrate 50 is suppressed by the process of transporting the semiconductor substrate 50 from the storage container 13 to the stage 22 of the measurement chamber 12b. Surface defects of the semiconductor substrate 50 can be measured by the surface defect measuring unit 20 while contamination of the semiconductor substrate 50 is suppressed.

Next, surface defects of the semiconductor substrate 50 are measured by the surface defect measurement unit 20 in the measurement chamber 12b. Thereby, the position information and size of defects such as foreign matter on the surface 50a of the semiconductor substrate 50 are detected. For example, defects 51 can be shown on surface 50a of semiconductor substrate 50 as shown in FIG. Showing the defects 51 on the surface 50a of the semiconductor substrate 50 is called mapping. Position information and size information of the defect 51 on the surface 50 a of the semiconductor substrate 50 are stored in the storage unit 29 . The position information and size information of the defect 51 on the surface 50a of the semiconductor substrate 50 are called mapping information.

Next, the semiconductor substrate 50 whose surface defects have been measured is transferred from the measurement chamber 12b to the analysis chamber 12d by the transfer device 16 of the second transfer chamber 12c shown in FIG.
Next, in the analysis chamber 12d, analysis is performed by the analysis unit 30 based on the position information and size information of the defect 51 on the surface 50a of the semiconductor substrate 50, ie, mapping information. As shown in FIG. 11, the analysis is performed with the entire semiconductor substrate 50 housed in the container portion 33 and the carrier gas supplied from the carrier gas supply portion 38 into the container portion 33 . During the analysis, the position of the defect 51 is identified based on the mapping information, and the semiconductor substrate 50 is moved to the irradiation position of the laser beam La using the stage 32, for example.
Next, as shown in FIG. 11, the defect 51 on the surface 50a of the semiconductor substrate 50 is irradiated with laser light La. An analysis sample 51a obtained by irradiating the defect 51 with the laser beam La is moved to the analysis unit 36 by carrier gas. An analysis sample 51a originating from the defect 51 and transferred by the carrier gas is subjected to inductively coupled plasma mass spectrometry in the analysis unit 36 to identify the element of the defect 51. FIG. Mass spectrometric data of the defect 51 is thereby obtained.

The analysis method preferably includes a step of cleaning the inside of the container part 33 using a cleaning gas before the step of analyzing. Specifically, in the cleaning process, before the semiconductor substrate 50 is transported into the container portion 33, a cleaning gas is supplied into the container portion 33, the inside of the container portion 33 is heated using a heater, and a flushing process is performed. It is a process to carry out. By the cleaning step, foreign matter such as ablated deposits, adsorbed gas, or the like in the container portion 33 is removed.

In addition, in the analysis apparatus 10, a device other than the analysis device 10, for example, a surface defect measurement device 70 (see FIG. 8), is used to measure the defects 51 on the surface 50a of the semiconductor substrate 50. Positional information of the defects 51 on the surface 50a of the substrate 50 can be used. The position information of the defect 51 on the surface 50a of the semiconductor substrate 50 is mapping information as shown in FIG. 10, for example. 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 having the defects 51 on the surface 50 a measured is stored in, for example, the storage container 13 and transported to the analysis device 10 . The semiconductor substrate 50 is transferred to the analysis chamber 12d through the first transfer chamber 12a, the measurement chamber 12b, and the second transfer chamber 12c.
Next, the control unit 42 reads the mapping information from the storage unit 29 and identifies the position of the defect 51 on the surface 50a of the semiconductor substrate 50 based on the mapping information. Next, the stage 32 is used to move the semiconductor substrate 50 to the position where the defect 51 is irradiated with the laser beam La. Next, the defect 51 on the surface 50a of the semiconductor substrate 50 is irradiated with laser light La. An analysis sample 51a obtained by irradiating the defect 51 with the laser beam La is moved to the analysis unit 36 by carrier gas. An analysis sample 51a originating from the defect 51 and transferred by the carrier gas is subjected to inductively coupled plasma mass spectrometry in the analysis unit 36 to identify the element of the defect 51. FIG. Mass spectrometric data of the defect 51 is thereby obtained.

As described above, when the defect 51 is analyzed using the mapping information as shown in FIG. measurement becomes unnecessary. Needless to say, the analyzer 10 may be configured without the surface defect measuring device 70 shown in FIG.
The positional 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 that measured by the surface defect measuring device 70 (see FIG. 8). The surface defect measuring device 70 may have, for example, a storage unit (not shown) that stores position information. Moreover, the surface defect measuring device 70 may have the same configuration as the surface defect measuring section 20 . For this reason, the surface defect measurement apparatus 70 includes, for example, an incident part 23 that makes the incident light Ls incident on the surface 50a of the semiconductor substrate 50, and a defect 51 on the surface 50a of the semiconductor substrate 50 that reflects or scatters the incident light Ls. and a light-receiving portion 26 for receiving radiation light emitted by the laser beam.

[Second example of analyzer]
FIG. 12 is a schematic diagram showing a second example of the analyzer according to the embodiment of the invention. 12, the same components as those of the analyzer 10 shown in FIG. 8 are denoted by the same reference numerals, and detailed description thereof will be omitted.
Compared to the analysis apparatus 10 shown in FIG. 8, the analysis apparatus 10a shown in FIG. The configuration is similar to that of the analysis device 10 shown in FIG. 8, except that it is provided in 12e.

In the analysis apparatus 10 a , surface defect measurement and analysis are performed with the entire semiconductor substrate 50 housed in the container portion 33 .
In the analysis unit 30 , the light source unit 34 is arranged with the optical axis of the laser beam La inclined with respect to the surface 50 a of the semiconductor substrate 50 .
By providing the surface defect measuring section 20 and the analyzing section 30 in one processing chamber 12e, the analyzing apparatus 10a can be made smaller than the analyzing apparatus 10 shown in FIG.
In addition, in a state in which the entire semiconductor substrate 50 is accommodated in the container portion 33, the surface defect measurement section 20 can measure surface defects and the analysis section 30 can perform inductively coupled plasma mass spectrometry. Transportation is reduced, and contamination of the surface 50a of the semiconductor substrate 50 can be further suppressed. As a result, the measurement accuracy of defects on the surface 50a of the semiconductor substrate 50 can be increased, and contamination in the processing chamber 12e of the analyzer 10a can be suppressed.

[Second example of analysis method]
A second example of the analysis method is basically the same as the first example of the analysis method described above. In the second example of the analysis method, surface defects are measured by the surface defect measurement unit 20 while the entire semiconductor substrate 50 is housed in the container 33, compared to the first example of the analysis method described above. and that the transfer device 16 does not transfer the semiconductor substrate 50 on which the surface defects have been measured from the measurement chamber 12b to the analysis chamber 12d after the measurement of the surface defects. Same as the first example.
In the second example of the analysis method, while the entire semiconductor substrate 50 is housed in the container portion 33, surface defects are measured by the surface defect measurement section 20 and inductively coupled plasma mass spectrometry is performed by the analysis section 30. , contamination of the surface 50a of the semiconductor substrate 50 can be further suppressed, and contamination in the processing chamber 12e of the analysis device 10a can be suppressed.
Further, as described above, in a state in which the entire semiconductor substrate 50 is accommodated in the container portion 33, the surface defect measurement section 20 measures the surface defects and the analysis section 30 performs the inductively coupled plasma mass spectrometry. This eliminates the need to transport the semiconductor substrate 50 between them, and the analysis time can be shortened compared to the first example of the analysis method. Furthermore, contamination of the surface 50a of the semiconductor substrate 50 can be further suppressed as described above.

