Component analysis apparatus and component analysis method

Abstract

To provide an optical nuclear magnetic resonance apparatus that can be mounted on an apparatus executing an optically detected magnetic resonance method, and has a cleaning mechanism mounted thereon capable of removing an attachment on a sensor surface and can determine that contamination on the sensor surface has been removed.SOLUTION: In a component analyzer according to the present invention, a sensor has therein a defect having an electron spin causing electron spin resonance. A direction of the electron spin can be optically detected. During cleaning of the sensor, an ozone generating device and an oxygen radical generating device are driven.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a technique for analyzing the components of a sample using an optical nuclear magnetic resonance method.

Background Art

[0002] In recent years, an optical nuclear magnetic resonance technique using diamond has been proposed. The electron spin existing on a nitrogen-vacancy complex defect (referred to as an NV center) present in diamond has the property of absorbing light with a wavelength of 532 nm and emitting red fluorescence. When no external static magnetic field is applied, this electron spin is excited to an excited state by irradiating microwaves of about 2.87 GHz. Along with this, the intensity of the red fluorescence when irradiating light with a wavelength of about 532 nm decreases. This is called the electron spin resonance phenomenon. On the other hand, when an external static magnetic field is present, since the wavelength of the absorbed microwaves is proportional to the value of the applied static magnetic field, the wavelength of the microwaves at which the electron spin resonance phenomenon occurs changes from about 2.87 GHz. Therefore, by measuring the wavelength dependence of the intensity of the red fluorescence when irradiating light with a wavelength of about 532 nm on the wavelength of the irradiated microwaves, the magnetic field strength felt by the NV center of diamond can be quantified. Furthermore, by making the microwave and the irradiated light with a wavelength of about 532 nm pulsed irradiation instead of continuous irradiation over time, the magnetic field strength can be detected with higher sensitivity. Using this pulsed irradiation method, it becomes possible to detect not only a static magnetic field but also an alternating magnetic field with a specific frequency.

[0003] When molecules containing hydrogen, fluorine, etc., are present near the NV center of a diamond, the nuclear magnetic field of the alternating current formed by the nuclei of these atoms can be detected. The method for detecting this nuclear magnetic field is called nuclear magnetic resonance (NMU). To distinguish the NMU used in this specification from the conventional NMU, the method described herein will be called optical NMU. Optical NMU can calculate the frequency of the nuclear magnetic field by converting the time evolution of the detected alternating current's nuclear magnetic field into frequency. From this frequency, the molecular structure of molecules containing hydrogen, fluorine, etc., can be determined. Furthermore, the abundance of molecules can be quantified from the magnitude of the detected nuclear magnetic field. Optical NMU is known to have superior detection sensitivity compared to conventional NMU.

[0004] Patent Document 1 describes a method for obtaining a two-dimensional image of magnetic field strength by placing a nanopillar made of diamond containing NV centers at the tip of a probe microscope and scanning the nanopillar over a sample to be measured. The same document further describes a method for removing foreign matter attached to the nanopillar. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] US2015 / 0253355 [Overview of the project] [Problems that the invention aims to solve]

[0006] Patent Document 1 describes a cleaning method in which, when foreign matter adheres to a nanopillar, which is a detector, the nanopillar is used to scan a separately prepared diamond surface to physically remove the foreign matter. However, there have been no reports, including in Patent Document 1, on how to remove minute amounts of deposits (for example, a few molecular layers) from the diamond surface, or how to confirm whether or not such deposits have been removed.

[0007] When using optical nuclear magnetic resonance (NMU) spectroscopy, the sample must be placed near the NV centers in the diamond. This is because, in optical NMU, the closer the distance between the target elements (such as hydrogen and fluorine) in the sample and the NV centers in the diamond, the higher the detection sensitivity. Therefore, the sample must be in close contact with the surface of the diamond.

[0008] However, if a diamond is left in a vacuum or in an environment other than under an inert gas, moisture and organic matter from the environment will adhere to its surface. When these surface deposits are present, even when the sample to be measured is brought close to the diamond surface, a gap equal to the thickness of the surface deposits will be created between the sample and the diamond surface. This gap reduces the detection sensitivity of optical nuclear magnetic resonance (MRI). If these surface deposits contain hydrogen or fluorine, the MRI measurement data will include a nuclear magnetic field signal from the surface deposits in addition to the nuclear magnetic field signal from the sample. This nuclear magnetic field signal from the surface deposits is an undesirable signal and a disturbance that makes it difficult to interpret the measurement data. Therefore, it is necessary to remove any deposits from the diamond surface before bringing the sample to close contact with the diamond.

