Management method, measurement method, measurement device, quartz crystal sensor, and set

Abstract

To provide a management method for managing a purity of a chemical solution containing an organic solvent more simply, a measurement method, a measurement device, a crystal oscillator sensor, and a set.SOLUTION: A management method for sensing impurities in a chemical solution containing an organic solvent to manage a purity of a chemical solution, comprises: a step 1 of preparing a target chemical solution containing an organic solvent; a step 2 of contacting a target chemical solution with a crystal oscillator sensor including an adsorption layer that adsorbs impurities and a crystal oscillator, to obtain an amount of change in a resonant frequency of the crystal oscillator due to contact with the target chemical solution; and a step 3 of comparing whether the obtained amount of change in the resonance frequency is included in a preset allowable range of the amount of change in the resonance frequency based on the purity of the target chemical solution, to manage a purity of the chemical solution. In the step 2, at least a part of a liquid contact part contacting the target chemical solution is made of a fluororesin.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a management method, a measurement method, a measurement device, a quartz crystal sensor, and a set. [Background technology]

[0002] The manufacturing process of semiconductor devices includes various steps such as a lithography step, an etching step, an ion implantation step, a stripping step, etc. Various chemical liquids used in such manufacturing processes of semiconductor devices, such as a developer, a rinse liquid, a pre-wet liquid, and a stripping liquid, are required to be highly pure.

[0003] One method for evaluating the characteristics of a high-purity chemical liquid is to apply the high-purity chemical liquid onto a substrate and measure the number of defects on the substrate, thereby evaluating the characteristics of the chemical liquid. For example, in Patent Document 1, the above evaluation is carried out using a surface inspection device (SP-5; manufactured by KLA Tencor). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017 / 169834 Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, the measurement using the surface inspection device (SP-5; manufactured by KLA Tencor) described in Patent Document 1 is complicated in its measurement procedure, takes a long time to perform, and lacks versatility. For this reason, it is not preferable from an industrial point of view to carry out the above-mentioned measurements to measure the purity of the chemical solution every time the chemical solution is produced, and there has been a demand for a method for more easily controlling the purity of the chemical solution that is produced.

[0006] In view of the above-mentioned circumstances, an object of the present invention is to provide a method for more simply managing the purity of a chemical solution containing an organic solvent. Another object of the present invention is to provide a measurement method, a measurement device, a quartz crystal sensor, and a set thereof. [Means for solving the problem]

[0007] As a result of intensive research, the present inventors have found that the above problems can be solved by the following configuration.

[0008] (1) A method for detecting impurities in a chemical solution containing an organic solvent and managing the purity of the chemical solution, comprising the steps of: A step 1 of preparing a target chemical solution containing an organic solvent; a step 2 of contacting a quartz crystal sensor including an adsorption layer for adsorbing impurities and a quartz crystal oscillator with a target liquid drug, and obtaining a change in the resonant frequency of the quartz crystal oscillator due to contact with the target liquid drug; and a step 3 of controlling the purity of the chemical by comparing whether or not the obtained change in resonance frequency is within a preset allowable range of the change in resonance frequency based on the purity of the target chemical, A management method, wherein in step 2, at least a portion of the liquid contact part that comes into contact with the target chemical liquid is made of a fluorine-based resin. (2) The management method according to (1), further comprising: feeding the target chemical solution to a quartz crystal sensor to bring the target chemical solution into contact with the quartz crystal sensor. (3) The management method according to (1) or (2), further comprising flowing the target chemical solution in one direction through the quartz crystal sensor to bring the target chemical solution into contact with the quartz crystal sensor. (4) The management method according to any one of (1) to (3), wherein the target chemical solution is circulated and supplied to the quartz crystal sensor, and the circulating flow rate of the target chemical solution is 0.01 to 1000 ml / s. (5) The management method according to any one of (1) to (4), wherein the adsorption layer is composed of at least one material selected from the group consisting of Si, Au, SiO2, SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, and a photosensitive resin composition. (6) The quartz crystal sensor has a plurality of adsorption layers; step 2 is a step of obtaining a change in resonant frequency for each of a plurality of adsorption layers; The method for managing the purity of the chemical solution according to any one of (1) to (5), wherein step 3 is a step of calculating the difference between the amounts of change in the resonant frequency of each of a plurality of adsorption layers, and comparing whether or not the obtained value is within a preset allowable range of the amount of change in the resonant frequency based on the purity of the target chemical solution, thereby managing the purity of the chemical solution. (7) The management method according to (6), wherein at least one of the multiple adsorption layers is an Au layer. (8) Step 1 of preparing a target chemical solution containing an organic solvent; and a step 2 of contacting the target chemical solution with a quartz crystal oscillator sensor including a quartz crystal oscillator and an adsorption layer for adsorbing impurities in the target chemical solution, and obtaining a change in the resonant frequency of the quartz crystal oscillator due to contact with the target chemical solution, A method for measuring a chemical liquid, wherein in step 2, at least a part of a liquid contact part that comes into contact with the target chemical liquid is made of a fluorine-based resin. (9) The measurement method according to (8), further comprising: delivering the target liquid drug to a quartz crystal sensor to bring the target liquid drug into contact with the quartz crystal sensor. (10) The measurement method according to (8) or (9), in which the target chemical solution is caused to flow in one direction through the quartz crystal sensor to bring the target chemical solution into contact with the quartz crystal sensor. (11) The measurement method according to any one of (8) to (10), in which the target chemical solution is circulated and supplied to the quartz crystal sensor, and the circulating flow rate of the target chemical solution is 0.01 to 1000 ml / s. (12) The measurement method according to any one of (8) to (11), wherein the adsorption layer is composed of at least one material selected from the group consisting of Si, Au, SiO2, SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, and a photosensitive resin composition. (13) The quartz crystal sensor has a plurality of adsorption layers, The measurement method according to any one of (8) to (12), wherein step 2 is a step of obtaining the amount of change in resonant frequency for each of a plurality of adsorption layers. (14) The measurement method according to (13), wherein at least one of the multiple adsorption layers is an Au layer. (15) A measuring device for detecting impurities in a chemical solution containing an organic solvent, comprising: a quartz crystal sensor including an adsorption layer for adsorbing impurities and a quartz crystal oscillator, the quartz crystal sensor being brought into contact with a target chemical solution including an organic solvent; an oscillator that vibrates a crystal unit at a resonant frequency; a detection unit connected to the quartz crystal sensor and detecting a change in the resonant frequency of the quartz crystal sensor due to contact with the target liquid medicine; A supply unit that supplies a target chemical solution to the quartz crystal sensor and brings the target chemical solution into contact with the quartz crystal sensor, At least a part of the liquid contacting part that comes into contact with the target chemical solution is made of a fluorine-based resin. Measuring equipment. (16) The measuring device according to (15), further comprising a display unit for displaying an amount of change in the resonant frequency. (17) The measuring device according to (15) or (16), wherein the supply unit supplies the target chemical solution to the quartz crystal sensor by flowing it in one direction. (18) The measuring device according to any one of (15) to (17), wherein the supply unit circulates and supplies the target chemical solution to the quartz crystal sensor, and the circulation flow rate of the target chemical solution is 0.01 to 1000 ml / s. (19) The measuring device according to any one of (15) to (18), wherein the adsorption layer is composed of at least one material selected from the group consisting of Si, Au, SiO2, SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, and a photosensitive resin composition. (20) The quartz crystal sensor has a plurality of adsorption layers, The measuring device according to any one of (15) to (19), wherein the detection unit detects the amount of change in the resonant frequency for each of the plurality of adsorption layers. (21) The measuring device according to (20), wherein at least one of the multiple adsorption layers is an Au layer. (22) a seal portion disposed on the quartz crystal sensor; a block disposed on the quartz crystal sensor via a seal portion, the block including a supply path for supplying the target chemical solution to the quartz crystal sensor and a discharge path for discharging the target chemical solution from the quartz crystal sensor; A liquid delivery section including a first tube connected to the supply path and a second tube connected to the discharge path, A measuring device described in any one of (15) to (21), wherein at least one of the liquid contacting part of the seal part that comes into contact with the target chemical liquid, the liquid contacting part of the block that comes into contact with the target chemical liquid, and the liquid contacting part of the liquid delivery part that comes into contact with the target chemical liquid is made of a fluorine-based resin. (23) The measuring device according to (22), wherein a liquid-contacting portion of the block that comes into contact with the target chemical solution is made of a fluororesin exhibiting a tensile strength of 20 to 60 MPa and a Shore D hardness of 60 to 80. (24) The measuring device according to (22) or (23), wherein the liquid contact portion of the block that comes into contact with the target chemical solution is made of a fluororesin selected from the group consisting of perfluoroalkoxyalkane, ethylene tetrafluoroethylene copolymer, perfluoroethylene propene copolymer, polychlorotrifluoroethylene, and polyvinylidene fluoride. (25) The measuring device described in (22), wherein the liquid contact part of the liquid delivery part that comes into contact with the target chemical liquid is made of a fluorine-based resin having repeating units that contain fluorine atoms, carbon atoms, and atoms other than fluorine atoms and carbon atoms. (26) The measuring device according to (22) or (25), wherein the liquid contacting part of the liquid delivery part that comes into contact with the target chemical liquid is made of a fluorine-based resin selected from the group consisting of a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer, and polychlorotrifluoroethylene. (27) The measuring device according to (22), wherein the liquid-contacting portion of the seal portion that comes into contact with the target chemical liquid is made of a fluororesin having a tensile strength of 20 to 40 MPa, a Shore D hardness of 56 to 70, and a flexural modulus of elasticity of 0.5 to 3 GPa. (28) The measuring device according to (22) or (27), wherein the liquid-contacting portion of the seal portion that comes into contact with the target chemical liquid is made of a fluororesin selected from the group consisting of perfluoroalkoxyalkane, perfluoroethylene propene copolymer, ethylene chlorotrifluoroethylene copolymer, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene, and polyvinylidene fluoride. (29) A quartz crystal sensor for use in the measuring device according to any one of (15) to (28), A crystal oscillator and an adsorption layer disposed on the crystal oscillator, The adsorption layer is a quartz crystal sensor composed of at least one material selected from the group consisting of Si, Au, SiO2, SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, and a photosensitive resin composition. (30) The quartz crystal sensor according to (29), wherein at least two adsorption layers are disposed on the quartz crystal. (31) The quartz crystal sensor according to (30), wherein at least one of the plurality of adsorption layers is an Au layer. (32) a chemical solution; An information display unit that displays or stores information about the resonant frequency of the chemical solution, a change in the resonant frequency of the quartz oscillator caused by contacting the liquid medicine with a quartz oscillator sensor including a quartz oscillator and an adsorption layer for adsorbing impurities in the liquid medicine is obtained, the change in the resonant frequency obtained is compared with a change in the resonant frequency based on a preset purity of the liquid medicine, and an evaluation of the purity of the liquid medicine is given for the change in the resonant frequency obtained based on the evaluation, and the change in the resonant frequency obtained based on the evaluation is associated with the purity of the liquid medicine and recorded as resonant frequency information of the liquid medicine; The resonant frequency information of the chemical solution is used to obtain information of the purity of the chemical solution. (33) The set according to (32), further comprising a container for storing the medicinal liquid, the information display unit being provided on the container. (34) The set according to (32) or (33), wherein the resonant frequency information of the chemical solution is displayed on the information display unit using at least one of letters, symbols, and barcodes. Effect of the Invention