Also, in the analysis apparatus 10a, similarly to the analysis apparatus 10, the defects 51 on the surface 50a of the semiconductor substrate 50 are measured by another apparatus different from the analysis apparatus 10a, for example, the surface defect measurement apparatus 70 (see FIG. 12). Mapping information obtained as shown in FIG. 10 can be used. 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 apparatus 70, the semiconductor substrate 50 whose surface 50a has been measured for defects 51 is stored in, for example, the storage container 13 and transported to the analysis apparatus 10a.
In the analysis apparatus 10a, based on the mapping information, the analysis unit 30 in the processing chamber 12e as described above performs inductively coupled plasma mass spectrometry on the analysis sample 51a derived from the defect 51 in the analysis unit 36d. Elements are identified. Mass spectrometric data of the defect 51 is thereby obtained.
Even in this case, if the mapping information measured by the surface defect measuring device 70 (see FIG. 12) is used, the surface defect measuring unit 20 and the measurement of the surface defects of the semiconductor substrate 50 become unnecessary. It goes without saying that the analyzing apparatus 10a may also be configured without the surface defect measuring apparatus 70 shown in FIG. Further, the positional 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 that measured by the surface defect measuring device 70 (see FIG. 12).

[Third example of analyzer]
As described above, when mapping information measured by a device other than the analysis device, for example, the surface defect measurement device 70, is used, the surface defect measurement unit is not necessarily required in the analysis device. A configuration without In this case, the analysis device is configured to have only the analysis section 30 .
FIG. 13 is a schematic diagram showing a third example of the analyzer according to the embodiment of the invention. In FIG. 13, the same components as those of the analysis apparatus 10 shown in FIG. 8 and the analysis apparatus 10a shown in FIG.
Compared with the analysis apparatus 10 shown in FIG. 8, the analysis apparatus 10b shown in FIG. It is a configuration without The analysis device 10b has the above-described surface defect measuring device 70 and a mass spectrometer 72, with the analysis unit 30 (see FIG. 8) serving as a mass spectrometer 72. FIG. Since the mass spectrometer 72 has the same configuration as the analysis unit 30 (see FIG. 8) described above, detailed description of the mass spectrometer 72 is omitted.

In the analyzer 10b, the surface defect measurement device 70 and the mass spectrometer 72 are separate devices, not integrated. 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 measurement device 70 , the semiconductor substrate 50 with the defects 51 on the surface 50 a measured is stored in, for example, the storage container 13 and transported to the mass spectrometer 72 . The semiconductor substrate 50 is transferred to the analysis chamber 12d through the first transfer chamber 12a.
Next, in the mass spectrometer 72, the control unit 42 reads the mapping information from the storage unit 29, and based on the mapping information, the analysis sample 51a derived from the defect 51 in the analysis chamber 12d as described above is transferred to the analysis unit 36d. Inductively coupled plasma mass spectrometry is performed to identify the element of defect 51 . Mass spectrometric data of the defect 51 is thereby obtained. Further, as the positional information of the defects 51 on the surface 50a of the semiconductor substrate 50 supplied to the storage unit 29, positional information other than that measured by the surface defect measuring device 70 (see FIG. 13) can be used.

The analysis unit 30 of the analysis device 10, analysis device 10a, and analysis device 10b described above is not limited to the configuration described above. Here, FIG. 14 is a schematic diagram showing a modification of the analysis section of the analysis device of the embodiment of the present invention. 14, the same components as those of the analyzer 10 shown in FIG. 8 are denoted by the same reference numerals, and detailed description thereof will be omitted.
In the analysis unit 30, 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 may be provided.
The imaging unit 60 can observe the irradiation position of the laser beam La on the surface 50 a of the semiconductor substrate 50 , that is, the position of the defect 51 . The imaging unit 60 includes a CCD (Charge Coupled Device) sensor and a CMOS (Complementary Metal Oxide Semiconductor) sensor. Examples of the display unit 62 include a liquid crystal monitor and an organic EL (Electro Luminescence) monitor.
The light source unit 34 and the imaging unit 60 are arranged, for example, with their optical axes (not shown) orthogonal to each other. The imaging unit 60 is arranged to face the surface 50 a of the semiconductor substrate 50 .
A half mirror 64 is arranged where the optical axis of the light source section 34 and the optical axis of the imaging section 60 intersect. A laser beam La emitted by the light source unit 34 is reflected by the half mirror 64 , passes through the condenser lens 35 , and is irradiated onto the surface 50 a of the semiconductor substrate 50 .

[Semiconductor substrate]
The semiconductor substrate is not particularly limited, and various semiconductor substrates such as a silicon (Si) substrate, a sapphire substrate, a SiC substrate, a GaP substrate, a GaAs substrate, an InP substrate, or a GaN substrate can be used. As a semiconductor substrate, a silicon semiconductor substrate is often used.

In addition, the following are illustrated as a semiconductor device.
[Semiconductor device]
The semiconductor device is not particularly limited, for example, logic LSI (Large Scale Integration) (e.g., ASIC (Application Specific Integrated Circuit), FPGA (Field Programmable Gate Array), ASSP (Application Specific Standard Product), etc.), Microprocessor (e.g., CPU (Central Processing Unit), GPU (Graphics Processing Unit), etc.), memory (e.g., DRAM (Dynamic Random Access Memory), HMC (Hybrid Memory Cube), MRAM (Magnetic RAM: magnetic memory) and PCM (Phase-Change Memory), ReRAM (Resistive RAM), FeRAM (Ferroelectric RAM), Flash memory (NAND (Not AND) flash), LED (Light Emitting) Diode) (e.g., microflash for mobile terminals, automotive, projector light source, LCD backlight, general lighting, etc.), power devices, analog IC (Integrated Circuit) (e.g., DC (Direct Current) - DC (Direct Current) converter, insulated gate bipolar transistor (IGBT), etc.), MEMS (Micro Electro Mechanical Systems) (e.g., acceleration sensor, pressure sensor, oscillator, gyro sensor, 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 elements, BSI (Back Side Illumination), CIS (Contact Image S sensor), camera modules, CMOS (Complementary Metal Oxide Semiconductor), passive devices, SAW (Surface Acoustic Wave) filters, RF (Radio Frequency) filters, RFIPD (Radio Frequency Integrated Passive Devices), BB (Broadband), and the like.

The present invention is basically configured as described above. As described above, the method for inspecting a chemical solution, the method for producing a chemical solution, the method for managing a chemical solution, the method for producing a semiconductor device, the method for inspecting a resist composition, the method for producing a resist composition, the method for managing a resist composition, and the semiconductor production of the present invention. Although the method for checking the contamination state of the apparatus has been described in detail, the present invention is not limited to the above-described embodiments, and various improvements and modifications may be made without departing from the scope of the present invention. .

[Chemical solution]
The chemical liquid contains an organic solvent as a main component.
In the present specification, the organic solvent is intended to be a liquid organic compound contained in a content exceeding 10000 ppm by mass per component with respect to the total mass of the chemical solution. In other words, in the present specification, the liquid organic compound contained in an amount exceeding 10000 ppm by mass with respect to the total mass of the chemical solution corresponds to the organic solvent.
In addition, the term “liquid” as used herein means liquid at 25° C. under atmospheric pressure.