[0009] Traditionally, acid solution cleaning methods have been used to remove deposits from diamond surfaces, involving heating the diamond in a mixture of sulfuric acid and nitric acid, or a mixture of sulfuric acid and hydrogen peroxide, for a certain period of time. While these methods can remove deposits from the diamond surface, subsequent cleaning with organic solvents or pure water to remove residual acid residue leads to the re-adhesion of organic matter and moisture to the diamond surface. Therefore, when using acid solution cleaning, the adhesion of organic matter and moisture to the diamond surface is unavoidable. Consequently, even when the diamond surface and the sample being measured are in close contact, a gap exists between them due to the deposits, inevitably leading to a decrease in the detection sensitivity of optical nuclear magnetic resonance (OCR) spectroscopy. Furthermore, acid solution cleaning requires specialized equipment for handling the acid, making it difficult to integrate into an OCR spectrometer.

[0010] In other words, there is no established cleaning method that can be mounted on an optical nuclear magnetic resonance spectrometer, allows for in-situ cleaning of the diamond surface, and removes deposits from the diamond surface. Furthermore, there is no established method to confirm whether the impact of deposits on the diamond surface on the optical nuclear magnetic resonance measurement data has been reduced to a negligible degree.

[0011] The present invention has been made in view of the above problems, and aims to provide an optical nuclear magnetic resonance apparatus that can be mounted on an apparatus for performing optical magnetic resonance spectroscopy, and that is equipped with a cleaning mechanism capable of removing deposits from the sensor surface, and that can determine whether the contamination on the sensor surface has been removed. [Means for solving the problem]

[0012] In the component analysis apparatus according to the present invention, the sensor has a defect inside which has an electron spin that causes electron spin resonance, the direction of the electron spin is optically detectable, and an ozone generating device and an oxygen radical generating device are driven when the sensor is cleaned. [Effects of the Invention]

[0013] According to the component analysis apparatus of the present invention, deposits on the sensor surface can be removed using an optical magnetic resonance apparatus, and the cleanliness of the sensor surface can be determined. [Brief explanation of the drawing]

[0014] [Figure 1] This is a schematic side view showing the configuration of the component analyzer 100. [Figure 2] This is a schematic side view showing another configuration example of the optical nuclear magnetic resonance measurement chamber 101. [Figure 3] This is a perspective view showing another configuration example of the microwave emission device 102. [Figure 4] This is a schematic side view showing another configuration example of the microwave emission device 102. [Figure 5] This is a schematic side view showing another configuration example of an oxygen radical generation device. [Figure 6] It is a side schematic view showing another configuration example of an oxygen radical generation device. [Figure 7] It is a flowchart explaining the procedure for the component analyzer 100 to measure the components of a sample using optical nuclear magnetic resonance. [Figure 8] It is a flowchart explaining the measurement procedure of optical nuclear magnetic resonance generally used to clean the diamond surface. [Figure 9] It is a side schematic view showing the state where foreign matter adheres in the conventional measurement procedure. [Figure 10] It is a side schematic view showing the state where the measurement sample 1001 is placed on the diamond 103 in the measurement procedure of the embodiment. [Figure 11] Shows the experimental conditions for cleaning the diamond surface using oxygen radicals. [Figure 12] The results of a contact angle experiment using pure water as a probe for the diamond surface subjected to the cleaning treatment under the experimental conditions shown in FIG. 11 are shown with the horizontal axis being the cleaning treatment time and the vertical axis being the contact angle. [Figure 13] Shows the results of quantifying the amount of organic substances and moisture adhering to the diamond surface when the diamond subjected to the cleaning treatment using oxygen radicals to remove the deposits on its surface is left in the atmosphere by optical nuclear magnetic resonance measurement.