[0009] According to the present invention, a method for more simply managing the purity of a chemical solution containing an organic solvent can be provided. Furthermore, according to the present invention, a measurement method, a measurement device, a quartz crystal sensor, and a set can be provided. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic diagram illustrating an example of a measuring device according to an embodiment of the present invention. [Diagram 2] 1 is a schematic cross-sectional view showing a first example of a quartz crystal oscillator sensor according to an embodiment of the present invention. [Diagram 3] 1 is a graph showing an example of a calibration curve showing the relationship between the amount of impurities and the resonance frequency of a quartz crystal resonator. [Figure 4] FIG. 2 is a schematic diagram showing an example of a flow cell unit of the measurement apparatus according to the embodiment of the present invention. [Diagram 5] FIG. 4 is a schematic diagram showing a second example of a quartz crystal oscillator sensor according to an embodiment of the present invention. [Figure 6] FIG. 4 is a schematic cross-sectional view showing a second example of a quartz crystal oscillator sensor according to an embodiment of the present invention. [Figure 7] FIG. 4 is a schematic diagram showing a third example of a quartz crystal oscillator sensor according to an embodiment of the present invention. [Figure 8] FIG. 11 is a schematic cross-sectional view showing a third example of a quartz crystal oscillator sensor according to an embodiment of the present invention. [Figure 9] FIG. 1 is a schematic perspective view showing an example of a set according to an embodiment of the present invention. [Figure 10] FIG. 2 is a schematic diagram showing an example of an information display section of a set according to an embodiment of the present invention. [Figure 11] 1 is a graph plotting the results of Example A on an orthogonal coordinate system with the amount of change in resonance frequency on the horizontal axis and the number of defects on the vertical axis. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the management method, measurement method, measurement device, quartz crystal sensor, and set of the present invention will be described in detail based on the preferred embodiments shown in the accompanying drawings. It should be noted that the drawings described below are illustrative for explaining the present invention, and the present invention is not limited to the drawings shown below. In the following, the symbol "~" indicating a numerical range includes the numerical values ​​written on both sides. For example, if ε is numerical value α to numerical value β, the range of ε includes numerical values ​​α and β, and expressed in mathematical notation, α≦ε≦β.

[0012] [Measuring equipment] FIG. 1 is a schematic diagram showing an example of a measuring device according to an embodiment of the present invention, and FIG. 2 is a schematic cross-sectional view showing a first example of a quartz crystal resonator sensor according to an embodiment of the present invention. 1 is a device for detecting impurities in a chemical solution containing an organic solvent. The measuring device 10 can be used to manage the purity of the target chemical solution. The measurement device 10 includes a flow cell unit 12, an oscillation section 14, a detection section 15, a calculation section 16, a memory 18, a supply section 20, and a control section 22. The measurement device 10 further includes a display section 23, an output section 24, and an input section 25. The control unit 22 controls the operations of the flow cell unit 12, the oscillation unit 14, the detection unit 15, the calculation unit 16, the memory 18, and the supply unit 20. The control unit 22 also controls the operations of the display unit 23 and the output unit 24, and controls each component of the measurement device 10 based on input information from the input unit 25.

[0013] The flow cell unit 12 has an adsorption layer 34 (see FIG. 2) that adsorbs impurities, a quartz oscillator sensor 26 including a quartz oscillator 27 (see FIG. 2), and a temperature adjustment unit 28 for maintaining the liquid temperature of the target liquid drug supplied to the flow cell unit 12. The flow cell unit 12 will be described in detail later.

[0014] The oscillator 14 is electrically connected to the crystal oscillator sensor 26. The oscillator 14 vibrates the crystal oscillator 27 at a resonant frequency. The oscillator 14 applies a sine wave high frequency signal as a frequency signal to the crystal oscillator sensor 26, and has an oscillation circuit (not shown). In addition, the detection unit 15 is electrically connected to the oscillation unit 14. The detection unit 15 measures the resonance frequency of the quartz crystal oscillator 27, and detects the amount of change in the resonance frequency of the quartz crystal oscillator due to contact with the target liquid drug. The detection unit 15 may detect the difference in the amount of change in multiple resonance frequencies obtained by using multiple adsorption layers, as described later.

[0015] The detection unit 15 receives the frequency signal from the oscillation unit 14, samples the frequency signal, for example, every second, and stores it as time-series data in the memory 18. The measurement time and the frequency allowable value are stored in the memory 18. The detection unit 15 measures the resonant frequency of the crystal oscillator 27 based on the measurement time and the frequency allowable value, and detects the amount of change in the resonant frequency of the crystal oscillator due to contact with the target chemical solution. The measurement time is the time required to obtain the amount of change in the resonant frequency caused by the contact of impurities with the adsorption layer 34. The measurement time is not particularly limited and is appropriately determined depending on the supply flow rate of the target chemical solution, etc., and is, for example, preferably 10 minutes or more, and more preferably 30 minutes or more. There is no particular upper limit, but from the viewpoint of productivity, it is preferably 3 hours or less, and more preferably 2 hours or less. The frequency tolerance is a threshold value for judging whether the value that serves as an index of frequency stabilization has become a sufficiently small value corresponding to stabilization when judging whether the frequency has stabilized. The frequency tolerance is set appropriately according to the set measurement sensitivity, for example. For example, when the resonant frequency is 30 MHz, the allowable error range in the measurement time when the measurement sensitivity is 5 Hz is set to, for example, 0.5 Hz. This corresponds to 0.0167 ppm. The allowable value corresponding to this error range is 1.67×10 -8 (0.0167 ppm) or less.

[0016] In the detection unit 15, the frequency is detected by, for example, a frequency counter, which is a known circuit. Alternatively, as described in, for example, JP-A-2006-258787, the frequency signal may be converted from analog to digital, processed by a carrier move to generate a rotation vector that rotates with the frequency of the frequency signal, and the speed of this rotation vector may be calculated to detect the frequency. In the detection unit 15, it is preferable to use such digital processing because it provides higher frequency detection accuracy.

[0017] The calculation unit 16 reads out the allowable range of the change in the resonant frequency based on the purity of the target liquid medicine, which is preset and stored in the memory 18, and compares the allowable range of the change in the resonant frequency stored in the memory 18 with the change in the resonant frequency obtained by the detection unit 15 to manage the purity of the liquid medicine. For example, if the purity of the liquid medicine is within the allowable range as a result of the above-mentioned comparison, the display unit 23 displays that the purity of the liquid medicine is within the allowable range. On the other hand, if the purity of the liquid medicine is beyond the allowable range, the display unit 23 displays that the purity of the liquid medicine is beyond the allowable range. In addition to this, if the purity of the liquid medicine is within the allowable range, the output unit 24 may output that the purity of the liquid medicine is within the allowable range. On the other hand, if the purity of the liquid medicine is beyond the allowable range, the output unit 24 may output that the purity of the liquid medicine is beyond the allowable range.

[0018] The memory 18 stores the above-mentioned preset amount of change in resonance frequency based on the purity of the target liquid drug and its allowable range. The memory 18 may also store the resonance frequency of the quartz crystal oscillator and the like. As described later, in a configuration in which a plurality of electrodes are provided on the quartz crystal oscillator, the resonance frequency for each electrode and the difference in resonance frequency between the electrodes may also be stored. The amount of change in the resonant frequency stored in the memory 18 can be obtained by, for example, obtaining a calibration curve L showing the relationship between the amount of impurities in a specific target chemical liquid and the resonant frequency of the crystal oscillator 27 as shown in FIG. 3, and based on this calibration curve L, the relationship between the amount of impurities in a specific target chemical liquid and the amount of change in the resonant frequency can be obtained. In addition, the allowable range of the amount of change in the resonant frequency can be set by setting an allowable range for the calibration curve L. The amount of impurities in the calibration curve L shown in FIG. 3 is, for example, the amount of impurities measured using a surface inspection device. More specifically, after applying a predetermined amount of the target chemical liquid to a predetermined substrate (e.g., a silicon wafer), the number of defects on the substrate to which the target chemical liquid has been applied can be measured using the surface inspection device, and the number of defects obtained can be regarded as the amount of impurities. An example of a surface inspection device is a device that detects impurities on a substrate by irradiating a laser beam onto the substrate coated with a target chemical solution and detecting the laser beam scattered by defects on the substrate. When irradiating the laser beam, the substrate is rotated while measuring, and the coordinate position of the defect can be calculated from the rotation angle of the substrate and the radial position of the laser beam. An example of such a device is the "SP-5" manufactured by KLA Tencor, but other surface inspection devices (typically successors to the "SP-5") that have a resolution equal to or higher than that of the "SP-5" may also be used.