The fact that the organic solvent is the main component in the chemical solution means that the content of the organic solvent in the chemical solution is 98.0% by mass or more with respect to the total mass of the chemical solution, and exceeds 99.0% by mass. is preferred, 99.90% by mass or more is more preferred, and more than 99.95% by mass is even more preferred. The upper limit is less than 100% by mass.
An organic solvent may be used individually by 1 type, or may use 2 or more types. When two or more organic solvents are used, the total content is preferably within the above range.

The type of organic solvent is not particularly limited, and known organic solvents can be used. Organic solvents include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound which may have a ring. (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, dialkyl sulfoxides, cyclic sulfones, dialkyl ethers, monohydric alcohols, glycols, alkyl acetates, and N-alkylpyrrolidones. .

Organic solvents include, for example, 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, diisoamyl ether, isoamyl acetate, dimethyl sulfoxide, N- At least one selected from the group consisting of methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, and 2-heptanone is preferred.
Examples of using two or more organic solvents include combined use of PGMEA and PGME and combined use of PGMEA and PC.
The type and content of the organic solvent in the chemical can be measured using a gas chromatograph-mass spectrometer.

The chemical solution may contain impurities in addition to the organic solvent.
Impurities include metal impurities.
By metal impurities, we mean metal ions and metal impurities contained in the chemical solution as solids (elemental metals, particulate metal-containing compounds, etc.).
The types of metal elements contained in the metal impurities are not particularly limited. ), Li (lithium), Al (aluminum), Cr (chromium), Ni (nickel), Ti (titanium), and Zn (zirconium).
The metal impurities may be components that are unavoidably contained in each component (raw material) contained in the chemical solution, or components that are unavoidably included during the manufacture, storage, and/or transfer of the chemical solution. may be added to

The chemical solution may contain water. The type of water is not particularly limited, and for example, distilled water, ion-exchanged water, and pure water can be used.
Water may be added to the chemical solution, or may be unavoidably mixed in the chemical solution during the manufacturing process of the chemical solution. Examples of cases where water is unavoidably mixed in the manufacturing process of the chemical solution include, for example, when water is included in the raw materials (e.g., organic solvent) used in manufacturing the chemical solution, and when water is mixed in the chemical solution manufacturing process (e.g., contamination ) and the like.

Although the content of water in the chemical solution is not particularly limited, it is generally preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and further less than 0.5% by mass, relative to the total mass of the chemical solution. preferable.
When the water content in the chemical solution is 1.0% by mass or less, the production yield of semiconductor chips is more excellent.
Although the lower limit is not particularly limited, it is often about 0.01% by mass. For production reasons, it is difficult to reduce the water content to below the above figures.

The method of preparing the above-mentioned chemical solution is not particularly limited, and examples thereof include a method of procuring an organic solvent by purchase or the like, and a method of reacting raw materials to obtain an organic solvent. As the chemical solution, it is preferable to prepare a chemical solution having a low impurity content (for example, a chemical solution having an organic solvent content of 99% by mass or more) as already described. Commercial products of such organic solvents include, for example, those called “high-purity grade products”.
In addition, you may perform a refinement|purification process with respect to a chemical|medical solution as needed.
Purification methods include, for example, distillation and filtration.

The chemical solution contains at least one metal 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 metal elements is preferably 10 mass ppb or less with respect to the total mass of the chemical solution.
When it exceeds 10 mass ppb, the surface inspection device (SurfScan SP5; manufactured by KLA Co., Ltd.) and the indices such as mass ppb by ICP-MS and the like cannot be correlated and the coefficient of determination becomes small.
The contents of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn in the chemical solution were measured using NexION350 (trade name, manufactured by PerkinElmer) by ICP-MS ( It can be measured using the inductively coupled plasma mass spectrometry method. Specific measurement conditions by the ICP-MS method are as follows. The detected amount is measured at the peak intensity for a standard solution of known concentration, converted to the mass of the metal component, and the content of the metal component (total metal content) in the treatment solution used for measurement is calculated.
The content of metal components was measured by a conventional ICP-MS method. Specifically, software for ICP-MS is used as software used for analysis of metal components.

The measurement of 0.01 mass ppq mentioned above will be explained.
First, 1 mL of chemical solution is applied as droplets on a silicon wafer having a diameter of approximately 300 mm (12 inches). After that, it is dried without rotation. After measuring the defect position of the silicon wafer with a surface inspection device (SurfScan SP7; manufactured by KLA Corporation), the coordinate file acquired by the surface inspection device (SurfScan SP7) is scanned with FIB-SEM (HELIOS G4-EXL manufactured by Thermo Fisher). A cross section near the defect site is cut out from the base.
FIB (Focused Ion Beam)-SEM (Scanning Electron Microscope) or TEM (Transmission Electron Microscope) acquires three-dimensional shape information and elemental information by EDX while performing cross-sectional etching. These are performed for all defects.
For example, if one spherical particle of Fe 13.5 nm (the limit of the surface inspection device (SurfScan SP7)) is found in 1 mL (density of 1 g/cm ³ ) of the chemical solution, in principle, approximately 0.01 mass ppq can be measured.

[Usage of chemical solution]
A chemical liquid containing an organic solvent as a main component is used, for example, in a method for manufacturing a semiconductor device and a method for cleaning a semiconductor manufacturing apparatus. Specifically, the chemical liquid is used, for example, as a developer, a rinse liquid, and a pre-wet liquid. In addition, the chemical solution is used as an edge rinse, a back rinse, a resist remover, and a thinner for dilution.
The pre-wet liquid is to be supplied onto the semiconductor substrate before forming the resist film, so that the resist liquid can be easily spread over the semiconductor substrate and a uniform resist film can be formed by supplying a smaller amount of the resist liquid. is used for
The above edge rinse is a rinse that is supplied to the peripheral portion of the semiconductor substrate and used to remove the resist film on the peripheral portion of the semiconductor substrate.
For example, butyl acetate (nBA) is used as the developer. Butyl acetate (nBA) can also be used for cleaning of pipes, cleaning of semiconductor wafers, etc., in addition to developing solutions.
Also, 4-methyl-2-pentanol (MIBC) is used as the rinse liquid. Propylene glycol monomethyl ether acetate (PGMEA) and isopropanol (IPA) are used as the cleaning liquid. Cyclohexanone (CHN) is used as the prewetting liquid.

[Resist composition]
The type of resist composition is not particularly limited, and known resist compositions can be used.
For example, as a resist composition, a resin (hereinafter simply referred to as "acid-decomposable resin") having a group that generates a polar group by the action of an acid (hereinafter also simply referred to as "acid-decomposable group"), a photoacid A resist composition containing a generator and a solvent (hereinafter also referred to as "first resist composition") can be used.
The acid-decomposable group preferably has a structure in which the polar group is protected with a leaving group that leaves under the action of an acid. That is, the acid-decomposable resin has a repeating unit having an acid-decomposable group. A resin having this repeating unit has an increased polarity under the action of an acid, thereby increasing the solubility in an alkaline developer and decreasing the solubility in an organic solvent.
The polar group is preferably an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl) Methylene group, acidic group such as tris(alkylsulfonyl)methylene group, and alcoholic hydroxyl group.