Mode for Carrying Out the Invention

[0015] <Embodiment 1> Hereinafter, embodiments of the present invention will be described based on the drawings. In this embodiment, a step of removing deposits on the diamond surface using an oxygen radical generation device in the presence of oxygen, a step of determining the cleanliness of the diamond surface by optical nuclear magnetic resonance measurement, and a step of closely attaching a measurement sample onto the diamond and performing optical nuclear magnetic resonance measurement of the measurement sample are provided.

[0016] The oxygen radical generation device used in this embodiment is described as an ultraviolet light source emitting wavelengths of approximately 185 nm and 254 nm, but a combination of an ultraviolet light source or LED (Light Emitting Diode) emitting a wavelength of 254 nm and a discharge tube that generates ozone may also be used. The ultraviolet light source or LED may be installed inside the optical nuclear magnetic resonance measurement chamber, or light may be guided from an ultraviolet light source or LED installed outside the chamber to the optical nuclear magnetic resonance measurement chamber. Furthermore, the ultraviolet light source or LED may be installed in a purification chamber located near the optical nuclear magnetic resonance measurement chamber.

[0017] Figure 1 is a schematic side view showing the configuration of the component analyzer 100 according to this embodiment. Inside the optical nuclear magnetic resonance measurement chamber 101, a diamond 103 (nuclear magnetic field sensor) is placed on a microwave emission device 102. An ultraviolet light source 104 that emits ultraviolet light is installed above the microwave emission device 102 and the diamond 103. A lens 105 is positioned below the diamond 103. A laser 1061 with a wavelength of 532 nm is irradiated onto the diamond 103 from the laser light source 106 via the lens 105. The red fluorescence 107 emitted from the diamond 103 by the laser irradiation is detected by the detector 108 via the lens 105. The detector 108 measures the direction of electron spins inside the diamond 103 by measuring the fluorescence intensity. A magnet 109 that applies a static magnetic field to the diamond 103 is installed near the diamond 103. The controller 200 controls each component of the component analyzer 100.

[0018] In this invention, oxygen radicals are used to clean the surface of the diamond 103. Therefore, when ultraviolet light is irradiated from the ultraviolet light source 104, oxygen molecules must be present inside the optical nuclear magnetic resonance measurement chamber 101. Thus, the inside of the optical nuclear magnetic resonance measurement chamber 101 may have an atmosphere equivalent to that of air, or it may be equipped with an exhaust mechanism and a mechanism for introducing an oxygen-containing gas.

[0019] The ultraviolet light source 104 should be configured such that the wavelengths of ultraviolet light emitted from it include approximately 185 nm and approximately 254 nm, or so that the emitted wavelengths can be switched between these two wavelengths. The 185 nm ultraviolet light reacts with oxygen to generate ozone, and the 254 nm ultraviolet light reacts with the ozone to decompose it and generate oxygen radicals, which then clean the diamond 103. When generating ozone and oxygen radicals using a light source that emits two types of ultraviolet light in this way, the ozone generating device and the oxygen radical generating device can be considered to be substantially integrated.

[0020] Figure 2 is a schematic side view showing an alternative configuration of the optical nuclear magnetic resonance (NMS) measurement chamber 101. In Figure 1, the ultraviolet light source 104 for cleaning the surface of the diamond 103 is housed inside the optical nuclear magnetic resonance (NMS) measurement chamber 101. However, as shown in Figure 2, a separate cleaning chamber 201 containing the ultraviolet light source 104 may be provided in addition to the optical nuclear magnetic resonance (NMS) measurement chamber 101. The diamond 103 is cleaned inside the cleaning chamber 201, and then the diamond 103 is moved to the optical nuclear magnetic resonance (NMS) measurement chamber 101 using the movable mechanism 202, and placed on the microwave emission device 102 inside the optical nuclear magnetic resonance (NMS) measurement chamber 101. In Figure 2, the optical nuclear magnetic resonance (NMS) measurement chamber 101 and the cleaning chamber 201 may or may not be spatially connected. That is, it is sufficient that the diamond 103 can be moved between the chambers.