[0019] The display unit 23 displays the amount of change in the resonance frequency obtained by the calculation unit 16, and is composed of, for example, a display. The display is not particularly limited as long as it can display characters and images, and a liquid crystal display device or the like is used. Moreover, what is displayed on the display unit 23 is not limited to the amount of change in the obtained resonance frequency, and may be the resonance frequency, or the difference in the amount of change in multiple resonance frequencies obtained by using multiple adsorption layers as described later, or various setting items and input information set in the measurement device 10 may be displayed. The output unit 24 displays the obtained change in resonance frequency or the resonance frequency on a medium. More specifically, for example, it displays using at least one of characters, symbols, and barcodes. The output unit 24 is composed of a printer or the like. The output unit 24 can provide an information display unit on which the resonance frequency information of the medicinal liquid of the set described below is displayed. The input unit 25 is an input device such as a mouse and a keyboard for inputting various information according to an instruction from an operator. For example, the measurement device 10 is set, data is retrieved from the memory 18, and the like, via the input unit 25. The input unit 25 also includes an interface for inputting information to be stored in the memory 18, and the information is stored in the memory 18 via an external storage medium or the like. Note that the measuring device 10 only needs to be able to obtain the amount of change in the resonant frequency, and does not necessarily need any other configuration than that for obtaining the amount of change in the resonant frequency. For this reason, for example, the calculation unit 16 is necessary in the management method, but is not necessarily required in the measuring device 10 that obtains the amount of change in the resonant frequency.

[0020] The flow cell unit 12 is a sensing unit that senses impurities in a chemical solution containing an organic solvent. The flow cell unit 12 is connected to the supply unit 20 using a first tube 29a and a second tube 29b. The supply unit 20 passes the target chemical solution through the first tube 29a, supplies the target chemical solution to the quartz crystal oscillator, and passes the target chemical solution through the second tube 29b to collect the target chemical solution. The supply unit 20 passes the target chemical solution through the first tube 29a and the second tube 29b without contacting the target chemical solution, and for example, a peristaltic pump is used. The supply unit 20 is not particularly limited as long as it can deliver the target chemical solution without contacting the target chemical solution, and for example, a syringe pump can be used. The temperature adjustment unit 28 has, for example, a Peltier element. The Peltier element maintains the temperature of the target liquid medicine. This allows the temperature of the target liquid medicine to be kept constant, and the viscosity of the target liquid medicine to be within a certain range. This reduces fluctuations in the purity measurement conditions. Note that there are no particular limitations on the configuration of the temperature adjustment unit 28, so long as it is possible to maintain the temperature of the target liquid medicine.

[0021] [Quartz Oscillator Sensor] As described above, the quartz oscillator sensor 26 has the quartz oscillator 27, which is, for example, disk-shaped, with an electrode 30 provided on a front surface 27a of the quartz oscillator 27 and an electrode 31 provided on a back surface 27b. An adsorption layer 34 that adsorbs impurities is provided on a surface 27a of the quartz crystal oscillator 27 and a surface 30a of the electrode 30. The adsorption layer 34 is brought into contact with a target chemical solution containing an organic solvent. For example, an AT-cut type quartz crystal oscillator is used as the quartz crystal oscillator 27. An AT-cut type quartz crystal oscillator is an oscillator cut at an angle of 35°15′ from the Z axis of an artificial quartz crystal. The quartz crystal oscillator sensor 26 is not limited to the configuration shown in FIG.

[0022] The oscillator 14 is electrically connected to the electrodes 30 and 31. The oscillator 14 applies a sine wave high frequency signal as a frequency signal to the electrodes 30 and 31, and has, for example, an oscillator circuit. The oscillator 14 causes the crystal oscillator 27 to vibrate at a resonant frequency. The resonant frequency of the crystal oscillator 27 is, for example, 27 MHz or 30 MHz. The adsorption layer 34 is made of at least one of the following materials: Si, Au, SiO2, SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, and a photosensitive resin composition. The type of impurity that is easily adsorbed varies depending on the material that makes up the adsorption layer. Therefore, for example, when the amount of impurities in the target chemical solution is determined by the above-mentioned surface inspection device and the number of defects is correlated with the amount of change in the resonance frequency, it is preferable that the substrate to which the chemical solution used to measure the number of defects by the surface inspection device is applied and the adsorption layer are made of the same material. In other words, when a Si layer is used as the adsorption layer, it is preferable to use a Si substrate (silicon wafer) as the substrate. The adsorption layer 34 can be formed by a vapor phase method such as a sputtering method or a CVD (chemical vapor deposition) method, or a coating method. The type of the photosensitive resin composition is not particularly limited, and may be any known photosensitive resin composition. The components contained in the photosensitive resin composition may include, for example, a resin having a group that generates a polar group by the action of an acid, and a photoacid generator. The photosensitive resin composition may further include a basic compound, a hydrophobic resin, etc.

[0023] In the quartz crystal oscillator sensor 26, the resonant frequency of the quartz crystal oscillator 27 changes depending on the amount of impurities adsorbed in the adsorption layer 34. The amount of change in the resonant frequency can be obtained by measuring the resonant frequency before and after contact with the target chemical solution. The amount of change ΔF in the resonant frequency of the quartz crystal oscillator 27 can be expressed by the following formula, known as the Sauerbrey formula. In the formula, F0 is the resonant frequency, Δm is the amount of mass change, ρ is the density of the quartz crystal, μ is the shear stress of the quartz crystal, and A is the area of ​​the electrodes. From the formula, it is possible to increase the mass detection sensitivity, i.e., the measurement accuracy of impurities, by increasing the resonant frequency F0 of the quartz crystal oscillator.

[0024]

number

[0025] [Flow cell unit] FIG. 4 is a schematic diagram showing an example of a flow cell unit of the measurement device according to an embodiment of the present invention. In the flow cell unit 12, for example, the quartz crystal sensor 26 is disposed on the temperature adjustment section 28 via a seal section 43. A seal section 42 is provided on the quartz crystal sensor 26 along the periphery of the quartz crystal 27. A block 40 is disposed on the seal section 42. The block 40 is provided with a supply path 40a for supplying the target chemical solution to the quartz crystal sensor 26. The supply path 40a is connected to a first tube 29a. The block 40 is also provided with a discharge path 40b for discharging the target chemical solution from the quartz crystal sensor 26. The discharge path 40b is connected to a second tube 29b. In other words, the flow cell unit 12 further includes a seal portion 42 arranged on the quartz oscillator sensor 26, a block 40 arranged on the quartz oscillator sensor 26 via the seal portion 42 and provided with a supply path 40a for supplying the target chemical liquid to the quartz oscillator sensor 26 and a discharge path 40b for discharging the target chemical liquid from the quartz oscillator sensor 26, and a liquid delivery portion consisting of a first tube 29a connected to the supply path 40a and a second tube 29b connected to the discharge path 40b. The target chemical solution that has passed through the first tube 29a and the supply path 40a is supplied to an area 44 that is surrounded by the quartz crystal sensor 26, the seal portion 42, and the block 40. That is, the seal portion 42 is disposed outside the area 44. This causes the target chemical solution to come into contact with the adsorption layer 34 on the surface 30a of the electrode 30 of the quartz crystal oscillator 27 of the quartz crystal sensor 26. The target chemical solution also passes through the discharge path 40b and the second tube 29b, and is discharged from the area 44. The first tube 29a and the discharge path 40b, and the second tube 29b and the discharge path 40b form a circulation line.

[0026] The movement of the target liquid medicine through the first tube 29a and the supply path 40a and the second tube 29b and the discharge path 40b is controlled by the supply unit 20 (see FIG. 1) as described above. For example, the seal portion 42 and the seal portion 43 are the same size and are formed of, for example, an O-ring. Note that the target liquid medicine is not supplied to an area 45 surrounded by the quartz crystal sensor 26, the seal portion 43, and the temperature adjustment portion 28. Furthermore, in the flow cell unit 12, by forming at least a part of the liquid contacting portion that comes into contact with the target chemical solution from a fluororesin, elution into the target chemical solution is suppressed, and deterioration of the purity measurement accuracy can be suppressed, which is preferable. In the measuring device 10, the surface forming the region 44 for holding the target chemical liquid on the crystal oscillator sensor 26, which is surrounded by the crystal oscillator sensor 26, the seal portion 42, and the block 40, corresponds to a part of the liquid contacting portion that contacts the target chemical liquid. In addition to the region 44, in the supply portion that brings the target chemical liquid into contact with the crystal oscillator sensor 26, the part in contact with the target chemical liquid in the liquid sending portion that sends the target chemical liquid to the crystal oscillator sensor is also a liquid contacting portion. It is preferable that at least a part of these liquid contacting portions is made of a fluororesin. That is, it is preferable that at least a part of the liquid contacting portion that contacts the target chemical liquid in the measuring device that senses impurities in a chemical liquid containing an organic solvent (the measuring device having the crystal oscillator sensor described above) is made of a fluororesin. Note that the above liquid contacting portion is preferably a liquid contacting portion other than the adsorption layer and the crystal oscillator. Examples of the liquid sending portion include a supply line that sends the liquid in one direction and a circulation line that circulates and supplies the target chemical liquid to the crystal oscillator sensor. 4, the liquid contacting parts are surface 40c in contact with region 44 of block 40 of flow cell unit 12, surface 42a which is a part in contact with region 44 of seal part 42 that keeps the target chemical liquid arranged on quartz crystal sensor 26 in region 44, supply path 40a of block 40, and discharge path 40b of block 40. In addition, the inside of first tube 29a and the inside of second tube 29b are also liquid contacting parts in contact with the target chemical liquid, and the parts of first tube 29a and second tube 29b in contact with the target chemical liquid are preferably made of fluororesin. In particular, it is preferable that at least a portion of the liquid contacting portion of the seal portion 42 that comes into contact with the target chemical liquid, the liquid contacting portion of the block 40 that comes into contact with the target chemical liquid, and the liquid contacting portion that comes into contact with the target chemical liquid are made of a fluororesin.

[0027] The fluororesin may be any resin containing fluorine atoms. The fluorine-based resin is not particularly limited as long as it is a resin (polymer) containing fluorine atoms, and known fluorine-based resins can be used. Examples of the fluorine-based resin include polytetrafluoroethylene (PTFE, tensile strength: 20 to 35 MPa, Shore D hardness: 50 to 55), perfluoroalkoxyalkane, polychlorotrifluoroethylene, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer, ethylene chlorotrifluoroethylene copolymer, perfluoroethylene propene copolymer, tetrafluoroethylene perfluoroalkyl vinyl ether copolymer, and cyclized polymer of perfluoro(butenyl vinyl ether) (Cytop (registered trademark)).