The acid-decomposable resin contains repeating units other than repeating units having an acid-decomposable group (for example, repeating units having an acid group, repeating units having a lactone group, a sultone group, or a carbonate group, fluorine atoms or iodine atoms). such as repeating units having
A known acid-decomposable resin can be used as the acid-decomposable resin.

The photoacid generator is not particularly limited as long as it is known, but when exposed to actinic rays or radiation, preferably electron beams or extreme ultraviolet rays, organic acids such as sulfonic acid, bis(alkylsulfonyl)imide, and Compounds that generate at least one tris(alkylsulfonyl)methide are preferred.

Solvents include water and organic solvents. The type of organic solvent is not particularly limited, and includes alcohol solvents, ether solvents, ester solvents, ketone solvents, and hydrocarbon solvents.

The first resist composition may contain materials other than the acid-decomposable resin, the photoacid generator, and the solvent.
For example, the first resist composition may contain an acid diffusion control agent. The acid diffusion control agent includes a basic compound and a proton acceptor functional group, and is decomposed by irradiation with actinic rays or radiation to reduce or eliminate the proton acceptor property, or to generate an acidic compound.
Further, the first resist composition is selected from the group consisting of a hydrophobic resin, a surfactant, a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer. It may contain selected compounds.

The resist composition includes a cross-linking agent having a cross-linking group, a compound having a reactive group that reacts with the cross-linking group, and a solvent (hereinafter also referred to as "second resist composition"). may be
The combination of the crosslinkable group and the reactive group is not particularly limited, and known combinations are employed.
The crosslinkable group or reactive group may be protected by a protective group. For example, the second resist composition further contains a photoacid generator, and the protective group is protected by the acid generated by the photoacid generator. A mode of desorption may also be used. Alternatively, a crosslinked structure may be formed by causing a condensation reaction between the crosslinking agent and the resin by the acid generated by the photoacid generator.
In addition, in the above-described second resist composition, a mode in which two types of a cross-linking agent having a cross-linking group and a compound having a reactive group that reacts with the cross-linking group are contained is described. It may be an aspect including a reactive group and a reactive group.

The resist composition may be a resist composition containing a main chain scission type polymer and a solvent.
The fact that the polymer is “main chain scission type” means that the polymer has the property of severing the main chain when the polymer is irradiated with light such as ionizing radiation or ultraviolet rays.
Examples of the main chain scission type polymer include acrylic main chain scission type resists, polymethyl methacrylate (PMMA), ZEP (manufactured by Nippon Zeon Co., Ltd.), which is a copolymer of α-chloromethacrylate and α-methylstyrene. ), and poly 2,2,2-trifluoroethyl α-chloroacrylate (EBR-9, manufactured by Toray Industries, Inc.).

The resist composition may be a so-called metal resist composition.
The metal resist composition includes a photosensitive composition capable of forming a coating containing a metal oxo-hydroxo network having organic ligands via metal carbon bonds and/or metal carboxylate bonds.
Examples of the metal resist composition include compositions described in JP-A-2019-113855, the contents of which are incorporated herein.

The resist composition contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total of the metal elements The content is preferably 10 mass ppb or less with respect to the total mass of the resist composition.

The present invention will be described in further detail based on examples below. The materials, amounts used, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the examples shown below.

<Example A>
[Manufacturing of chemicals]
First, a chemical solution (PGMEA (propylene glycol monomethyl ether acetate)) was prepared for use in examples described later. Specifically, first, a high-purity grade organic solvent reagent having a purity of 99% by mass or more was purchased. After that, the purchased reagent was subjected to a filtration treatment using an appropriate combination of the following filters to prepare a drug solution.
・IEX-PTFE (15 nm): 15 nm IEX PTFE manufactured by Entegris
・ PTEE (12 nm): 12 nm PTFE manufactured by Entegris
UPE (3 nm): 3 nm PE filter manufactured by Entegris In addition, in order to adjust the amount of impurities in the chemical solution, the purchase source of the organic solvent reagent is changed as appropriate, the purity grade is changed, and the above filtration treatment Distillation treatment was performed before The conditions were adjusted so that Fe was the predominant nanoparticle on the silicon substrate.
The trace metal was measured in advance using an ICP-MS apparatus Agilent 8900 manufactured by Agilent Technologies.
Examples 1 to 13 and Comparative Examples 1 to 4 are described below. The results of Examples 1 to 13 and Comparative Examples 1 to 4 are shown in Table 1 below.

(Examples 1 to 13)
In Examples 1 to 13, the chemicals were prepared on a silicon substrate having a diameter of 300 mm so that the particles had the values shown in the table. Using a coating and developing apparatus, the prepared chemical solution was applied onto a silicon substrate having a diameter of 300 mm.
The silicon substrate coated with the chemical solution was placed in a storage container capable of storing the entire silicon substrate, and transported to the surface defect measuring section.
A surface inspection device (SurfScan SP7; manufactured by KLA Corporation) was used for the surface defect measuring unit. In the surface inspection device, by optical defect inspection, laser light is incident on the surface of the silicon substrate and scattered light is measured to measure the position and size of the defect on the silicon substrate, the position information of the defect, and Information on the size of the defect was obtained and stored in the storage unit.
Here, regarding the silicon substrate used for applying the chemical solution, the defect position information and size are measured in advance by a surface inspection device (SurfScan SP7). It was calculated as the derived foreign matter.
Next, the silicon substrate subjected to surface defect measurement was transported to the analysis section. A laser ablation ICP mass spectrometer (LA-ICP-MS) was used for the analysis part. In transporting the silicon substrate, the silicon substrate was loaded into a cell capable of storing the entire silicon substrate, and a carrier gas was allowed to flow into the cell.

Based on the obtained defect position information and defect size information (klarf file), a laser ablation ICP mass spectrometer is used to perform elemental analysis of the defect by laser ablation. was confirmed to be detectable.
The laser ablation was performed with the silicon substrate housed in the container and with the carrier gas supplied. An analytical sample obtained by laser ablation was recovered with a carrier gas and subjected to inductively coupled plasma mass spectrometry. A femtosecond laser was used for laser ablation.
Argon gas was used as the carrier gas. The carrier gas flow rate was 1.69×10 ⁻² Pa·m ³ /sec (10 sccm). The water content in the carrier gas is shown in Table 1 below.
A FOUP (Front Opening Unified Pod) was used as a storage container for storing semiconductor substrates.
Prior to ablation, pre-cleaning was performed by flowing a cleaning gas at 1.69×10 ⁻¹ Pa·m ³ /sec (100 sccm (standard cubic centimeter per minute)) into the cell for 1 minute.

(Comparative Examples 1 to 4)
In Comparative Examples 1 to 4, a surface inspection device (SurfScan SP7; manufactured by KLA Corporation) was used, a laser was incident on the surface of the silicon substrate, and scattered light was measured to measure the position and size of defects on the silicon substrate. Then, defect position information and defect size information were obtained and stored in the storage unit.
Next, in Comparative Examples 1 to 4, based on the obtained defect position information and defect size information, a defect review device (SEMVision G6 (manufactured by Applied Materials)) was used to apply the chemical solution. qualitative elemental analysis of defects on silicon substrates. Qualitative elemental analysis of defects on silicon substrates after applying the chemical solutions of Comparative Examples 1 to 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. For this reason, Comparative Examples 1 to 4 are marked with "-" in the column of "moisture content of carrier gas" in Table 1 below.