[0021] Figure 3 is a perspective view showing another configuration example of the microwave emission device 102. The microwave emission device 102 does not necessarily have to be fixed in position; it may be movable. For example, as shown in Figure 3, multiple microwave emission devices 102 are installed on a movable support member 302 (rotating plate) that rotates around a rotation axis 301, and a diamond 103 is placed on top of the microwave emission devices 102. The movable support member 302 is then rotated in the direction of the 303. An ultraviolet light source 104 is installed on the movable support member 302, and ultraviolet light 305 is irradiated onto the diamond 103, which has moved directly beneath the ultraviolet light source 104. This generates ozone (and oxygen radicals, hereafter the same) and cleans the surface of the diamond 103. As the movable support member 302 rotates further, the diamond 103, which has been cleaned by ultraviolet light, also rotates, moving out of the ultraviolet irradiation area and into the measurement position. A measurement sample 306 is placed on the diamond 103 in the measurement position, and optical nuclear magnetic resonance measurement is performed. By repeating this process, it becomes possible to perform optical nuclear magnetic resonance measurements continuously over time. The movable support member 302 (and 401 described later) can be controlled by the controller 200.

[0022] Figure 4 is a schematic side view showing another configuration example of the microwave emission device 102. The microwave emission device 102 may be mounted on a belt-shaped movable support member 401, as shown in Figure 4. Multiple microwave emission devices 102 are mounted on the movable support member 401, and a diamond 103 is placed on top of the microwave emission devices 102. When the movable support member 401 moves in a linear direction 402 and reaches directly below the ultraviolet light source 104, ultraviolet light 305 is irradiated from the ultraviolet light source 104 onto the surface of the diamond 103. This generates ozone and cleanses the surface of the diamond 103. The movable support member 401 moves further, and the cleaned diamond 103 moves out of the ultraviolet irradiation area of ​​the ultraviolet light source 104 and moves to the measurement position. The measurement sample 306 is placed on the diamond 103 that has moved to the measurement position, and optical nuclear magnetic resonance measurement is performed. By repeating this, it is possible to perform optical nuclear magnetic resonance measurements continuously over time.

[0023] Figure 5 is a schematic side view showing another configuration example of the oxygen radical generation device. Instead of the ultraviolet light source 104, the device can also be configured using, for example, the combination shown in Figure 5, an LED or ultraviolet light source 501 that emits ultraviolet light with a wavelength of approximately 254 nm, and a discharge tube 502 for generating ozone. The discharge tube 502 may be installed outside the optical nuclear magnetic resonance measurement chamber 101 and configured to introduce ozone into the optical nuclear magnetic resonance measurement chamber 101 through piping.

[0024] Figure 6 is a schematic side view showing another configuration example of the oxygen radical generation device. As shown in Figure 6, ultraviolet light may be guided from an ultraviolet power supply 601 that emits ultraviolet light with wavelengths of approximately 185 nm and 254 nm using a fiber 602 (optical path), and the ultraviolet light may be irradiated onto the diamond 103 through a hole 603 made in the upper part of the optical nuclear magnetic resonance measurement chamber 101.

[0025] Nuclear magnetic resonance (NMU) spectroscopy is often performed in a chamber covered by a magnetic shield. Since magnetic shields are generally made of expensive metals, it is difficult to enlarge the overall apparatus. Consequently, the chamber tends to be smaller, and sometimes there is insufficient space to accommodate an ultraviolet light source within the chamber. The configuration shown in Figure 6 has the advantage of allowing the construction of an ozone generation device even in such cases.

[0026] Figure 7 is a flowchart illustrating the procedure by which the component analyzer 100 measures the components of a sample using optical nuclear magnetic resonance. Each step in this flowchart is performed by the controller 200 controlling each component of the component analyzer 100. The steps in Figure 7 will be described below.

[0027] In S701, the diamond 103 is placed on top of the microwave emission device 102 installed inside the optical nuclear magnetic resonance measurement chamber 101.

[0028] In S702, ultraviolet light with wavelengths of approximately 185 nm and 254 nm is irradiated onto the diamond 103 from the ultraviolet light source 104 to clean the diamond 103. After the cleaning process, irradiation from the ultraviolet light source 104 is stopped.

[0029] In S703, optical nuclear magnetic resonance (NMS) measurements are performed on the cleaned diamond 103, and the measurement results are recorded as measurement data. Optical nuclear magnetic resonance is a method for analyzing the components of a sample using electron spin resonance in NV centers present within the diamond 103. The specific details are described in the background technology section, so they will not be explained in detail here.