[0028] In particular, when the liquid contact portion (portion in contact with the target chemical liquid) of block 40 of flow cell unit 12 is made of a fluororesin, the tensile strength of the fluororesin is preferably 20-60 MPa. Also, the Shore D hardness of the fluororesin is preferably 60-80. The fluorine-based resin constituting the liquid-contacting portion of block 40 that comes into contact with the target chemical solution is preferably perfluoroalkoxyalkane (PFA, tensile strength: 25-35 MPa, Shore D hardness: 62-66), ethylene tetrafluoroethylene copolymer (ETFE, tensile strength: 38-42 MPa, Shore D hardness: 67-78), perfluoroethylene propene copolymer (FEP, tensile strength: 20-30 MPa, Shore D hardness: 60-65), polychlorotrifluoroethylene (PCTFE, tensile strength: 31-41 MPa, Shore D hardness: 75-80), or polyvinylidene fluoride (PVDF, tensile strength: 30-60 MPa, Shore D hardness: 64-79). The tensile strength is measured in accordance with JIS K 7161. The Shore D hardness is measured in accordance with JIS K 7215.

[0029] In addition, the fluororesin constituting the liquid contacting part (part in contact with the target liquid) of the liquid delivery part that delivers the target liquid to the region 44 preferably has a repeating unit containing fluorine atoms, carbon atoms, and other atoms other than fluorine atoms and carbon atoms (hereinafter, also simply referred to as a "specific repeating unit"). Examples of the other atoms include hydrogen atoms and chlorine atoms. In other words, the specific repeating unit preferably contains at least one other atom selected from the group consisting of fluorine atoms, carbon atoms, and hydrogen atoms and chlorine atoms. The fluororesin constituting the part of the liquid delivery section that comes into contact with the target liquid drug is preferably a ternary copolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV soft fluororesin), polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer, or polychlorotrifluoroethylene. The methods for measuring the tensile strength and Shore D hardness are as described above.

[0030] The portion of the seal portion 42 that contacts the target chemical liquid arranged on the quartz crystal sensor 26 and keeps the target chemical liquid in the region 44 (the surface 42a that contacts the region 44) is preferably made of a fluorine-based resin. The tensile strength of the fluororesin constituting the portion of the seal portion 42 that comes into contact with the target chemical liquid is preferably 20 to 40 MPa. The Shore D hardness of the fluororesin constituting the portion of the seal portion 42 that comes into contact with the target chemical liquid is preferably 56 to 70. The flexural modulus of the fluororesin constituting the portion of the seal portion 42 that comes into contact with the target chemical liquid is preferably 0.5 to 3 GPa. When the fluororesin constituting the portion of the sealing portion 42 that comes into contact with the target chemical liquid satisfies the above-mentioned tensile strength, Shore D hardness, and flexural modulus, it does not impede the vibration of the quartz crystal sensor 26, and more stable measurements can be performed. The methods for measuring the tensile strength and Shore D hardness are as described above. The flexural modulus is measured in accordance with JIS K 7171. The fluorine-based resin constituting the portion of the seal portion 42 that comes into contact with the target chemical liquid is preferably perfluoroalkoxyalkane, perfluoroethylenepropene copolymer, ethylene chlorotrifluoroethylene copolymer, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene, or polyvinylidene fluoride.

[0031] The supply unit 20 circulates the target liquid medicine using the first tube 29a and the second tube 29b, but is not limited to this and may be a system in which the target liquid medicine flows in one direction. In this case, for example, a syringe pump can be used. When the target chemical liquid is circulated and supplied to the quartz crystal oscillator 27, the circulation flow rate of the target chemical liquid is preferably 0.01 to 1000 ml / s. If the circulation flow rate is 0.01 to 1000 ml / s, a sufficient amount of impurities for detection can be attached to the surface of the adsorption layer 34. It is preferable that the increase in impurities when the target chemical solution is circulated for one hour be 1000 mass ppt or less, since this does not decrease the accuracy of the purity measurement. The arrangement of the crystal oscillator sensor 26 in the flow cell unit 12 is not particularly limited.

[0032] [Management method] Next, a method for detecting impurities in a chemical solution containing an organic solvent and controlling the purity of the chemical solution will be described. The management method includes a step 1 of preparing a target chemical solution containing an organic solvent, a step 2 of contacting the target chemical solution with a quartz oscillator sensor including a quartz oscillator and an adsorption layer that adsorbs impurities (in a measuring device that senses impurities in the chemical solution containing an organic solvent) and obtaining a change in resonant frequency of the quartz oscillator due to contact with the target chemical solution, and a step 3 of managing the purity of the chemical solution by comparing whether the obtained change in resonant frequency is within a preset allowable range of a change in resonant frequency based on the purity of the target chemical solution. As shown in the above-mentioned measuring device 10, in step 2, at least a part of the liquid-contacting portion of the measuring device 10 that comes into contact with the target chemical liquid is made of a fluorine-based resin. In the management method, the target liquid medicine is sent to the quartz crystal sensor and brought into contact with the quartz crystal sensor, as in the above-mentioned measuring device. The target liquid medicine may be made to flow in one direction to the quartz crystal sensor and adhere to the quartz crystal sensor. The target liquid medicine may be circulated and supplied to the quartz crystal sensor, and the circulating flow rate of the target liquid medicine may be set to 0.01 to 1000 ml / s.

[0033] The management method will be described in more detail below, taking as an example the measurement device 10 shown in Fig. 1. In the management method, for example, the target chemical solution is circulated and supplied. As described above, a target chemical solution containing an organic solvent to be controlled in purity is prepared (step 1), and the target chemical solution is stored in the supply unit 20 of the measurement device 10. The target chemical solution contains impurities. Next, the target chemical solution is passed from the supply unit 20 through the first tube 29a and the supply path 40a of the block 40 to the flow cell unit 12, and then passed through the discharge path 40b of the block 40 and the second tube 29b to return to the supply unit 20, and then passed through the first tube 29a and the supply path 40a of the block 40 again to be supplied to the region 44. This process is repeated. The target chemical solution is circulated and supplied to the quartz crystal oscillator 27, and brought into contact with the adsorption layer 34 of the quartz crystal oscillator 27.

[0034] A sine wave high frequency signal is applied from the oscillator 14 to the crystal oscillator sensor 26 as a frequency signal, and the crystal oscillator 27 is vibrated at the resonant frequency before the target liquid medicine is supplied, and the detection unit 15 obtains the resonant frequency before the supply of the target liquid medicine. Thereafter, for example, the target liquid medicine is supplied to the crystal oscillator 27 for a predetermined time, and then the detection unit 15 obtains the resonant frequency and obtains the amount of change in the resonant frequency (step 2). In other words, the amount of change in the resonant frequency can be obtained by implementing the method for measuring the liquid medicine having steps 1 and 2. The amount of change in the resonant frequency obtained by the detection unit 15 is output to the calculation unit 16, and stored in the calculation unit 16. The calculation unit 16 reads out the allowable range of the amount of change in the resonant frequency based on the purity of the target liquid drug, which is preset and stored in the memory 18, and compares the allowable range of the amount of change in the resonant frequency stored in the memory 18 with the amount of change in the resonant frequency obtained by the detection unit 15 to manage the purity of the liquid drug (step 3). For example, if the above comparison shows that the purity of the liquid drug is within the allowable range, the display unit 23 displays that the purity of the liquid drug is within the allowable range. On the other hand, if the purity of the liquid drug is beyond the allowable range, the display unit 23 displays that the purity of the liquid drug is beyond the allowable range. In the control method, the purity of the liquid medicine can be easily obtained, and the purity of the target liquid medicine can be controlled based on the obtained purity, thereby making it possible to control the quality of the liquid medicine. The amount of change in the resonant frequency stored in the memory 18 and its allowable range can be obtained, for example, based on the calibration curve L shown in FIG. 3 as described above. The above-mentioned management method is preferably carried out in a clean room. More specifically, it is preferably carried out in a clean room that satisfies the cleanliness class 2 or higher defined in the international standard ISO14644-1:2015 established by the International Organization for Standardization.

[0035] [Other examples of quartz crystal sensors] Fig. 5 is a schematic diagram showing a second example of a quartz oscillator sensor according to an embodiment of the present invention, and Fig. 6 is a schematic cross-sectional view showing the second example of the quartz oscillator sensor according to an embodiment of the present invention. Fig. 7 is a schematic diagram showing a third example of a quartz oscillator sensor according to an embodiment of the present invention, and Fig. 8 is a schematic cross-sectional view showing the third example of the quartz oscillator sensor according to an embodiment of the present invention. In the quartz oscillator sensor 26 shown in Figs. 4 to 8, the same components as those in the quartz oscillator sensor 26 shown in Fig. 2 are denoted by the same reference numerals, and detailed description thereof will be omitted. The quartz crystal sensor 26 shown in FIG. 2 has one electrode 30 on the surface 27a of the quartz crystal oscillator 27, but is not limited thereto. As shown in FIG. 5 and FIG. 6, the quartz crystal sensor 26 may have a first electrode 50 and a second electrode 51 on the surface 27a of the quartz crystal oscillator 27. The first electrode 50 and the second electrode 51 are, for example, rectangular conductive layers and are arranged parallel to each other with a gap therebetween. The first electrode 50 and the second electrode 51 are electrically insulated from each other. A first adsorption layer 35 is provided on the surface 50a of the first electrode 50, and a second adsorption layer 36 is provided on the surface 51a of the second electrode 51.

[0036] The first electrode 50 and the electrode 31 are electrically connected to the first oscillation unit 14a. The second electrode 51 and the electrode 31 are electrically connected to the second oscillation unit 14b. The first oscillation unit 14a and the second oscillation unit 14b are provided in the oscillation section 14, and a sine wave high frequency signal can be applied as a frequency signal to the first electrode 50 and the electrode 31, and the second electrode 51 and the electrode 31, independently of each other, thereby vibrating the crystal oscillator 27 at a resonant frequency. Moreover, the first oscillation unit 14a and the second oscillation unit 14b are each electrically connected to the detection unit 15. The detection unit 15 has a switch unit (not shown) that switches the connection between the first oscillation unit 14a and the second oscillation unit 14b. The frequency signal of the first oscillation unit 14a and the frequency signal of the second oscillation unit 14b are alternately input to the detection unit 15 by the switch unit. This allows the detection unit 15 to obtain the resonant frequency of the first electrode 50 and the resonant frequency of the second electrode 51 independently of each other.