In Examples 1 to 13 and Comparative Examples 1 to 4, defect position information and size were measured using a surface inspection apparatus (SurfScan SP7) after applying the chemical solution. The results are shown in the column of "NP of 20 nm or less on substrate after chemical application (SP7)".
In Examples 1 to 13 and Comparative Examples 1 to 4, after measuring defects in the chemical solution, defect position information and size were measured using a surface inspection apparatus (SurfScan SP7). The results are shown in the column of "NPs on substrate of 20 nm or less after analysis (SP7)".
In addition, "the number of Fe detected in NPs of 20 nm or less" in Table 1 below shows the results of measurement of defects in the chemicals of Examples 1 to 13 and Comparative Examples 1 to 4. In addition, in Table 1 below, nanoparticles are indicated as "NP".

In Examples 1 to 13, the Fe element was detected even in fine nanoparticle defects of 20 nm or less, indicating that fine metal foreign matter in the manufactured chemical can be inspected. On the other hand, in Comparative Examples 1 to 4, almost no Fe element having a size of 20 nm or less could be detected.
In Examples 1 to 13, similar results to the surface inspection apparatus (SurfScan SP7) were obtained in the measurement of defects.
Also, in Examples 1 to 13, LA-ICP-MS was used. For this reason, the nanoparticles on the silicon substrate were ablated and disappeared by the measurement of the defects, so the nanoparticles decreased after the measurement of the defects.
Comparative Examples 1-4 used SEM-EDX or SEM-EDS. Therefore, nanoparticles did not decrease after defect measurements.
Furthermore, by setting the water content of the carrier gas to a range of 0.00001 volume ppm or more and 0.1 volume ppm or less, the adhesion of nanoparticles due to contamination of the silicon substrate surface during measurement is suppressed, and contamination is suppressed. was confirmed. From the above, the effectiveness of the present invention was confirmed.

<Example B>
[Manufacturing of chemicals]
The same chemical solution as in Example A was used, except that the type of chemical solution was different. Liquid types include wafer cleaning liquid (PGMEA (propylene glycol monomethyl ether acetate)), prewetting liquid (CHN (cyclohexanone)), developing liquid (nBA (butyl acetate)), rinse liquid (MIBC (4-methyl-2-pentane tanol)) was prepared.
In addition, it was confirmed that the trace metal was 10 mass ppb or less for any metal element.
Examples 15 to 18 are described below. The results of Examples 15 to 18 are shown in Table 2 below.

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

(Chemical management)
The allowable control value for the number of metal foreign particles on the silicon substrate during chemical application was set to 150 metal foreign particles less than 20 nm/substrate.
Those that satisfy the control allowable value are indicated as "A" in the allowable judgment column of Table 2 below, and those that do not satisfy the control allowable value are indicated as "B" in the allowable judgment column of Table 2 below. In addition, in Table 2 below, nanoparticles are indicated as "NP".
The control allowable value was calculated by calculating the average +σ of the number of metal particles of less than 20 nm using LA-ICPMS in the production of the chemical solution in the past.
By using such a management method, advanced processes for forming patterns of 20 nm or less in various chemical liquids such as wafer cleaning liquid, prewetting liquid, developer, and rinse liquid used for the purpose of coating on silicon substrates. It was found that metal particles smaller than 20 nm, that is, nanoparticles, which are critical particles in , can be managed.
The control method is also effective for chemical solutions containing more than 10 mass ppb of any of the various metal elements, but ultrafine foreign matter of less than 20 nm becomes dominant foreign matter at 10 mass ppb. Since the purity range is as follows, such a chemical solution cannot be managed by the conventional technology, so the above management method was a more effective management method.

(device manufacturing)
The following lithography process was carried out using the chemical solution that was confirmed to be below the control allowable value. The number of defects was measured after the lithography process. Clearly, it was confirmed that the number of defects after the lithography process was small when using the chemical solution that was confirmed to be within the allowable range.
The number of defects after the lithography process is obtained by ashing the resist after lithography with oxygen plasma using an etching device TactrasVigus manufactured by Tokyo Electron Co., Ltd., and then optical defect inspection using a surface inspection device (SurfScan SP5; manufactured by KLA Corporation). The number of defects was measured by performing The results are shown in the column "Number of NPs after lithography (≦20 nm)" in Table 2 below. In Table 2 below, ≦20 nm indicates that the size of the nanoparticles is 20 nm or less.

(lithography process)
First, a silicon substrate having a diameter of about 300 mm (12 inches) was pre-wet using cyclohexanone (CHN). Next, the resist resin composition was spin-coated onto the pre-wet silicon substrate. Then, it was dried by heating on a hot plate at a temperature of 150° C. for 90 seconds to form a resist film with a thickness of 90 nm.
An ArF excimer laser scanner (manufactured by ASML, XT: 1700i, wavelength 193 nm), NA=1.20, Dipole (oσ/iσ)=0.981/0.859, Y-polarized light exposure conditions. After irradiation, it was baked at a temperature of 120° C. for 60 seconds. After that, development and rinsing were performed, and baking was performed at a temperature of 110° C. for 60 seconds to form a resist pattern with a line width of 45 nm and a space width of 45 nm.
The following resist resin compositions were used.

(Resist resin composition)
The resist resin composition will be explained. A resist resin composition was obtained by mixing the following components.

Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 7500): the numerical value described in each repeating unit means mol %): 100 parts by mass

Photoacid generator shown below: 8 parts by mass

Quencher shown below: 5 parts by mass (mass ratio was 0.1:0.3:0.3:0.2 from left to right). Among the quenchers below, polymer type quenchers have a weight average molecular weight (Mw) of 5,000. Moreover, the numerical value described in each repeating unit means a molar ratio.

Hydrophobic resin shown below: 4 parts by mass (mass ratio was set to (1):(2)=0.5:0.5).
Among the hydrophobic resins 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. . In addition, in each hydrophobic resin, the numerical value described in each repeating unit means a molar ratio.

solvent:
PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass Cyclohexanone: 600 parts by mass γ-BL (γ-butyrolactone): 100 parts by mass

<Example C>
[Production of resist composition]
As the resist composition, the resist composition shown in Example B above was used. The resist composition was filtered and purified.
After that, it was filled in a gallon bottle and connected to a coating and developing apparatus LITHIUS PRO (registered trademark)-Z (manufactured by Tokyo Electron Ltd.). Furthermore, a silicon substrate having a diameter of about 300 mm (12 inches) was pre-wet using cyclohexanone (CHN). Next, the resist resin composition was spin-coated onto the pre-wet silicon substrate. Then, it was dried by heating on a hot plate at a temperature of 150° C. for 90 seconds to form a resist film with a thickness of 45 nm. Filtration conditions were adjusted such that Fe was the predominant nanoparticle on the silicon substrate. The trace metal was measured in advance using an ICP-MS apparatus Agilent 8900 manufactured by Agilent Technologies.