[0030] In S704, based on the optical nuclear magnetic resonance measurement data obtained in S703, it is determined whether any deposits such as organic matter or moisture remain on the surface of the diamond 103. In other words, it is determined whether the diamond 103 has been cleaned (or whether it needs to be cleaned again). If the presence of deposits is confirmed on the diamond 103, the process returns to S702 and the cleaning process using the ultraviolet light source 104 is performed again. If the presence of deposits is not confirmed on the diamond 103, it is determined that the deposits on the surface of the diamond 103 have been removed to an amount that does not affect the optical nuclear magnetic resonance measurement data, and the process proceeds to S705.

[0031] In S705, the sample to be measured is brought into close contact with the top of the diamond 103.

[0032] In S706, optical nuclear magnetic resonance (NMS) measurements are performed to obtain optical NMS measurement data for the sample being measured. In this step, the ozone generating device and the oxygen radical generating device may or may not be driven.

[0033] Figure 8 is a flowchart illustrating a measurement procedure for optical nuclear magnetic resonance commonly used to clean diamond surfaces. The general procedure shown in Figure 8 is described for comparison with the measurement procedure in the present invention.

[0034] In S801, the diamond 103 is cleaned with an acid solution (e.g., a mixed solution of sulfuric acid and nitric acid) using dedicated cleaning equipment such as an organic fume hood located outside the optical nuclear magnetic resonance apparatus. In S802, any remaining acid solution residue on the surface of the diamond 103 after S801 is cleaned by ultrasonic cleaning using an organic solvent such as acetone, and then further cleaned with pure water. In S803, the diamond 103 is placed on the microwave emission device 102 installed inside the optical nuclear magnetic resonance measurement chamber 101. In S804, the measurement sample is brought into close contact with the top of the diamond 103. In S805, optical nuclear magnetic resonance measurement data of the measurement sample is acquired.

[0035] In the measurement procedure shown in Figure 8, organic solvents such as acetone used in S802, as well as pure water, adhere to the surface of the diamond 103. This acts as noise in the measurement results, reducing the accuracy of the measurement.

[0036] Figure 9 is a schematic side view showing the state when foreign matter is attached in a conventional measurement procedure. As shown in Figure 9, when the measurement sample 901 is placed on the diamond 103 in S804, the attached material 902 is present between the diamond 103 and the measurement sample 901, creating a gap between the diamond 103 and the measurement sample 901, which reduces the detection sensitivity of optical nuclear magnetic resonance. In addition, the signal from hydrogen atoms contained in the attached material 902 will be mixed with the signal from the measurement sample 901, which will cause disturbance to the optical nuclear magnetic resonance signal.

[0037] Figure 10 is a schematic side view showing the state in which the measurement sample 1001 is placed on the diamond 103 in the measurement procedure of this embodiment. In the optical nuclear magnetic resonance measurement protocol of Figure 7, the surface of the diamond 103 can be cleaned without using a solution, and the degree of cleanliness can be determined from the optical nuclear magnetic resonance. If any deposits remain, the cleaning treatment in S702 can be performed until it is completely clean. Therefore, when the measurement sample is placed on the diamond 103 in S705, as shown in Figure 10, there are no deposits on the surface of the diamond 103, so the measurement sample 1001 and the diamond 103 can be in close contact.

[0038] <Embodiment 1: Summary> The component analyzer 100 according to this first embodiment removes deposits on the diamond 103 using oxygen radicals, and then determines the cleanliness of the diamond 103 surface by optical nuclear magnetic resonance (NMS) measurement. After confirming that the deposits do not affect the NMS measurement data, that is, that the deposits on the diamond surface have been reliably removed, the measurement sample is brought into close contact with the diamond 103. This reduces the gap between the diamond 103 and the measurement sample, ensuring that they are in close contact. This improves the detection sensitivity of the NMS measurement and reduces disturbances in the NMS measurement data caused by deposits.

[0039] <Embodiment 2> Embodiment 2 of the present invention describes another example of the configuration of the components of the component analyzer 100. Since the other components are the same as in Embodiment 1, their description is omitted in Embodiment 2.

[0040] The microwave emission device 102 may be made of a printed circuit board or a small microwave emission antenna made of wire. The microwave emission device 102 does not necessarily have to be located below the diamond 103, but can be installed in a position that allows microwaves to be irradiated onto the diamond 103.