[0037] The first adsorption layer 35 on the surface 50a of the first electrode 50 and the second adsorption layer 36 on the surface 51a of the second electrode 51 may be the same or different from each other. When the first adsorption layer 35 and the second adsorption layer 36 are different, the purity can be easily estimated by using the difference in the resonance frequency between the first electrode 50 and the second electrode 51 and depending on whether the difference is included in the allowable range of the change in the resonance frequency based on the purity of the target liquid drug that is set in advance. This makes it easier to obtain the purity of the liquid drug, makes it easier to manage the purity, and makes it easier to manage the quality of the liquid drug. It is preferable that at least one of the first adsorption layer 35 and the second adsorption layer 36 is an Au layer. By using an Au layer, one of the first electrode 50 and the second electrode 51 can be used as a reference electrode.

[0038] 7 and 8, an electrode 52 may be provided on the surface 27a of the crystal unit 27. The electrode 52 has a first electrode portion 52a, a second electrode portion 52b, and a connecting portion 52c that connects the first electrode portion 52a and the second electrode portion 52b at one end. The first electrode portion 52a and the second electrode portion 52b are, for example, formed of a rectangular conductive layer, and are arranged parallel to each other with a gap therebetween. The first electrode portion 52a and the second electrode portion 52b are electrically connected. An adsorption layer 34 is provided on the electrode 52.

[0039] The first electrode portion 52a and the electrode 31 are electrically connected to the first oscillation unit 14a. The second electrode portion 52b and the electrode 31 are electrically connected to the second oscillation unit 14b. The first oscillation unit 14a and the second oscillation unit 14b are provided in the oscillation unit 14, and can apply a sine wave high frequency signal as a frequency signal to the first electrode 50 and the electrode 31, and the second electrode 51 and the electrode 31, independently of each other, thereby vibrating the crystal oscillator 27 at a resonant frequency. In addition, the first oscillation unit 14a and the second oscillation unit 14b are each electrically connected to the detection unit 15. The detection unit 15 has a switch unit (not shown) that switches the connection between the first oscillation unit 14a and the second oscillation unit 14b. The frequency signal of the first oscillation unit 14a and the frequency signal of the second oscillation unit 14b are alternately input to the detection unit 15 by the switch unit. This allows the detection unit 15 to obtain the resonant frequency of the first electrode portion 52a and the resonant frequency of the second electrode portion 52b independently of each other.

[0040] In the quartz crystal sensor 26 shown in FIG. 8, the adsorption layer 34 is provided on the first electrode portion 52a and the second electrode portion 52b, but the first electrode portion 52a and the second electrode portion 52b may have different resonant frequencies. In the case where the first electrode portion 52a and the second electrode portion 52b have different resonant frequencies, the purity can be easily estimated by using the difference in resonant frequency between the first electrode portion 52a and the second electrode portion 52b. This makes it possible to easily obtain the purity of the liquid medicine, and to easily manage the purity and the quality of the liquid medicine. It is preferable to form an Au layer on at least one of the first electrode portion 52a and the second electrode portion 52b. By forming the Au layer, one of the first electrode portion 52a and the second electrode portion 52b can be used as a reference electrode.

[0041] [set] As a method of indicating the quality of a liquid medicine, the purity measured by the above-mentioned measuring device 10 or the like is associated with the liquid medicine, thereby making it possible to easily manage the quality of the liquid medicine. Such an association between a liquid medicine and its purity is called a set. The set includes a liquid medicine and an information display unit that displays or stores resonant frequency information of the liquid medicine. The amount of change in the resonant frequency of the quartz oscillator caused by contacting the liquid medicine with a quartz oscillator sensor including an adsorption layer that adsorbs impurities in the liquid medicine and a quartz oscillator is obtained, and the amount of change in the resonant frequency obtained is compared with an amount of change in the resonant frequency based on a preset purity of the liquid medicine, and an evaluation of the purity of the liquid medicine is given for the amount of change in the resonant frequency obtained. The amount of change in the resonant frequency obtained based on the evaluation is associated with the purity of the liquid medicine and recorded as resonant frequency information of the liquid medicine, and the resonant frequency information of the liquid medicine is used to obtain information on the purity of the liquid medicine. The information on the purity of the liquid medicine can be obtained from the resonant frequency information of the liquid medicine. The above evaluation is given by measuring the purity of the liquid chemical using the measuring device 10 described above.

[0042] The set will be described in more detail below. Fig. 9 is a schematic perspective view showing an example of the set according to the embodiment of the present invention, and Fig. 10 is a schematic view showing an example of the information display section of the set according to the embodiment of the present invention. 9, the set 60 has a container 64 that stores, for example, a liquid medicine 62 in an interior 64a. The container 64 is, for example, cylindrical, and has an information display unit 66 provided on a side surface 64b. The information display unit 66 may be provided on an upper surface 64c. The information display unit 66 displays or stores resonance frequency information of the liquid medicine. 10, the information display unit 66 displays the resonant frequency information of the liquid medicine using characters. However, this is not limited to this, and the resonant frequency information of the liquid medicine can be displayed on the information display unit 66 using at least one of characters, symbols, and barcodes. The barcode is not particularly limited, and may be a secondary code.

[0043] The information display unit 66 is not limited to displaying characters as shown in Fig. 10, and may be, for example, an information recording medium such as an IC (integrated circuit) tag. In the case of an IC tag, the resonant frequency information of the liquid medicine can be read in a non-contact manner using an IC tag reader. By making the information display unit 66 a barcode or an IC tag, for example, it is possible to manage the quality of the liquid medicine using a reader. The information display section 66 on which the resonant frequency information of the liquid medicine is displayed can be obtained by the output section 24 of the measuring device 10 .

[0044] The management method, measurement method, measurement device, quartz crystal sensor, and set of the present invention are basically configured as described above. Although the management method, measurement method, measurement device, quartz crystal sensor, and set of the present invention have been described in detail above, the present invention is not limited to the above-mentioned embodiment, and various improvements and modifications may be made without departing from the spirit of the present invention.

[0045] The subject chemical solution used in the present invention (hereinafter, simply referred to as "chemical solution") contains an organic solvent. In this specification, the organic solvent refers to a liquid organic compound contained in an amount exceeding 10,000 ppm by mass per component relative to the total mass of the chemical solution. In other words, in this specification, a liquid organic compound contained in an amount exceeding 10,000 ppm by mass relative to the total mass of the chemical solution corresponds to an organic solvent. In addition, in this specification, the term "liquid" means that the material is liquid at 25° C. and atmospheric pressure.

[0046] The content of the organic solvent in the chemical solution is not particularly limited, but is preferably 98.0% by mass or more, more preferably more than 99.0% by mass, even more preferably 99.90% by mass or more, and particularly preferably more than 99.95% by mass, based on the total mass of the chemical solution. The upper limit is less than 100% by mass. The organic solvent may be used alone or in combination of two or more. When two or more organic solvents are used, the total content is preferably within the above range.

[0047] The type of organic solvent is not particularly limited, and known organic solvents can be used. Examples of the organic solvent include 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 carbonate, alkyl alkoxyacetate, alkyl pyruvate, dialkyl sulfoxide, cyclic sulfone, dialkyl ether, monohydric alcohol, glycol, alkyl acetate, and N-alkylpyrrolidone.

[0048] The organic solvent is preferably at least one selected from the group consisting of, 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-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, and 2-heptanone. Examples of using two or more organic solvents include a combined use of PGMEA and PGME, and a combined use of PGMEA and PC. The type and content of the organic solvent in the chemical solution can be measured using a gas chromatograph mass spectrometer.

[0049] The chemical solution may contain impurities other than the organic solvent. As described above, the resonant frequency changes when the impurities are adsorbed on the adsorption layer. The impurities include metallic impurities and organic impurities. The metal impurities refer to metal ions and metal impurities contained in the chemical solution as solids (such as simple metals and particulate metal-containing compounds). The type of metal contained in the metal impurities is not particularly limited, and examples include Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Al (aluminum), Cr (chromium), Ni (nickel), Ti (titanium), and Zn (zirconium). The metal impurities may be components that are inevitably contained in each component (raw material) contained in the chemical solution, or may be components that are inevitably contained during the production, storage, and / or transportation of the chemical solution, or may be intentionally added. When the chemical solution contains metal impurities, the content thereof is not particularly limited, and may be 0.01 to 500 ppt by mass relative to the total mass of the chemical solution.

[0050] In this specification, the organic impurity refers to a compound different from the organic solvent, which is the main component contained in the chemical solution, and is an organic substance contained in an amount of 10,000 ppm by mass or less relative to the total mass of the chemical solution. In other words, in this specification, an organic substance contained in an amount of 10,000 ppm by mass or less relative to the total mass of the chemical solution corresponds to an organic impurity, but does not correspond to an organic solvent. In addition, when organic impurities consisting of multiple types of compounds are contained in a chemical solution, if each compound corresponds to the above-mentioned organic matter contained in an amount of 10,000 mass ppm or less, each of the compounds corresponds to an organic impurity. Water is not included in the organic impurities.

[0051] The organic impurities may be added to the chemical solution, or may be mixed into the chemical solution unavoidably during the manufacturing process of the chemical solution. Examples of the organic impurities being mixed into the chemical solution unavoidably during the manufacturing process of the chemical solution include, but are not limited to, the organic impurities being contained in the raw materials (e.g., organic solvents) used in the manufacturing process of the chemical solution, and the organic impurities being mixed into the chemical solution during the manufacturing process of the chemical solution (e.g., contamination). The total content of organic impurities in the chemical solution is not particularly limited, but may be 0.1 to 5000 ppm by mass relative to the total mass of the chemical solution. The organic impurities may be used alone or in combination of two or more. When two or more organic impurities are used in combination, the total content is preferably within the above range.

[0052] Examples of organic impurities include antioxidants such as dibutylhydroxytoluene (BHT), distearyl thiodipropionate (DSTP), 4,4'-butylidenebis-(6-t-butyl-3-methylphenol), 2,2'-methylenebis-(4-ethyl-6-t-butylphenol), and antioxidants described in JP 2015-200775 A; unreacted raw materials; structural isomers and by-products generated during the production of organic solvents; leachates from components constituting an organic solvent production apparatus (for example, plasticizers leachate from rubber components such as O-rings); and the like.