Examples 20 to 32 and Comparative Examples 20 to 23 are described below. The results of Examples 20-32 and Comparative Examples 20-23 are shown in Table 3 below.
In Examples 20 to 32, the resist compositions were prepared on a silicon substrate having a diameter of 300 mm so that the particles had the values shown in the table. Using a coating and developing apparatus, the prepared resist composition was coated on a silicon substrate having a diameter of 300 mm.
The silicon substrate coated with the resist composition was placed in a storage container capable of storing the entire silicon substrate, and transported to the surface defect measuring section.
A surface inspection device (SurfScan SP7; manufactured by KLA Corporation) was used for the surface defect measuring unit. In the surface inspection device, by optical defect inspection, laser light is incident on the surface of the silicon substrate and scattered light is measured to measure the position and size of the defect on the silicon substrate, the position information of the defect, and Information on the size of the defect was obtained and stored in the storage unit.
Here, regarding the silicon substrate used for coating the resist composition, the defect position information and size are measured in advance by a surface inspection device (SurfScan SP7), and from the number of foreign substances after the application of the resist composition, the number of foreign substances before the application of the resist composition is calculated. The difference in the number was calculated as foreign matter derived from the resist composition.
Next, the silicon substrate subjected to surface defect measurement was transported to the analysis section. A laser ablation ICP mass spectrometer (LA-ICP-MS) was used for the analysis part. In transporting the silicon substrate, the silicon substrate was loaded into a cell capable of storing the entire silicon substrate, and a carrier gas was allowed to flow into the cell.

Based on the obtained defect position information and defect size information (klarf file), a laser ablation ICP mass spectrometer is used to perform elemental analysis of the defect by laser ablation. was confirmed to be detectable.
The laser ablation was performed with the silicon substrate housed in the container and with the carrier gas supplied. An analytical sample obtained by laser ablation was collected with a carrier gas and subjected to inductively coupled plasma mass spectrometry. A femtosecond laser was used for laser ablation.
Argon gas was used as the carrier gas. The carrier gas flow rate was 1.69×10 ⁻² Pa·m ³ /sec (10 sccm). The water content in the carrier gas is shown in Table 3 below.
A FOUP (Front Opening Unified Pod) was used as a storage container for storing semiconductor substrates.
Prior to ablation, pre-cleaning was performed by flowing a cleaning gas at 1.69×10 ⁻¹ Pa·m ³ /sec (100 sccm (standard cubic centimeter per minute)) into the cell for 1 minute.

(Comparative Examples 20-23)
In Comparative Examples 20 to 23, a surface inspection device (SurfScan SP7; manufactured by KLA Corporation) was used, a laser was incident on the surface of the silicon substrate, and scattered light was measured to measure the position and size of defects on the silicon substrate. Then, defect position information and defect size information were obtained and stored in the storage unit.
Next, in Comparative Examples 20 to 23, based on the obtained defect position information and defect size information, a defect review apparatus (SEMVision G6 (manufactured by Applied Materials)) was used to apply a resist composition. A qualitative elemental analysis of defects on the silicon substrate after sintering was attempted. Qualitative elemental analysis of defects on silicon substrates after coating the resist compositions of Comparative Examples 20 to 23 was carried out using SEM-EDS (Scanning Electron Microscope-Energy Dispersive X-ray Spectroscopy). SEM-EDS does not use a carrier gas because it is performed under vacuum with an electron beam. For this reason, Comparative Examples 20 to 23 are marked with "-" in the column of "moisture content of carrier gas" in Table 3 below. In addition, in Table 3 below, nanoparticles are indicated as "NP".

In Examples 20 to 32 and Comparative Examples 20 to 23, after coating the resist composition, defect position information and size were measured using a surface inspection apparatus (SurfScan SP7). The results are shown in the column of "NP of 20 nm or less on substrate after application of resist composition (SP7)".
In Examples 20 to 32 and Comparative Examples 20 to 23, after measuring defects in the resist composition, defect position information and size were measured using a surface inspection apparatus (SurfScan SP7). The results are shown in the column of "NPs on substrate of 20 nm or less after analysis (SP7)".
In Table 3 below, "the number of Fe detected in NPs of 20 nm or less" shows the results of measurement of defects in the resist compositions of Examples 20-32 and Comparative Examples 20-23. In addition, in Table 3 below, nanoparticles are indicated as "NP".

In Examples 20 to 32, the Fe element was detected even in fine nanoparticle defects of 20 nm or less, indicating that fine metal foreign matter in the manufactured chemical can be inspected. On the other hand, in Comparative Examples 20 to 23, almost no Fe element having a size of 20 nm or less could be detected.
In Examples 20 to 32, similar results to the surface inspection apparatus (SurfScan SP7) were obtained in defect measurement.
Also, in Examples 20 to 32, LA-ICPMS was used. For this reason, the nanoparticles on the silicon substrate were ablated and disappeared by the measurement of the defects, so the nanoparticles decreased after the measurement of the defects.
Comparative Examples 20-23 used SEM-EDX or SEM-EDS. Therefore, nanoparticles did not decrease after defect measurements.
Furthermore, by setting the moisture content of the carrier gas to a range of 0.00001 volume ppm or more and 0.1 volume ppm or less, the adhesion of nanoparticles due to contamination of the silicon substrate surface during measurement is suppressed, and contamination is suppressed. was confirmed. From the above, the effectiveness of the present invention was confirmed.

<Example D>
[Production of resist composition]
As the resist composition, the resist composition shown in Example B above was used.
In addition, it was confirmed that the trace metal was 10 mass ppb or less for any metal element.
Example 33 will be described below. The results of Example 33 are shown in Table 4 below.

(Example 33)
In Example 33, in the same manner as in Examples 20 to 32, an optical defect inspection was performed using a surface inspection device (SurfScan SP5; manufactured by KLA Corporation), followed by inductively coupled plasma mass spectrometry. The water content of the carrier gas was set to 0.1 ppm by volume.

(Resist composition management)
The permissible control value for the number of metal foreign particles on the silicon substrate during coating of the resist composition was set to 500 (pieces/substrate) or less for metal foreign particles having a size of less than 20 nm.
Those that satisfy the control allowable value are indicated as "A" in the allowable judgment column of Table 4 below, and those that do not satisfy the control allowable value are indicated as "B" in the allowable judgment column of Table 4 below. In addition, in Table 4 below, nanoparticles are indicated as "NP".
The control allowable value was calculated by calculating the average +σ of past production results for the number of metal particles less than 20 nm using LA-ICPMS in the production of the resist composition.
It has been found that by using such a control method, it is possible to control metal particles of less than 20 nm, which are critical particles in advanced processes for forming patterns of 20 nm or less in resist compositions.
The control method is also effective for a resist composition containing more than 10 ppb by mass of any of various metal elements, but ultrafine foreign matter of less than 20 nm becomes dominant foreign matter at 10 Since the purity range is ppb or less by mass, such a resist composition cannot be controlled by the conventional technology, so the above control method was a more effective control method.

(device manufacturing)
The same lithography process as in Example B above was performed using the resist composition that was confirmed to be at or below the control allowable value. The number of defects was measured after the lithography process. Clearly, it was confirmed that the number of defects after the lithography process was small when using the resist composition that was confirmed to be within the allowable range.
The number of defects after the lithography process is obtained by ashing the resist after lithography with oxygen plasma using an etching device TactrasVigus manufactured by Tokyo Electron Co., Ltd., and then optical defect inspection using a surface inspection device (SurfScan SP5; manufactured by KLA Corporation). The number of defects was measured by performing The results are shown in the column of "Number of NPs after lithography" in Table 4 below. In Table 4 below, ≦20 nm indicates that the size of the nanoparticles is 20 nm or less.