[0041] The ultraviolet light source 104 does not necessarily have to be placed on top of the diamond 103; it is sufficient if it is positioned so that the emitted ultraviolet light preferably irradiates the diamond 103.

[0042] The lens 105 does not necessarily have to be located below the diamond 103, as long as it is positioned so that the laser 1061 can irradiate the diamond 103 and the red fluorescence 107 can be focused. Any optical element may be present between the lens 105 and the detector 108, and the lens 105 and detector 108 may be located outside the optical nuclear magnetic resonance measurement chamber 101.

[0043] Magnet 109 may be a permanent magnet or an electromagnet. The wavelength of laser 1061 is not necessarily limited to 532 nm; any wavelength at which the sensor material fluoresces is acceptable.

[0044] <Embodiment 3> Embodiment 3 of the present invention will specifically describe the cleaning effect of the diamond surface using oxygen radicals. The configuration of the component analyzer 100 is the same as in Embodiments 1 and 2, so its description will be omitted in Embodiment 3.

[0045] Figure 11 shows the experimental conditions for cleaning a diamond surface using oxygen radicals. The ultraviolet intensity was 1.2 mW / cm². 2 From 9.6 mW / cm² 2 The distance between the ultraviolet light source emitting ultraviolet rays and the diamond surface is 0.5 cm and 1.2 cm, but these values ​​are arbitrary. However, since the time required for cleaning should preferably be within 1 hour, the ultraviolet intensity should be 4.8 mW / cm². 2 In summary, a distance of 1.2 cm or less between the ultraviolet light source and the diamond is preferable. If the ultraviolet intensity is stronger, the distance between the ultraviolet light source and the diamond may be greater than 1.2 cm.

[0046] Figure 12 shows the results of a contact angle experiment using pure water as a probe on a diamond surface that had been cleaned under the experimental conditions shown in Figure 11, with the cleaning treatment time on the horizontal axis and the contact angle on the vertical axis. From the contact angle value of 1201 measured on the diamond surface immediately after cleaning with an acid solution, i.e., the contact angle value on the clean diamond surface, it can be seen that the contact angle of the clean diamond surface is approximately 12 degrees. This value also depends on the surface irregularities of the diamond, so it may not always be exactly 12 degrees.

[0047] After leaving this diamond in the air for a week, the contact angle of the diamond surface increased to approximately 50 degrees. This change is due to organic matter in the air adhering to the diamond surface. This value depends on the environment in which it is left, so it may not always be approximately 50 degrees.

[0048] Conditions 1101 and 1102 involve cleaning a diamond with surface deposits by irradiating it with ultraviolet light only (i.e., without generating oxygen radicals). Contact angle values ​​1202 and 1203 correspond to these conditions. Since the contact angle remained almost constant regardless of the intensity of the ultraviolet light, it can be seen that the deposits on the diamond surface cannot be removed by irradiation with ultraviolet light alone, and the diamond is not cleaned.

[0049] Condition 1105 involves exposing a diamond with surface deposits to ozone only. The contact angle value 1206 corresponds to this. The contact angle showed a gradual decrease. However, calculating the time required for the diamond surface to be completely cleaned, i.e., the time required for the contact angle to decrease to approximately 12, from this rate of decrease, reveals that it is a long period of several months or more, making it unsuitable for a cleaning process.

[0050] Condition 1104 involves irradiation with ultraviolet light at wavelengths of approximately 185 nm and 254 nm (i.e., treatment using oxygen radicals). The contact angle value 1205 corresponds to this. When the distance between the ultraviolet lamp and the diamond surface is 1.2 cm, the measured contact angle becomes approximately 12 degrees in about 60 minutes, which is almost equal to the value of the cleaned surface. In other words, it can be seen that deposits on the diamond surface can be removed in a short time when using oxygen radicals for cleaning.

[0051] Condition 1103 further reduces the distance between the UV lamp and the diamond surface to 0.5 cm. The contact angle value 1204 corresponds to this. In this case, the measured contact angle becomes approximately 12 degrees in about 15 minutes. Therefore, it can be seen that the shorter the distance between the UV lamp and the diamond, the faster the diamond surface can be cleaned.