[0053] The chemical liquid 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 mixed into the chemical solution unavoidably during the manufacturing process of the chemical solution. Examples of cases where water is mixed into the chemical solution unavoidably during the manufacturing process of the chemical solution include cases where water is contained in a raw material (e.g., an organic solvent) used in the manufacturing of the chemical solution, and cases where water is mixed into the chemical solution during the manufacturing process (e.g., contamination).

[0054] The water content in the chemical solution is not particularly limited, but in general, it is preferably 2.0 mass % or less, more preferably 1.0 mass % or less, and even more preferably less than 0.5 mass %, based on the total mass of the chemical solution. If the water content in the chemical solution is 1.0 mass % or less, the manufacturing yield of semiconductor chips will be superior. Although there is no particular lower limit, it is often about 0.01% by mass, since it is difficult to keep the water content below the above limit in manufacturing.

[0055] The method for preparing the above-mentioned chemical solution is not particularly limited, and examples thereof include procuring an organic solvent by purchase or the like, and reacting raw materials to obtain an organic solvent. It is preferable to prepare a chemical solution with a low content of impurities as described above (for example, an organic solvent content of 99% by mass or more). Examples of commercially available products of such organic solvents include those called "high purity grade products." If necessary, the chemical solution may be subjected to a purification treatment. Purification methods include, for example, distillation and filtration. EXAMPLES

[0056] The present invention will be described in more detail below based on examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0057] <Example A> [Production of drug solutions] First, the chemical solutions used in the examples described below were prepared. Specifically, first, high-purity grade organic solvent reagents with a purity of 99% by mass or more were purchased. Then, the purchased reagents were subjected to a filtration process using an appropriate combination of the following filters to prepare chemical solutions (A1 to A20, B1 to B7, C1 to C5, D1 to D5, E1 to E7) with different amounts of impurities. IEX-PTFE(15nm): 15nm IEX PTFE manufactured by Entegris PTEE(12nm): 12nm PTFE manufactured by Entegris UPE(3nm): 3nm PE filter manufactured by Entegris In order to adjust the amount of impurities in the chemical solutions described below, the source of purchase of the organic solvent reagent was changed, the purity grade was changed, or a distillation process was performed before the above-mentioned filtration process, as appropriate.

[0058] [Evaluation using a quartz crystal sensor (part 1)] A quartz crystal sensor (see Figure 2) with a Si layer formed as an adsorption layer on the electrode part was prepared, and the quartz crystal sensor was immersed for 60 minutes in the chemical solution shown in Table 1 below, and the final change in the resonance frequency of the quartz crystal was determined (Hz). The resonance frequency of the quartz crystal sensor before immersion in the chemical solution was 27 MHz. The results are summarized in Table 1.

[0059] [Evaluation using surface inspection equipment (part 1)] First, a silicon wafer having a diameter of about 300 mm (12 inches) was prepared. Next, a surface inspection device (SP-5; manufactured by KLA Tencor) was used to count the number of defects present on the silicon wafer (this was taken as the initial value). Next, each chemical solution was spin-coated onto a silicon wafer at 1500 rpm using a Tokyo Electron "CLEAN TRACK LITHIUS (trade name)", and then the silicon wafer was spin-dried. Next, the number of defects present on the silicon wafer after the chemical solution was applied was measured using the above-mentioned surface inspection device (this was taken as the measured value). The difference between the initial value and the measured value (measured value - initial value) was then calculated to obtain the number of defects. This number of defects represents the amount of impurities in the chemical solution remaining on the silicon wafer, and a smaller value means a smaller amount of impurities in the chemical solution. The results are summarized in Table 1. The above evaluation was carried out in a clean room that met the cleanliness class 2 or higher specified in the international standard ISO14644-1:2015 established by the International Organization for Standardization.

[0060] In Table 1, the "chemical solution" column indicates the chemical solution used in each example. For example, in Example 1, chemical solutions A1 to A20 containing nBA (butyl acetate) were used, and the amounts of impurities differ between chemical solutions A1 to A20. The symbols of the chemicals in Table 1 represent the following chemicals. nBA: butyl acetate MIBC: 4-methyl-2-pentanol PGMEA: Propylene glycol monomethyl ether acetate IPA: Isopropanol CHN: Cyclohexanone

[0061] [Table 1]

[0062] As shown in Table 1, there is a correlation between the amount of change in resonance frequency and the number of defects, and when the amount of change in resonance frequency is large, the number of defects tends to increase. In addition, as shown in FIG. 3, the points for the amount of change in resonance frequency (evaluation by the quartz crystal sensor (amount of change in resonance frequency (Hz))) and the number of defects (evaluation by the surface inspection device (number of defects)) for all of the chemical solutions in Examples 1 to 5 are plotted on an orthogonal coordinate system with the amount of change in resonance frequency on the horizontal axis and the number of defects on the vertical axis. A calibration curve passing through the plotted points is created by the least squares method, and the coefficient of determination (R 2 ) was calculated to be 0.8004 (see Figure 11). The closer the coefficient of determination is to 1.000, the better the results are. The results in Table 1 show that there is a high correlation between the amount of change in resonant frequency and the number of defects.

[0063] In addition, the change in resonant frequency was measured following the same procedures as in Examples 1 to 5 above, except that the evaluation using a quartz crystal sensor (part 1) was performed in a clean room that met the cleanliness level of Class 2 or higher as defined in the international standard ISO14644-1:2015 established by the International Organization for Standardization, and that the temperature of the chemical solution was adjusted to 23°C. Table 2 shows the obtained results of the change in resonance frequency and the [evaluation using a surface inspection device] obtained above.

[0064] [Table 2]

[0065] The points for the amount of change in resonance frequency (evaluation by the quartz crystal sensor (amount of change in resonance frequency (Hz))) and the number of defects (evaluation by the surface inspection device (number of defects)) for all of the chemical solutions in Examples 6 to 10 were plotted on an orthogonal coordinate system with the amount of change in resonance frequency on the horizontal axis and the number of defects on the vertical axis, and a calibration curve passing through the plotted points was created by the least squares method, and the coefficient of determination (R 2 ) was calculated to be 0.9626. The results in Table 2 are better than those in Table 1.

[0066] <Example B> Following the same procedure as in Example A above, the chemical solutions used in each example (A21-A40, B8-B14, C6-C10, D6-D10, E8-E14) were prepared. The amount of impurities in each chemical solution was different. The impurity concentration in the chemical solution was obtained by LC / MS as the integral value of the peaks of all components except the main chemical solution, and the concentration was obtained in n-hexane equivalent.

[0067] [Evaluation using a quartz crystal sensor (part 2)] A quartz crystal sensor in which the adsorption layer shown in FIG. 2 is each layer (Si layer, SiO2 layer, SiOC layer, Cu layer, Co layer, Ti layer, W layer, TiN layer, Ta layer, TaN layer) shown in Table 3 was prepared, and each liquid medicine (A21 to A40, B8 to B14, C6 to C10, D6 to D10, E8 to E14) was brought into contact with the quartz crystal sensor using a measuring device (see FIG. 1) having a flow cell unit shown in FIG. 4 having the above quartz crystal sensor, and the amount of change in the resonant frequency of the quartz crystal was evaluated. Specifically, the temperature of the liquid medicine was adjusted to 23°C by a temperature adjustment unit, and the amount of change in the resonant frequency of the quartz crystal was obtained when each liquid medicine was circulated in the flow cell unit at a circulation flow rate of 20 ml / s for 60 minutes. The resonant frequency of the quartz crystal sensor before contact with the liquid medicine was 27 MHz. The results are summarized in Tables 3 to 7. The above evaluation was carried out in a clean room that met the cleanliness class 2 or higher specified in the international standard ISO14644-1:2015 established by the International Organization for Standardization. In addition, the liquid contact parts of each component of the flow cell unit in the above-mentioned resonant frequency measurement device (liquid contact parts of the block, seal part, and liquid contact parts of the liquid delivery part) were made of a fluorine-based resin similar to that of Example 24 described later.

[0068] [Evaluation using surface inspection equipment (part 2)] First, various substrates (Si substrate, SiO2 substrate, SiOC substrate, Cu substrate, Co substrate, Ti substrate, W substrate, TiN substrate, Ta substrate, and TaN substrate) were prepared. Next, the number of defects present on each substrate was counted (this was taken as the initial value) using a wafer surface inspection device (SP-5; manufactured by KLA Tencor). Next, using "CLEAN TRACK LITHIUS (product name)" manufactured by Tokyo Electron Ltd., each chemical solution (A21 to A40, B8 to B14, C6 to C10, D6 to D10, E8 to E14) was spin-coated onto the substrate at 1500 rpm, and then the substrate was spin-dried. Next, using the above-mentioned device (SP-5), the number of defects present on the substrate after the chemical solution was applied was counted (this was taken as the measured value). Next, the difference between the initial value and the measured value (measured value - initial value) was calculated and taken as the number of defects. The results are summarized in Tables 3 to 7. The above evaluation was carried out in a clean room that met the cleanliness class 2 or higher specified in the international standard ISO14644-1:2015 established by the International Organization for Standardization.

[0069] Tables 3 to 7 show the results of using the same metal adsorption layer and substrate. For example, the "Si" column in Table 3 shows the results of [Evaluation using a quartz crystal sensor (part 2)] using a "Si layer" as the adsorption layer and the results of [Evaluation using a surface inspection device (part 2)] using a Si substrate.

[0070] [Table 3]

[0071] [Table 4]

[0072] [Table 5]

[0073] [Table 6]

[0074] [Table 7]

[0075] As shown in the table above, when an adsorption layer and a substrate made of the same type of metal were used, there was a high correlation between the change in resonant frequency and the number of defects, and the number of defects tended to increase when the change in resonant frequency was large.

[0076] <Example C> Except for using an Au layer instead of a Si layer, [Evaluation using a quartz crystal sensor (part 2)] The change in the resonant frequency was measured according to the same procedure as described above. Next, the amount of change in resonance frequency obtained using the Au layer was subtracted from the amount of change in resonance frequency obtained using the Si layer to obtain the difference. The results are shown in Table 8.

