Flow nanoparticle measurement device and method for determining nanoparticles using the device

Abstract

The present application discloses a flow nanoparticle measurement device and a method for determining nanoparticles using the device. The nanoparticle measurement device includes: a flow chamber configured to form a flow path through which a liquid sample flows; a laser generator configured to generate a first laser beam and irradiate the flow chamber with the first laser beam; a plurality of detectors arranged in the flow chamber and configured to detect shock waves of plasma generated in the flow chamber by the first laser beam and generate detection signals; and a controller configured to obtain the detection signals from the plurality of detectors and determine the type and size of nanoparticles contained in the liquid sample in response to the detection signals.

Description

[0001] This application claims the benefit of priority to Korean Patent Application No. 10-2020-0136343, filed on October 20, 2020, which is hereby incorporated by reference for all purposes as if fully set forth herein. Technical Field

[0002] The present invention relates to a flow nanoparticle measurement device and a method for determining nanoparticles using the device. More particularly, the present invention relates to a measurement device for measuring trace nanoparticles present in a flow sample.

[0003] The present invention relates to a highly sensitive detection method capable of detecting samples with a low concentration of less than or equal to 100 nm at the ppt level when analyzing high-purity chemicals (such as liquid chemicals, i.e., solvents) in a state with a flow rate. The present invention also relates to a measuring device that collects and analyzes signals generated by induced plasma generated from nanoscale particles by a light source having a specific energy. Background Art

[0004] Various organic and inorganic chemicals used in the manufacturing processes of products requiring high precision (such as displays and semiconductors) require chemicals of higher purity than currently available to prevent yield reductions, and high-level analytical techniques have been developed and newly applied to check the quality of high-purity chemicals. Among them, the importance of particle analysis is gradually increasing. Since even small particles at the 10-nanometer level can affect yield reduction and the high integration of semiconductor manufacturing processes, it is necessary to develop stable analytical methods for quality control, and it is also necessary to ensure the scalability of the technology so that even the causes of defects that may occur in the manufacturing process can be analyzed.

[0005] Generally speaking, a substance uniformly dispersed in a liquid as molecules or ions is called a solution. When tiny particles larger than normal molecules or ions, with diameters ranging from approximately 1 to 1000 nm, are dispersed in such a solution without aggregation or precipitation, this state is called a colloidal state, and the particles in this colloidal state are called colloids.

[0006] Research on microcolloids present in solution has focused on obtaining information on the physical and chemical properties of the substances being analyzed or improving the detection capabilities of separation analyzers. Until recently, the analysis of colloidal particles was limited to a size of 100 nm, so there was a need to develop such techniques: for the accurate analysis of colloidal particles smaller than or equal to 100 nm, high sample concentrations were required.

[0007] Methods for measuring colloidal nanoparticles typically use light scattering analysis methods to examine the size of the particles using light scattering intensity. However, when measuring tiny nanoparticles less than 100 nm in size, even if scattered light is generated, the probability of detection at low concentrations decreases rapidly, making it difficult to obtain reliable results. In addition, the concentration of the particles must be limited to ppm (parts per million) or greater. The light scattering intensity increases as the particle size increases, while the light scattering area decreases as the particle size decreases. Therefore, it is difficult to measure the particle size due to the decrease in light scattering intensity. Since a relatively large number of particles can certainly contribute to scattering, the sensitivity is generally reduced when the concentration is less than ppm. Summary of the Invention

[0008] One aspect of the present invention provides a flow nanoparticle measurement apparatus and a method of determining nanoparticles using the apparatus, which are capable of detecting particles smaller than or equal to 100 nm with a concentration of parts per trillion (ppt).

[0009] Another aspect of the present invention provides a dynamic flow nanoparticle measurement device and a method for determining nanoparticles using the device, for improving the measurement reliability of nanoparticles.

[0010] Another aspect of the present invention provides a flow nanoparticle measuring device and a method for determining nanoparticles using the device, the device and the method using a chamber whose shape is designed so that nanoparticles can be detected in a flow sample, and the device includes a flow controller consisting of a piston pump and a magnetic valve, so that the flow can be controlled without vortices, unlike conventional nanoparticle analysis methods that produce vortices.

[0011] Another aspect of the present invention provides a flow nanoparticle measurement apparatus for determining the type and size of nanoparticles based on the natural frequency and amplitude of the nanoparticles detected by a plurality of detectors.