[0052] Figure 13 shows the quantitative results obtained by optical nuclear magnetic resonance (NMS) measurement of the amount of organic matter and water adhering to the surface of a diamond that has been cleaned using oxygen radicals to remove surface deposits and then left in the air. Optical NMS detects organic matter and hydrogen atoms contained in water. In the optical NMS spectrum of Figure 13, the horizontal axis represents the frequency of the nuclear magnetic field formed by the nuclear spin of hydrogen atoms, and the vertical axis represents the abundance of hydrogen atoms. This optical NMS spectrum was measured by placing the diamond in an optical NMS chamber after cleaning, leaving it in the air for 0 hours, 12 hours, and 120 hours, and then performing the measurement without further cleaning.

[0053] Spectrum 1301 is the result after 0 hours of standing, and since no signal is visible, it can be seen that the amount of deposits on the diamond surface is below the detection limit of this optical nuclear magnetic resonance measurement. Spectrum 1302 is the result after 12 hours of standing, and a peak is present around 200 kHz. This peak is due to hydrogen atoms contained in the deposits on the diamond surface, so it can be seen that organic matter and moisture present in the atmosphere adhered to the diamond surface after being left in the air for 12 hours. Spectrum 1303 was measured after 120 hours of standing, and a peak is present at the same 200 kHz position as in Spectrum 1302, and this peak has increased. Therefore, the peak in Spectrum 1303 has the same origin as Spectrum 1302, namely organic matter and hydrogen contained in the deposits on the diamond surface, and it means that the amount of deposits increased with the standing time. Spectrum 1304 is the result of optical nuclear magnetic resonance measurement measured after the diamond that gives Spectrum 1303 was subjected to the cleaning treatment using oxygen radicals of the present invention. Since there is no peak at spectral value 1304, it can be seen that the deposits on the diamond surface were removed by this cleaning treatment.

[0054] As shown in Figure 13, the effects of the present invention include the fact that by applying a cleaning treatment using oxygen radicals to diamonds with deposits on their surface, the deposits can be removed, and the degree of cleanliness can be determined. Therefore, the quality of optical nuclear magnetic resonance measurement data can be improved.

[0055] <Regarding variations of the present invention> In the embodiments described above, the wavelengths of ultraviolet light emitted by the ultraviolet light source 104 in Figure 1 and the ultraviolet power supply 601 in Figure 6 were explained to be approximately 185 nm and approximately 254 nm, or approximately 254 nm. However, the ultraviolet wavelengths are not limited to these, and any ultraviolet light with wavelengths of at least approximately 185 nm or less, which is the wavelength at which ozone is generated, and ultraviolet light around 254 nm, which is the wavelength at which oxygen radicals are generated from ozone, is acceptable.

[0056] In the embodiments described above, the diamond 103 and the sample do not necessarily have to be in strict, direct mechanical contact; a very small distance is acceptable as long as the nuclear magnetic field can be detected. For example, a gap of a few nanometers may exist between the diamond 103 and the sample. Therefore, it should be noted that the statement that the diamond 103 and the sample are in contact encompasses such arrangements that allow for the detection of the nuclear magnetic field.

[0057] In the embodiments described above, diamond was used as an example of a sensor material, but the present invention is not limited to this. That is, the present invention can also be applied when cleaning other types of sensor materials that can be used with optical nuclear magnetic resonance spectroscopy. In other words, other materials can be used instead of diamond 103 as long as they can be used as a nuclear magnetic field sensor that can detect the nuclear magnetic field of a sample by contacting the sample.

[0058] In the embodiments described above, the controller 200 can be configured by hardware such as a circuit device that implements its functions, or by software that implements its functions being executed by a computing unit (e.g., a Central Processing Unit, a Graphics Processing Unit, etc.) or other computer. [Explanation of symbols]

[0059] 100:Component analysis device 101: Optical nuclear magnetic resonance measurement chamber 102: Microwave Emission Devices 103: Diamond 104: Ultraviolet light source 105: Lens 106: Laser light source 107: Red fluorescence 108: Detector 109: Magnet

Claims

1. A component analysis device, A sensor that contacts the sample to detect the nuclear magnetic field of the sample, Ozone generating device, An oxygen radical generation device that decomposes ozone to generate oxygen radicals, Equipped with, The sensor has an electron spin that resonates with the nuclear spin of the sample, The direction of the electron spin is optically detectable, The ozone generating device and the oxygen radical generating device are activated when the sensor is being cleaned. The component analyzer further includes a controller that controls the ozone generating device and the oxygen radical generating device. The aforementioned controller is: While the sensor and the sample are not in contact, the sensor obtains the results of component measurement performed by nuclear magnetic resonance using electron spin resonance. Based on the above results, make one of the following decisions: Whether or not the sensor has been cleaned by the oxygen radicals, Whether or not the aforementioned sensor needs to be re-cleaned by the oxygen radicals, A component analyzer characterized by the following features.