[0077] In Table 8, the "Si layer - Au layer" column shows the difference obtained by subtracting the "Crystal oscillator sensor evaluation (resonant frequency change (Hz))" in the "Au layer" column from the "Crystal oscillator sensor evaluation (resonant frequency change (Hz))" in the "Si layer" column.

[0078] [Table 8]

[0079] The points for the amount of change in resonance frequency (evaluated by the quartz crystal sensor (amount of change in resonance frequency (Hz))) and the number of defects (evaluated by the surface inspection device (number of defects)) in the "Si layer" column of Examples 16 to 20 are plotted on an orthogonal coordinate system with the amount of change in resonance frequency on the horizontal axis and the number of defects on the vertical axis, and a calibration curve passing through the plotted points is created by the least squares method, and the coefficient of determination (R 2 ) was calculated to be 0.9915. In addition, the points for the difference in the amount of change in the resonance frequency in the "Si layer - Au layer" column of Examples 16 to 20 and the number of defects in the "Si layer" column (surface inspection device evaluation (number of defects)) were plotted, and a calibration curve passing through the plotted points was created by the least squares method, and the coefficient of determination (R 2 ) was calculated to be 0.996. From the above results, it was confirmed that when the Au layer was used as a reference, there was a higher correlation between the amount of change in resonant frequency and the number of defects.

[0080] <Example D> Following the same procedure as in Example A above, the chemical solutions (A41 to A140) used in each example were prepared.

[0081] A quartz crystal sensor having a Si layer as shown in FIG. 2 was prepared, and a measuring device (see FIG. 1) having a flow cell unit as shown in FIG. 4 having the above quartz crystal sensor was used to bring the liquid medicines (A41 to A140) into contact with the quartz crystal sensor, and to evaluate the amount of change in the resonant frequency of the quartz crystal. Specifically, the liquid medicine temperature was adjusted to 23°C by a temperature adjustment unit, and each liquid medicine was circulated in the flow cell unit at a circulation flow rate of 20 ml / s for 60 minutes, and the amount of change (Hz) in the resonant frequency of the quartz crystal was obtained. The resonant frequency of the quartz crystal before contact with the liquid medicine was 27 MHz. In the measuring device used, at least a part of the liquid-contacting portion was made of a fluorine-based resin. Specifically, if the liquid-contacting part (the part that comes into contact with the target chemical solution) of the block of the flow cell unit shown in Figure 4 is made of perfluoroethylene propene copolymer (FEP, tensile strength: 20 to 30 MPa, Shore D hardness: 60 to 65, flexural modulus: 0.55 to 0.67 GPa), the "Flow cell" column in Tables 9 to 10 is marked "Yes," and if it is not made of fluorine-based resin, it is marked "-." In addition, if the liquid-contacting part of the liquid delivery part (the part that comes into contact with the target chemical liquid) is made of THV soft fluororesin, the "Liquid delivery part" column in Tables 9 to 10 will be marked "Yes," and if it is not made of fluororesin, it will be marked "-." In addition, if the liquid-contacting part (the part in contact with the target chemical liquid) of the seal part that keeps the target chemical liquid within the area shown in Figure 4 is made of polyvinylidene fluoride (PVDF, tensile strength: 30 to 60 MPa, Shore D hardness: 64 to 79), the ``Seal Part A'' column in Tables 9 to 10 will be marked ``Yes,'' and if it is not made of the above-mentioned fluorine-based resin, it will be marked ``-.'' Furthermore, if the liquid-contacting part (the part in contact with the target chemical liquid) of the seal part that keeps the target chemical liquid within the area shown in Figure 4 is made of perfluoroalkoxyalkane (PFA, tensile strength: 25 to 35 MPa, Shore D hardness: 62 to 66), the ``Seal part B'' column in Tables 9 to 10 is marked ``Yes,'' and if the liquid-contacting part of the seal part is not made of fluorine-based resin, it is marked ``-.''

[0082] In addition, when measuring the amount of change in the resonant frequency, the amount of impurities eluted from the measuring device into the target chemical solution was measured using LC / MS (Thermo LC / MS QE plus).

[0083] [Table 9]

[0084] [Table 10]

[0085] As shown in Tables 9 and 10 above, in Examples 21 to 24, in which at least a portion of the liquid-contacting part of the measuring device with the target chemical liquid is made of a fluororesin, the amount of impurities eluted from the measuring device is smaller than in Example 25, in which a fluororesin is not used. As a result, it was confirmed that there is a higher correlation between the change in resonant frequency and the number of defects. The points for the amount of change in resonance frequency (evaluation by the quartz crystal sensor (amount of change in resonance frequency (Hz))) and the number of defects (evaluation by the surface inspection device (number of defects)) in Example 21 are plotted on an orthogonal coordinate system with the amount of change in resonance frequency on the horizontal axis and the number of defects on the vertical axis, and a calibration curve passing through the plotted points is created by the least squares method, and the coefficient of determination (R 2 ) was calculated to be 0.7318. The coefficients of determination were also calculated for Examples 22 to 25, and were 0.8086, 0.9843, 0.9936, and 0.3297, respectively. From these results, it was confirmed that Examples 21 to 24, in which at least a part of the liquid-contacting part of the measuring device was made of a fluororesin, showed a better correlation than Example 25, in which the liquid-contacting part of the measuring device was not made of a fluororesin.

[0086] In Example 23, when the resin constituting the liquid-contacting part (part contacting the target chemical solution) of the block shown in Figure 4 of the flow cell unit was changed from perfluoroethylene propene copolymer to perfluoroalkoxyalkane, ethylene tetrafluoroethylene copolymer, perfluoroethylene propene copolymer, polychlorotrifluoroethylene, or polyvinylidene fluoride, it was confirmed that all of them showed a correlation coefficient exceeding 0.95. However, these results were slightly inferior to the result of Example 23 (0.984). In addition, in Example 23, when the resin constituting the liquid-contacting part of the liquid delivery part (the part that comes into contact with the target chemical liquid) was changed from THV soft fluororesin to polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer, or polychlorotrifluoroethylene, it was confirmed that all of them showed a correlation coefficient exceeding 0.95. However, these results were slightly inferior to the result of Example 23 (0.984). In addition, in Example 23, when the resin constituting the liquid-contacting part (part in contact with the target chemical liquid) of the seal part that keeps the target chemical liquid in the area shown in Figure 4 was changed from polyvinylidene fluoride to perfluoroethylene propene copolymer, ethylene chlorotrifluoroethylene copolymer, ethylene tetrafluoroethylene copolymer, or polychlorotrifluoroethylene, it was confirmed that all of them showed a correlation coefficient exceeding 0.95. However, these results were slightly inferior to the result of Example 23 (0.984).

[0087] In Example 23, when any of the resin constituting the liquid-contacting part (part in contact with the target chemical liquid) of the block shown in Figure 4 of the flow cell unit, the resin constituting the liquid-contacting part (part in contact with the target chemical liquid) of the liquid delivery part, and the resin constituting the liquid-contacting part (part in contact with the target chemical liquid) of the seal part that keeps the target chemical liquid in its area shown in Figure 4 was changed to polytetrafluoroethylene, a correlation coefficient of more than 0.85 and less than 0.95 was obtained. These results confirmed that better effects could be obtained when a fluorine-based resin other than the above-mentioned polytetrafluoroethylene was used as the resin constituting the liquid-contacting part. In addition, when the resin constituting the liquid contact part (part in contact with the target chemical liquid) of the block shown in Figure 4 of the above-mentioned flow cell unit, the resin constituting the liquid contact part (part in contact with the target chemical liquid) of the liquid delivery part, and the resin constituting the liquid contact part (part in contact with the target chemical liquid) of the seal part that keeps the target chemical liquid within the area shown in Figure 4 were all made of polytetrafluoroethylene, the result was better than Example 22, but the correlation coefficient was below 0.85.

[0088] <Example E> [Production of drug solutions] High-purity grade nBA with a purity of 99% by mass or more was purchased and filtered using an appropriate combination of the following filters to prepare two types of chemical solutions with different impurity amounts (chemical solution X and chemical solution Y). IEX-PTFE(15nm): 15nm IEX PTFE manufactured by Entegris PTEE(12nm): 12nm PTFE manufactured by Entegris UPE(3nm): 3nm PE filter manufactured by Entegris

[0089] Next, in the above <Example D>, based on the data of the orthogonal coordinates with the amount of change in resonance frequency obtained from the results of the amount of change in resonance frequency (quartz crystal oscillator sensor evaluation (amount of change in resonance frequency (Hz))) and the number of defects (surface inspection device evaluation (number of defects)) of Example 24, the horizontal axis represents the amount of change in resonance frequency and the vertical axis represents the number of defects, a change in resonance frequency of 2000 Hz or less was set as the acceptable range. Next, using the above-mentioned chemical solutions X and Y, the "quartz crystal sensor evaluation (amount of change in resonant frequency (Hz))" was obtained according to the same procedure as in Example 24. Thereafter, the above-mentioned preset allowable range of the change in the resonant frequency (2000 Hz or less) was set in the memory of the measuring device, and the calculation unit determined whether the change in the resonant frequency obtained using the chemical solution X and the chemical solution Y was within the above-mentioned allowable range. As a result, the chemical solution X was within the allowable range, and the chemical solution Y was outside the allowable range. Using these chemical liquids X and Y, the evaluation using a surface inspection device (part 1) as described in Example A was carried out, and it was confirmed that the number of defects in chemical liquid X was small, at around 20 or less, whereas the number of defects in chemical liquid Y was large, at over 20. This result also confirmed that the purity of the chemical liquid can be controlled by measuring the amount of change in the resonant frequency of the chemical liquid. [Explanation of symbols]

[0090] 10. Measuring Equipment 12 Flow cell unit 14 Oscillator 14a First Oscillation Unit 14b Second Oscillation Unit 15 Detection section 16 Calculation section 20 Supply section 18 Memory 22 Control section 26 Quartz Crystal Sensor 27 Crystal Oscillator 27a surface 27b Back side 28 Temperature adjustment section 29a 1st tube 29b Second Tube 30 electrodes 30a surface 31 electrode 34 Adsorption layer 40 blocks 40a Supply route 40b Exhaust channel 40c, 42a side 42, 43 Seal part 44 areas 45 areas 50 First electrode 51 Second electrode 52 electrodes 52a first electrode portion 52b Second electrode part 52c connection part 60 sets 62 Chemical Solution 64 Container 64a Inside 64b side 64c top surface 66 Information display section

Claims

1. A measuring device for detecting impurities in a chemical solution containing an organic solvent, comprising: a quartz crystal oscillator sensor that includes an adsorption layer that adsorbs the impurities, an electrode, and a quartz crystal oscillator, and that is contacted with a target chemical solution that includes the organic solvent; an oscillation unit that oscillates the crystal oscillator at a resonance frequency; a detection unit connected to the quartz crystal sensor and detecting a change in a resonant frequency of the quartz crystal sensor due to contact with the target liquid medicine; a supply unit that supplies the target chemical solution to the quartz crystal sensor and brings the target chemical solution into contact with the quartz crystal sensor; At least a part of the liquid contact portion that comes into contact with the target chemical liquid is made of a fluorine-based resin, The adsorption layer is provided on a surface of the electrode. Measuring equipment.