[0012] To achieve the above and other objects of the present invention, in one aspect of the present invention, a flow nanoparticle measuring device is provided, comprising: a flow chamber configured to form a flow path through which a liquid sample flows; a laser generator configured to generate a first laser beam and irradiate the first laser beam to the flow chamber; a plurality of detectors arranged in the flow chamber and configured to detect shock waves of plasma generated by the first laser beam in the flow chamber and to generate detection signals; and a controller configured to obtain the detection signals from the plurality of detectors and determine the type and size of nanoparticles contained in the liquid sample in response to the detection signals.

[0013] In another aspect of the present invention, a flow nanoparticle measurement method (S200, S300) using a flow nanoparticle measurement apparatus is provided, the flow nanoparticle measurement apparatus comprising: a flow chamber forming a flow path through which a liquid sample flows; a laser generator generating a pulsed laser beam and irradiating a first laser beam split from the pulsed laser beam to the flow chamber; and a plurality of detectors arranged along a flow direction of the liquid sample and detecting shock waves of plasma generated in the flow chamber to generate detection signals, the flow nanoparticle measurement method comprising: steps of measuring an amplitude and a frequency of the shock wave in response to the detection signal (S210, S310); calculating an amplitude ratio based on the amplitude and a natural frequency detected by each of the plurality of detectors (S220, S320); and steps of specifying a type of nanoparticles contained in the liquid sample according to the measured natural frequency and determining a size of the nanoparticles based on the calculated amplitude ratio (S230, S330).

[0014] According to one aspect of the present invention, the present invention is capable of measuring nanoparticles in a liquid sample whose flow is controlled.

[0015] According to one aspect of the present invention, the present invention can reduce measurement errors that may occur when calculating the number of nanoparticles using measurement values ​​of a very small area in a static chamber by measuring nanoparticles in a flowing liquid sample, and thereby can improve the reliability of nanoparticle measurement.

[0016] According to one aspect of the present invention, the present invention can increase the probability of nanoparticle detection and thus improve the reliability of nanoparticle detection.

[0017] An object of the present invention is to improve the detection capability of trace particles of a sample smaller than or equal to 100 nm and at a low concentration by controlling a flow rate using a flow control device to detect a signal instantaneously generated in plasma detection.

[0018] The present invention can determine the size of nanoparticles based on the amplitude ratio by detecting shock wave signals generated by plasma using a plurality of detectors. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this invention, illustrate embodiments of the invention and together with the description serve to explain the principle of the invention.

[0020] Figure 1 A flow nanoparticle measurement device according to an embodiment of the present invention is schematically shown.

[0021] Figure 2 A configuration related to a flow device of a flow nanoparticle measuring device according to an embodiment of the present invention is shown.

[0022] Figure 3A and Figure 3B A flow chamber of a flow nanoparticle measurement apparatus according to an embodiment of the present invention is shown.

[0023] Figure 4 An example of a flow controller of a flow nanoparticle measuring apparatus according to an embodiment of the present invention is shown.

[0024] Figure 5 is a flowchart illustrating a flowing nanoparticle measurement method S100 according to an embodiment of the present invention.

[0025] Figure 6 The time-dependent operation in a flow nanoparticle measurement apparatus according to an embodiment of the present invention is shown.

[0026] Figure 7 A time-dependent operation in a flow nanoparticle measurement apparatus according to another embodiment of the present invention is shown.

[0027] Figure 8 Schematic illustration of plasma generation by a pulsed laser beam in a flow nanoparticle measurement apparatus according to an embodiment of the present invention.

[0028] Figure 9 is a block diagram illustrating a controller of a flow nanoparticle measuring apparatus according to an embodiment of the present invention.

[0029] Figure 10 (a) and (b) are graphs showing the frequency and amplitude of shock waves detected by a plurality of detectors, which is one configuration of a flow nanoparticle measurement apparatus according to an embodiment of the present invention.

[0030] Figure 11 is a flow chart illustrating a method S200 for determining the type and size of nanoparticles according to an embodiment of the present invention.

[0031] Figure 12 FIG. 4 is a flow chart illustrating a method S300 for determining the type and size of nanoparticles according to another embodiment of the present invention. DETAILED DESCRIPTION

[0032] The detailed description and specific examples (such as embodiments of the invention) are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from the detailed description.

[0033] Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts or components.