<Example E>
[Manufacturing of chemicals]
First, a cleaning chemical (PGMEA (propylene glycol monomethyl ether acetate)) was prepared for use in examples described later. Specifically, first, a high-purity grade organic solvent reagent having a purity of 99% by mass or more was purchased. After that, the purchased reagent was subjected to a filtration treatment using an appropriate combination of the following filters to prepare a washing chemical solution.
・IEX-PTFE (15 nm): 15 nm IEX PTFE manufactured by Entegris
・ PTEE (12 nm): 12 nm PTFE manufactured by Entegris
・ UPE (3 nm): 3 nm PE filter manufactured by Entegris In addition, in order to adjust the amount of impurities in the cleaning chemical solution described later, the purchase source of the organic solvent reagent may be changed, the purity grade may be changed, or the above-mentioned Distillation treatment was performed before the filtration treatment. The conditions were adjusted so that metals of 20 nm or less were predominant nanoparticles on the silicon substrate.

(Confirmation of performance of cleaning chemicals)
A gallon bottle was filled with the cleaning chemical solution described above and connected to a sufficiently cleaned coating and developing apparatus LITHIUS PRO (registered trademark)-Z (manufactured by Tokyo Electron Ltd.). After the connection, a cleaning chemical was applied onto a silicon substrate having a diameter of about 300 mm (12 inches), and the silicon substrate was recovered.
When the recovered silicon substrate was measured as follows, 50 nanoparticles of a metal element having a size of 20 nm or less were detected on the silicon substrate.
The recovered silicon substrate was placed in a storage container capable of storing the entire silicon substrate, and transported to the surface defect measuring section.
A surface inspection device (SurfScan SP5; manufactured by KLA Corporation) was used for the surface defect measurement unit. In the surface inspection device, by optical defect inspection, laser light is incident on the surface of the silicon substrate and scattered light is measured to measure the position and size of the defect on the silicon substrate, the position information of the defect, and Information on the size of the defect was obtained and stored in the storage unit.
Next, the silicon substrate subjected to surface defect measurement was transported to the analysis section. A laser ablation ICP mass spectrometer (LA-ICP-MS) was used for the analysis part. In transporting the silicon substrate, the silicon substrate was loaded into a cell capable of storing the entire silicon substrate, and a carrier gas was allowed to flow into the cell.
Based on the obtained defect position information and defect size information (klarf file), elemental analysis of the defect was performed by laser ablation using a laser ablation ICP mass spectrometer.
The laser ablation was performed with the silicon substrate housed in the container and with the carrier gas supplied. An analytical sample obtained by laser ablation was recovered with a carrier gas and subjected to inductively coupled plasma mass spectrometry. A femtosecond laser was used for laser ablation.
Argon gas was used as the carrier gas. The carrier gas flow rate was 1.69×10 ⁻² Pa·m ³ /sec (10 sccm).
Prior to ablation, pre-cleaning was performed by flowing a cleaning gas at 1.69×10 ⁻¹ Pa·m ³ /sec (100 sccm (standard cubic centimeter per minute)) into the cell for 1 minute.

(Confirmation method of degree of contamination of semiconductor manufacturing equipment)
The cleaning chemicals were filled in a gallon bottle and connected to an uncleaned coating and developing apparatus LITHIUS PRO (registered trademark)-Z (manufactured by Tokyo Electron Ltd.). After the connection, a cleaning chemical was applied onto the silicon substrate having a diameter of about 300 mm (12 inches).
At this time, every time 1 L (1000 mL) of the liquid was fed, 10 mL was applied on the silicon substrate, the silicon substrate was collected, and the measurement was performed as described above to try to detect nanoparticles of the metal element. When the cleaning chemical in the gallon bottle ran out, it was replaced with a gallon bottle filled with new cleaning chemical. Table 5 below shows the number of metal element nanoparticles detected at each liquid feeding amount.

As shown in Table 5, as the amount of liquid fed to the coating and developing apparatus was increased, the number of metal element nanoparticles detected in the cleaning chemical solution used for cleaning decreased. That is, it was confirmed that the contamination state of the coating and developing apparatus was improved.

Reference Signs List 10, 10a, 10b analysis device 12a first transfer chamber 12b measurement chamber 12c second transfer chamber 12d analysis chamber 12e processing chamber 12g introduction portion 12h wall 13 storage container 14 transfer device 14a attachment portion 15 transfer arm 16 transfer device 16a attachment portion 20 Surface defect measurement unit 22, 32 Stage 23 Incidence unit 24 Condensing lens 25, 26 Light receiving unit 27 Condensing lens 28 Calculation unit 29 Storage unit 30 Analysis unit 33 Container unit 34 Light source unit 35 Condensing lens 36 Analysis unit 38 Carrier gas supply Part 39 Piping 40 Cleaning gas supply part 41 Outflow part 42 Control part 44 Plasma torch 46 Mass analysis part 46a Ion lens part 46b Mass spectrometer part 47 Ion lens 48 Reflectron 49 Detector 50 Semiconductor substrate 50a Surface 51 Defect 51a Analysis sample 70 Surface defect measurement device 72 Mass spectrometer C ₁ , C ₂ , C ₃ Axis of rotation 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 Step V Height direction

Claims (31)