2. A measuring device for detecting impurities in a chemical solution containing an organic solvent, comprising: a quartz crystal oscillator sensor that includes an adsorption layer that adsorbs the impurities, an electrode, and a quartz crystal oscillator, and that is contacted with a target chemical solution that includes the organic solvent; an oscillation unit that oscillates the crystal oscillator at a resonance frequency; a detection unit connected to the quartz crystal sensor and detecting a change in a resonant frequency of the quartz crystal sensor due to contact with the target liquid medicine; a supply unit that supplies the target chemical solution to the quartz crystal sensor and brings the target chemical solution into contact with the quartz crystal sensor; At least a part of the liquid contact portion that comes into contact with the target chemical liquid is made of a fluorine-based resin, the electrodes are provided on a surface of the quartz crystal unit, The adsorption layer is provided on a surface of the electrode. Measuring equipment.

3. A measuring device for detecting impurities in a chemical solution containing an organic solvent, comprising: a quartz crystal oscillator sensor that includes an adsorption layer that adsorbs the impurities, a quartz crystal oscillator, and a plurality of electrodes, the quartz crystal oscillator being brought into contact with a target chemical solution that includes the organic solvent; an oscillation unit that oscillates the crystal oscillator at a resonance frequency; a detection unit connected to the quartz crystal sensor and detecting a change in a resonant frequency of the quartz crystal sensor due to contact with the target liquid medicine; a supply unit that supplies the target chemical solution to the quartz crystal sensor and brings the target chemical solution into contact with the quartz crystal sensor; At least a part of the liquid contact portion that comes into contact with the target chemical liquid is made of a fluorine-based resin, All of the electrodes are provided on the surface of the quartz crystal unit. Measuring equipment.

4. 4. The measuring device according to claim 1, further comprising a display unit that displays an amount of change in the resonant frequency.

5. 5. The measuring device according to claim 1, wherein the supply unit supplies the target chemical solution to the quartz crystal sensor by flowing the target chemical solution in one direction.

6. The measuring device according to any one of claims 1 to 5, wherein the supply unit circulates and supplies the target chemical solution to the quartz crystal sensor, and the circulation flow rate of the target chemical solution is 0.01 to 1000 ml / s.

7. The adsorption layer is made of Si, Au, SiO ２ The measuring device according to any one of claims 1 to 6, which is made of at least one material selected from the group consisting of SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, and a photosensitive resin composition.

8. the quartz crystal sensor has a plurality of the adsorption layers, 8. The measurement device according to claim 1, wherein the detection section detects the amount of change in the resonant frequency for each of the adsorption layers.

9. The measuring device according to claim 8 , wherein at least one of the plurality of adsorption layers is an Au layer.

10. a seal portion disposed on the quartz crystal sensor; a block disposed on the quartz crystal sensor via the seal portion, the block including a supply path for supplying the target chemical solution to the quartz crystal sensor and a discharge path for discharging the target chemical solution from the quartz crystal sensor; A liquid delivery section including a first tube connected to the supply path and a second tube connected to the discharge path, A measuring device as described in any one of claims 1 to 9, wherein at least one of the liquid contacting portion of the sealing portion that comes into contact with the target chemical liquid, the liquid contacting portion of the block that comes into contact with the target chemical liquid, and the liquid contacting portion of the liquid delivery portion that comes into contact with the target chemical liquid are made of a fluorine-based resin.

11. The measuring device according to claim 10, wherein the liquid contact portion of the block that comes into contact with the target chemical liquid is made of a fluorine-based resin exhibiting a tensile strength of 20 to 60 MPa and a Shore D hardness of 60 to 80.

12. The measuring device according to claim 10 or 11, wherein the liquid contact portion of the block that comes into contact with the target chemical solution is made of a fluororesin selected from the group consisting of perfluoroalkoxyalkane, ethylene tetrafluoroethylene copolymer, perfluoroethylene propene copolymer, polychlorotrifluoroethylene, and polyvinylidene fluoride.

13. The measuring device according to claim 10, wherein a liquid contacting part of the liquid delivery part that comes into contact with the target chemical liquid is made of a fluorine-based resin having a repeating unit containing fluorine atoms, carbon atoms, and atoms other than fluorine atoms and carbon atoms.

14. The measuring device according to claim 10 or 13, wherein a liquid contacting part of the liquid delivery part that comes into contact with the target chemical liquid is made of a fluorine-based resin selected from the group consisting of a ternary copolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer, and polychlorotrifluoroethylene.

15. The measuring device according to claim 10, wherein a liquid contact portion of the seal portion that comes into contact with the target chemical liquid is made of a fluorine-based resin having a tensile strength of 20 to 40 MPa, a Shore D hardness of 56 to 70, and a flexural modulus of 0.5 to 3 GPa.

16. The measuring device according to claim 10 or 15, wherein the liquid contact portion of the seal portion that comes into contact with the target chemical liquid is made of a fluorine-based resin selected from the group consisting of perfluoroalkoxyalkane, perfluoroethylene propene copolymer, ethylene chlorotrifluoroethylene copolymer, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene, and polyvinylidene fluoride.

17. A quartz crystal sensor for use in the measurement device according to claim 1, A crystal oscillator, an adsorption layer disposed on the crystal oscillator, and an electrode, the adsorption layer is provided on a surface of the electrode, The adsorption layer is made of Si, Au, SiO ２ A quartz crystal sensor comprising at least one material selected from the group consisting of SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, and a photosensitive resin composition.

18. A quartz crystal oscillator sensor for use in the measurement device according to claim 2, A crystal oscillator, an adsorption layer disposed on the crystal oscillator, and an electrode, the electrodes are provided on a surface of the quartz crystal unit, the adsorption layer is provided on a surface of the electrode, The quartz crystal sensor, wherein the adsorption layer is made of at least one material selected from the group consisting of Si, Au, SiO2, SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, and a photosensitive resin composition.

19. A quartz crystal oscillator sensor for use in the measurement device according to claim 3, A crystal oscillator, an adsorption layer disposed on the crystal oscillator, and a plurality of electrodes; the adsorption layer is provided on a surface of the electrode, All of the electrodes are provided on a surface of the quartz crystal unit, The quartz crystal sensor, wherein the adsorption layer is made of at least one material selected from the group consisting of Si, Au, SiO2, SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, and a photosensitive resin composition.

20. 20. The quartz crystal sensor according to claim 17, wherein at least two of the adsorption layers are disposed on the quartz crystal.

21. 21. The quartz crystal sensor of claim 20, wherein at least one of the plurality of adsorption layers is an Au layer.

22. A step 1 of preparing a target chemical solution containing an organic solvent; a step 2 of contacting the target drug solution with a quartz crystal oscillator sensor including an adsorption layer for adsorbing impurities in the target drug solution, an electrode, and a quartz crystal oscillator, and obtaining a change in the resonant frequency of the quartz crystal oscillator due to contact with the target drug solution; In the step 2, at least a part of the liquid contact portion that comes into contact with the target chemical liquid is made of a fluorine-based resin, In the step 2, the adsorption layer is provided on a surface of the electrode.

23. A process for preparing a target drug solution containing an organic solvent; a step 2 of contacting the target drug solution with a quartz crystal oscillator sensor including an adsorption layer for adsorbing impurities in the target drug solution, an electrode, and a quartz crystal oscillator, and obtaining a change in the resonant frequency of the quartz crystal oscillator due to contact with the target drug solution; In the step 2, at least a part of the liquid contact portion that comes into contact with the target chemical liquid is made of a fluorine-based resin, In the step 2, the electrode is provided on a surface of the quartz crystal unit, In the step 2, the adsorption layer is provided on a surface of the electrode.

24. A process for preparing a target drug solution containing an organic solvent; a step 2 of contacting the target chemical solution with a quartz crystal oscillator sensor including an adsorption layer for adsorbing impurities in the target chemical solution, a quartz crystal oscillator, and a plurality of electrodes, and obtaining a change in a resonant frequency of the quartz crystal oscillator due to contact with the target chemical solution; In the step 2, at least a part of the liquid contact portion that comes into contact with the target chemical liquid is made of a fluorine-based resin, The method for measuring a chemical solution, wherein in the step 2, all of the electrodes are provided on a surface of the quartz crystal oscillator.

25. The measurement method according to any one of claims 22 to 24, wherein the target liquid drug is sent to the quartz crystal sensor to bring the target liquid drug into contact with the quartz crystal sensor.

26. The measurement method according to any one of claims 22 to 25, wherein the target liquid drug is caused to flow in one direction through the quartz crystal sensor to bring the target liquid drug into contact with the quartz crystal sensor.

27. The measurement method according to any one of claims 22 to 26, wherein the target chemical solution is circulated and supplied to the quartz crystal sensor, and a circulation flow rate of the target chemical solution is 0.01 to 1000 ml / s.

28. The adsorption layer is made of Si, Au, SiO ２ The measurement method according to any one of claims 22 to 27, wherein the material is at least one of SiOC, Cu, Co, W, Ti, TiN, Ta, TaN, and a photosensitive resin composition.

29. the quartz crystal sensor has a plurality of the adsorption layers, The measurement method according to any one of claims 22 to 28, wherein the step 2 is a step of obtaining the amount of change in the resonant frequency for each of a plurality of the adsorption layers.

30. The measurement method according to claim 29 , wherein at least one of the plurality of adsorption layers is an Au layer.

Images