[0034] The terms used in the present invention are used to explain the embodiments and are not intended to limit and / or constrain the present invention. As long as there is no clear different meaning in the context, a singular expression may include a plural expression. In the present invention, the terms "including" and "having" should be understood to indicate the presence of the features, numbers, steps, operations, components, parts or combinations thereof shown, without excluding the possibility of the presence of one or more different features, numbers, steps, operations, components, parts or combinations thereof, or additions thereto.

[0035] Terms including ordinal numbers such as "first" and "second" may be used to describe various components, but these components are not limited by such terms. These terms are used only to distinguish one component from other components. For example, a first component may be referred to as a second component without departing from the spirit and scope of the present invention, and similarly, a second component may be referred to as a first component. The term "and / or" includes a combination of multiple or some of the multiple related items.

[0036] In addition, terms such as "component," "device," "block," "member," and "module" may refer to a unit that processes at least one function or operation. For example, these terms may mean at least one hardware such as a field programmable gate array (FPGA) / application specific integrated circuit (ASIC), at least one software stored in a memory, or at least one process processed by a processor.

[0037] Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The accompanying drawings illustrate embodiments of the present invention and are used to help easily understand various technical features, it being understood that the embodiments presented herein are not limited to the accompanying drawings.

[0038] Although the present invention can detect the light emitted by generating an induced plasma from microparticles using a laser, the description of the present invention focuses on a method for analyzing the size of shock waves and plasma. This is called laser induced breakdown detection (LIBD) technology and is a particle analysis method that can obtain information such as the size, concentration, distribution, and composition of nanoparticles by detecting the intensity and distribution of the induced plasma using various detection methods, wherein the induced plasma is generated by focusing a high-energy pulsed laser on particles present in an aqueous solution. Therefore, compared with existing light scattering methods, transmission electron microscopy, atomic force microscopy, etc., this method has a lower detection limit as the particle size decreases. It is reported that this method can theoretically measure particles up to 1 nanometer, and this method is a low-concentration nanoparticle analysis method, wherein the concentration range is the ppt concentration range.

[0039] Existing laser-induced breakdown detection methods measure shock waves and plasma scintillation generated when induced plasma is generated. Shock waves are measured acoustically, while plasma scintillation is measured by attaching a camera near the chamber. However, even if plasma is generated by impurities other than the target nanoparticles during the measurement of shock waves and plasma scintillation, this plasma may be detected and identified as a shock wave or scintillation. Alternatively, plasma can be generated again by continuously receiving energy from the generated plasma, and this plasma can be detected as noise.

[0040] The present invention proposes a method for detecting induced shock waves generated in a flowing liquid sample using a flow rate control device and quantifying them for size classification. When the control device is used to determine the size of nanoparticles in the flowing sample, the present invention achieves higher detection limits than existing detection methods by measuring a specific region, enabling non-contact, real-time measurement, and reliable results by changing the measurement path in real time. Furthermore, the present invention can measure nanoparticles in all samples, unlike existing measurement methods that only measure some samples, thereby improving the reliability of the results.

[0041] Measurement utilizes a practical laser light source to illuminate an area while maintaining a very high linear velocity within a narrow flow path, allowing for measurement of a sample flowing within a very small area. In this case, the high velocity causes significant distortion in the plasma image. In some cases, this can hinder detection due to changes in contrast ratio, resulting in reduced reproducibility and detection sensitivity. To improve this, the present invention attempts to detect images under transient static conditions using flow pulses, such as pulsed lasers. To achieve this, a flow chamber is required that allows flow without eddy currents and is fabricated to maximize the laser beam incident signal. Furthermore, a flow controller capable of controlling the velocity under transient static conditions controls the linear velocity by temporarily operating an internal piston pump with a pulse width. More specifically, the flow controller can be configured to control the flow rate of the liquid sample in accordance with the pulse width. By detecting the plasma signal value generated by the pulsed laser beam under transient static conditions of the liquid sample generated by the flow controller, the present invention increases the probability and sensitivity of plasma detection and improves associated issues such as distortion, contrast ratio, and shock wave sensitivity, thereby effectively improving the reliability of the results.

[0042] The flow nanoparticle measurement device can use the LIBD method. The LIBD method allows a pulsed laser beam with a time width of several nanoseconds to be incident through a lens, and uses the principle of laser beam-induced plasma generated in the focal area of ​​the lens when the laser beam is incident. More specifically, when the pulsed laser beam is irradiated to the nanoparticles, the energy level of the nanoparticles becomes an excited state, and then the energy is released to be in a stable state, that is, the ground state (or excited state). Due to the energy released in this process, plasma or shock waves are generated in the nanoparticles.