2. A component analysis device, A sensor that contacts the sample to detect the nuclear magnetic field of the sample, Ozone generating device, An oxygen radical generation device that decomposes ozone to generate oxygen radicals, Equipped with, The sensor has an electron spin that resonates with the nuclear spin of the sample, The direction of the electron spin is optically detectable, The ozone generating device and the oxygen radical generating device are activated when the sensor is being cleaned. The aforementioned component analyzer further, When performing component measurement by nuclear magnetic resonance using the aforementioned electron spin resonance, the measurement chamber containing the sample, A cleaning chamber housing the sensor when cleaning the sensor, A mechanism for moving the sensor between the measuring chamber and the cleaning chamber, Equipped with, The ozone generating device and the oxygen radical generating device are located within the washing chamber. A component analyzer characterized by the following features.

3. A component analysis device, A sensor that contacts the sample to detect the nuclear magnetic field of the sample, Ozone generating device, An oxygen radical generation device that decomposes ozone to generate oxygen radicals, Equipped with, The sensor has an electron spin that resonates with the nuclear spin of the sample, The direction of the electron spin is optically detectable, The ozone generating device and the oxygen radical generating device are activated when the sensor is being cleaned. The aforementioned component analyzer further, A microwave emitting device that irradiates the sensor with microwaves, A magnet that applies a static magnetic field to the aforementioned sensor, A laser light source that irradiates the sensor with laser light used to read the direction of the electron spin, A lens that collects the fluorescence emitted from the sensor when the laser light is irradiated onto the sensor. A detector for measuring the intensity of the fluorescence, Equipped with, The aforementioned component analyzer further, A movable support member on which two or more pairs of the microwave emission device and the sensor are mounted, A controller that controls the movable support member, the ozone generating device, and the oxygen radical generating device. Equipped with, The aforementioned controller is: After moving the movable support member so that the first pair is positioned at the first position where cleaning is performed by the oxygen radicals, cleaning is performed on the first pair. After cleaning of the first pair is completed, the movable support member is moved so that the first pair is positioned at a second position for performing component measurement by nuclear magnetic resonance on the first pair, and the movable support member is moved so that the second pair is positioned at the first position. A component analyzer characterized by the following features.

4. A component analyzer according to claim 1, When the controller performs component measurement by nuclear magnetic resonance after the sensor has been cleaned by the oxygen radicals, it performs the component measurement regardless of whether the oxygen radical generation device is being driven or not. A component analyzer characterized by the following features.

5. A component analyzer according to claim 3, The movable support member is composed of either a rotating plate that rotates around a rotation axis, or a belt-shaped member that moves in a linear direction. A component analyzer characterized by the following features.

6. A component analyzer according to any one of claims 1 to 3, The ozone generating device and the oxygen radical generating device are A light source capable of emitting two ultraviolet wavelengths, or A light source that emits one ultraviolet wavelength and a discharge tube that generates ozone, It is composed of one of the following: A component analyzer characterized by the following features.

7. A component analyzer according to any one of claims 1 to 3, The ozone generating device and the oxygen radical generating device are composed of a light source capable of emitting two ultraviolet wavelengths. The light source is located outside the chamber housing the sensor. The component analysis apparatus further includes an optical path that guides the light emitted from the light source into the chamber. A component analyzer characterized by the following features.

8. A component analyzer according to any one of claims 1 to 3, The aforementioned sensor is made of diamond material. A component analyzer characterized by the following features.

9. A method for cleaning a sensor of a component analyzer according to any one of claims 1 to 3, The sensor has an electron spin that resonates with the nuclear spin of the sample, The direction of the electron spin is optically detectable, The aforementioned cleaning method is: Ozone is generated inside the chamber in which the sensor is housed. Inside the chamber, ozone is decomposed to generate oxygen radicals. Our method for analyzing components.

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