A step 1X of preparing a chemical solution;
a step 2X of applying the chemical solution onto the semiconductor substrate;
measuring the presence or absence of defects on the surface of the semiconductor substrate, obtaining position information on the semiconductor substrate of the defects on the surface of the semiconductor substrate, and determining the position of the defects on the surface of the semiconductor substrate based on the position information; A method of inspecting a chemical liquid, comprising a step 3X of irradiating a defect with a laser beam, recovering an analysis sample obtained by the irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry. 2. The chemical liquid inspection method according to claim 1, further comprising a step 4X for determining the presence or absence of a metal element in said defect from the mass spectrometry data in said defect obtained in said step 3X. 3. The chemical liquid inspection method according to claim 2, further comprising a step 5X of measuring the number of defects containing said metal element after said step 4X. 2. The chemical liquid inspection method according to claim 1, further comprising step 5X of measuring the number of defects containing a metal element in said defects based on the mass spectrometry data of said defects obtained in said step 3X. The chemical solution contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total of the metal elements The chemical liquid inspection method according to any one of claims 1 to 4, wherein the content is 10 mass ppb or less with respect to the total mass of the chemical liquid. The chemical liquid inspection method according to any one of claims 1 to 4, wherein the carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less. A method for producing a chemical liquid, comprising the method for inspecting a chemical liquid according to any one of claims 1 to 4. A step 1X of preparing a chemical solution;
a step 2X of applying the chemical solution onto the semiconductor substrate;
measuring the presence or absence of defects on the surface of the semiconductor substrate, obtaining position information on the semiconductor substrate of the defects on the surface of the semiconductor substrate, and determining the position of the defects on the surface of the semiconductor substrate based on the position information; A step 3X of irradiating the defect with a laser beam, recovering the analysis sample obtained by the irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry;
a step 4X for determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in the step 3X; and a step 5X for measuring the number of defects containing the metal element; Or having a step 5X of measuring the number of defects containing a metal element in the defects based on the mass spectrometry data in the defects obtained in the step 3X,
and a step 6X for determining whether the number of defects obtained in the step 5X is within an allowable range. The chemical solution contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total of the metal elements 9. The chemical management method according to claim 8, wherein the content is 10 mass ppb or less with respect to the total mass of the chemical. 9. The method of managing a chemical liquid according to claim 8, wherein the carrier gas has a water content of 0.00001 ppm by volume or more and 0.1 ppm by volume or less. A step 1X of preparing a chemical solution;
a step 2X of applying the chemical solution onto the semiconductor substrate;
measuring the presence or absence of defects on the surface of the semiconductor substrate, obtaining positional information on the semiconductor substrate of the defects on the surface of the semiconductor substrate, and determining the position of the defects on the surface of the semiconductor substrate based on the positional information; A step 3X of irradiating the defect with a laser beam, recovering the analysis sample obtained by the irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry;
a step 4X for determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in the step 3X; and a step 5X for measuring the number of defects containing the metal element; Or having a step 5X of measuring the number of defects containing a metal element in the defects based on the mass spectrometry data in the defects obtained in the step 3X,
a step 6X of determining whether the number of defects obtained in step 5X is within an acceptable range;
A method of manufacturing a semiconductor device, comprising a step 7X of manufacturing a semiconductor device using the chemical determined to be within the allowable range in the step 6X. 12. The method of manufacturing a semiconductor device according to claim 11, wherein said chemical liquid is a prewet liquid, a developer, a rinse liquid, or a cleaning liquid. The chemical solution contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the total of the metal elements 12. The method of manufacturing a semiconductor device according to claim 11, wherein the content is 10 mass ppb or less with respect to the total mass of said chemical solution. 14. The method of manufacturing a semiconductor device according to claim 11, wherein said carrier gas has a moisture content of 0.00001 ppm by volume or more and 0.1 ppm by volume or less. Step 1Y of preparing a resist composition;
Step 2Y of applying the resist composition onto a semiconductor substrate;
The presence or absence of defects in the coating film of the resist composition is measured, the positional information of the defects in the coating film of the resist composition on the semiconductor substrate is obtained, and the positional information of the semiconductor substrate is determined based on the positional information. A method for inspecting a resist composition, comprising a step 3Y of irradiating the defect on the surface with a laser beam, recovering an analysis sample obtained by the irradiation with a carrier gas, and subjecting it to inductively coupled plasma mass spectrometry. 16. The method of inspecting a resist composition according to claim 15, further comprising a step 4Y for determining the presence or absence of a metal element in said defect from the mass spectrometry data in said defect obtained in said step 3Y. 17. The method of inspecting a resist composition according to claim 16, further comprising a step 5Y of measuring the number of defects containing said metal element after said step 4Y. 16. The resist composition inspection method according to claim 15, comprising a step 5Y of measuring the number of defects containing a metal element in the defects based on the mass spectrometry data in the defects obtained in the step 3Y. . The resist composition contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the metal element The method for inspecting a resist composition according to any one of claims 15 to 18, wherein the total content of is 10 mass ppb or less with respect to the total mass of the resist composition. The method for inspecting a resist composition according to any one of claims 15 to 18, wherein the carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less. A method for producing a resist composition, comprising the method for inspecting the resist composition according to any one of claims 15 to 18. Step 1Y of preparing a resist composition;
Step 2Y of applying the resist composition onto a semiconductor substrate;
The presence or absence of defects in the coating film of the resist composition is measured to obtain positional information on the semiconductor substrate of the defects in the coating film of the resist composition, and based on the positional information, the surface of the semiconductor substrate A step 3Y of irradiating the above defect with a laser beam, collecting an analysis sample obtained by irradiation with a carrier gas, and performing inductively coupled plasma mass analysis;
a step 4Y for determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in the step 3Y; and a step 5Y for measuring the number of defects containing the metal element; or Step 5Y of measuring the number of defects containing a metal element in the defects based on the mass spectrometry data of the defects obtained in Step 3Y,
and Step 6Y of determining whether the number of defects obtained in Step 5Y is within an allowable range. The resist composition contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the metal element 23. The method of controlling a resist composition according to claim 22, wherein the total content of is 10 mass ppb or less with respect to the total mass of said resist composition. 23. The method of managing a resist composition according to claim 22, wherein the carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less. Step 1Y of preparing a resist composition;
Step 2Y of applying the resist composition onto a semiconductor substrate;
The presence or absence of defects in the coating film of the resist composition is measured, the positional information of the defects in the coating film of the resist composition on the semiconductor substrate is obtained, and the positional information of the semiconductor substrate is determined based on the positional information. A step 3Y of irradiating the defect on the surface with a laser beam, recovering the analysis sample obtained by the irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry;
a step 4Y for determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in the step 3Y; and a step 5Y for measuring the number of defects containing the metal element; or Step 5Y of measuring the number of defects containing a metal element in the defects based on the mass spectrometry data of the defects obtained in Step 3Y,
A step 6Y of determining whether the number of defects obtained in the step 5Y is within an acceptable range;
A method for manufacturing a semiconductor device, comprising a step 7Y of manufacturing a semiconductor device using the resist composition determined to be within the allowable range in the step 6Y. The resist composition contains at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti and Zn, and the metal element is 10 mass ppb or less with respect to the total mass of said resist composition. 26. The method of manufacturing a semiconductor device according to claim 25, wherein said carrier gas has a water content of 0.00001 ppm by volume or more and 0.1 ppm by volume or less. Step 1Z of preparing a chemical solution;
Step 2Z of cleaning the semiconductor manufacturing equipment using the chemical solution;
a step 3Z of applying the chemical solution after cleaning in the step 2Z onto a semiconductor substrate;
measuring the presence or absence of defects on the surface of the semiconductor substrate, obtaining position information on the semiconductor substrate of the defects on the surface of the semiconductor substrate, and determining the position of the defects on the surface of the semiconductor substrate based on the position information; A step 4Z of irradiating the defect with a laser beam, recovering the analysis sample obtained by the irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry;
A method for confirming the contamination state of a semiconductor manufacturing apparatus, comprising a step 5Z for determining the presence or absence of a metal element in the defect from the mass spectrometry data in the defect obtained in the step 4Z. 29. The method for confirming the state of contamination in a semiconductor manufacturing apparatus according to claim 28, further comprising step 6Z of measuring the number of defects containing said metal element. Step 1Z of preparing a chemical solution;
Step 2Z of cleaning the semiconductor manufacturing equipment using the chemical solution;
a step 3Z of applying the chemical solution after cleaning in the step 2Z onto a semiconductor substrate;
measuring the presence or absence of defects on the surface of the semiconductor substrate, obtaining position information on the semiconductor substrate of the defects on the surface of the semiconductor substrate, and determining the position of the defects on the surface of the semiconductor substrate based on the position information; A step 4Z of irradiating the defect with a laser beam, recovering the analysis sample obtained by the irradiation with a carrier gas, and performing inductively coupled plasma mass spectrometry;
A method for confirming the contamination state of a semiconductor manufacturing apparatus, comprising a step 6Z of measuring the number of defects containing a metal element among the defects based on the mass spectrometry data of the defects obtained in the step 4Z. 31. The method for checking a contamination state of a semiconductor manufacturing apparatus according to claim 28, wherein said carrier gas has a water content of 0.00001 volume ppm or more and 0.1 volume ppm or less.

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