[0043] In this case, the phenomenon of plasma or shock wave generation is called breakdown, and it requires a minimum energy for particles to generate plasma, known as the minimum energy threshold. The minimum energy threshold depends on the phase of the material, as the required ionization energy varies for each material. The minimum energy threshold is highest in the gaseous state and decreases in the order of liquid and solid.

[0044] The energy required for the laser beam to generate laser-induced plasma increases in the order of solid, liquid, and gas. Therefore, when using appropriate laser beam energy, a laser-induced plasma state can be generated by only breaking down solid particles in an aqueous solution.

[0045] The concentration and size of nanoparticles can be analyzed by taking advantage of the following properties: the breakdown probability varies with particle concentration under conditions of fixed laser beam energy; and the minimum energy of the laser beam required for breakdown varies with particle size.

[0046] Flow nanoparticle measurement equipment can compensate for the reliability issues that can occur when detecting particles based on the above theory. In most particle analysis devices, contamination can occur during sample collection and analysis, potentially misinterpreting the value as due to contamination. Because high-purity materials are susceptible to contamination, the developed device minimizes contamination through the use of a specially designed flow chamber, allowing for direct sample injection and analysis.

[0047] Figure 1 A flow nanoparticle measurement device according to an embodiment of the present invention is schematically shown.

[0048] The flow nanoparticle measurement device 1 may include a laser generator 10 and a flow device 20. The flow device 20 may include a flow chamber 30, an inlet portion 41, and an outlet portion 42. A liquid sample may enter the flow device 20 through the inlet portion 41. The liquid sample entering the flow device 20 may pass through the flow chamber 30. The liquid sample passing through the flow chamber 30 may be discharged to the outside through the outlet portion 42.

[0049] The laser generator 10 may include a laser generating device 12 , an aperture 13 , a reflective mirror 14 , a beam splitter 16 , an energy detector 17 , a lens 18 , and a beam stop 19 .

[0050] The laser generating device 12 can generate a pulsed laser beam B. The wavelength of the pulsed laser beam B is not limited. The pulsed laser beam B can be irradiated using a Q switch. The predetermined period T1 (see Figure 6 ) pulses repeatedly irradiate the pulsed laser beam B. That is, the laser generating device 12 may irradiate the pulsed laser beam B so that on / off repeats with a first period T1. The pulsed laser beam B generated by the laser generating device 12 may include an Nd:YAG pulsed laser beam having a wavelength of 532 nm. However, the present invention is not limited thereto, and the type and energy level of the laser beam irradiated by the laser generating device 12 may be applied differently.

[0051] The aperture 13 may be provided at one side of the laser generating device 12 and may adjust the diameter of the pulse laser beam emitted and then incident by the laser generating device 12. The aperture 13 may variously adjust the diameter of the laser beam emitted by the laser generating device 12.

[0052] The reflection mirror 14 is provided on the path of the pulsed laser beam B and can convert the path of the pulsed laser beam B. Furthermore, at least one reflection mirror is arranged on the path of the pulsed laser beam B and thus can allow only the pulsed laser beam B having a desired wavelength to reach the flow cell 30 .

[0053] The beam splitter 16 can adjust the path of the pulsed laser beam B. The beam splitter 16 can split the pulsed laser beam B into several paths at a predetermined ratio. The beam splitter 16 can adjust the intensity of the laser beam split from the pulsed laser beam B.

[0054] The beam splitter 16 can adjust the path of at least a portion of the beam B1 of the incident pulsed laser beam B to point to the flow chamber 30. For example, the beam splitter 16 can split the pulsed laser beam B into a first laser beam B1 and a second laser beam B2. That is, the pulsed laser beam B incident on the beam splitter 16 can be split into a first laser beam B1 and a second laser beam B2. The optical characteristics of the first laser beam B1 can correspond to the optical characteristics of the pulsed laser beam B. For example, the first laser beam B1 can be a pulsed laser with a predetermined period. For example, the pulse period of the first laser beam B1 can be a first period T1 (see Figure 6 and Figure 7 ).

[0055] For example, the traveling direction of the first laser beam B1 may be different from the traveling direction of the pulsed laser beam B incident on the beam splitter 16. For example, the traveling direction of the first laser beam B1 may be perpendicular to the traveling direction of the pulsed laser beam B incident on the beam splitter 16. For example, the traveling direction of the second laser beam B2 may be the same as or parallel to the traveling direction of the pulsed laser beam B incident on the beam splitter 16.

[0056] For example, the power of the first laser beam B1 generated by the beam splitter 16 may be less than the power of the pulsed laser beam B incident on the beam splitter 16. For example, the power of the first laser beam B1 generated by the beam splitter 16 may be the same as the power of the second laser beam B2 generated by the beam splitter 16.

[0057] The energy detector 17 may measure the power (or energy) of the second laser beam B2. The energy detector 17 may face the beam splitter 16. The second laser beam B2 generated by the beam splitter 16 may be incident on the energy detector 17. The traveling direction of the second laser beam B2 may form an angle with the traveling direction of the first laser beam B1.

[0058] The power (or energy) of the first laser beam B1 may correspond to the power (or energy) of the second laser beam B2. Therefore, the power (or energy) measurement value measured by the energy detector 17 may be used to calculate the power (or energy) of the first laser beam B1. For example, if the power of the first laser beam B1 is the same as the power of the second laser beam B2, the power measured by the energy detector 17 may be the power of the first laser beam B1.

[0059] The lens 18 may be disposed between the beam splitter 16 and the flow cell 30. For example, the first laser beam B1 generated by the beam splitter 16 may be incident on the lens 18. The optical characteristics of the first laser beam B1 may change when passing through the lens 18. For example, the focus of the first laser beam B1 passing through the lens 18 may be a point in the flow cell 30.

[0060] In other words, lens 18 can adjust the irradiation area and focal length of first laser beam B1 incident on flow cell 30. The focal length of first laser beam B1 may refer to the distance between the focal point of first laser beam B1 passing through lens 18 and lens 18. Lens 18 improves the ability to detect nanoparticles by adjusting the irradiation area of ​​first laser beam B1 incident on flow cell 30. The focal length of lens 18 can be adjusted based on the Gaussian distribution of the induced plasma of nanoparticles generated by first laser beam B1. The focal length of first laser beam B1 can be set to 10 mm to 40 mm, but is not limited thereto.

[0061] The location where the induced plasma is generated in the flow chamber 30 may correspond to the location where the first laser beam B1 strikes the nanoparticles. The liquid sample flowing in the flow chamber 30 may have a unique refractive index. Therefore, the focal length of the first laser beam B1 may vary depending on the type of liquid sample flowing in the flow chamber 30. To measure various liquid samples, it may be necessary to appropriately adjust the focal length. To this end, the location where the induced plasma is generated in the flow chamber 30 may be controlled by adjusting the distance between the lens 18 and the flow chamber 30 according to the type of liquid sample. The distance between the lens 18 and the flow chamber 30 may be adjusted by the controller 70. For example, the controller 70 may control the position of the lens 18 by moving the lens 18.

[0062] Beam stop 19 may face flow cell 30. Flow cell 30 may be located between lens 18 and beam stop 19. For example, first laser beam B1 may be incident on beam stop 19 after passing through flow cell 30. Beam stop 19 may suppress the travel of incident first laser beam B1. For example, beam stop 19 may block (or shield) incident first laser beam B1.

[0063] The flow chamber 30 may form a flow path F. Figure 1 In the figure, the flow path F may be indicated by a dotted line. The flow path F may be formed outside and inside the flow chamber 30. The flow path F may indicate the path through which the liquid sample flows. The flow path F may indicate the direction in which the liquid sample flows. In this context, the flow path F may be referred to as the "flow direction."

[0064] In a narrow sense, the flow path F may refer to a path through which the liquid sample flows in the flow chamber 30. The flow chamber 30 may include a chamber inlet 32 ​​and a chamber outlet 34.

[0065] The flow path F formed inside the flow chamber 30 may extend from the chamber inlet 32 ​​to the chamber outlet 34. For example, a liquid sample may enter the flow chamber 30 through the chamber inlet 32 ​​and may be discharged to the outside of the flow chamber 30 through the chamber outlet 34.

[0066] In a broad sense, the flow path F may refer to a path through which the liquid sample flows within the flow device 20. The flow path F formed within the flow device 20 may extend from the inlet portion 41 and lead to the outlet portion 42.

[0067] The flow nanoparticle measurement apparatus 1 may include a detector 60, a flow controller 50, and a controller 70. The description of the detector 60, the flow controller 50, and the controller 70 may be included in the description of the flow nanoparticle measurement apparatus 1. Figure 2 's description.

[0068] Figure 2A configuration related to a flow device of a flow nanoparticle measuring device according to an embodiment of the present invention is shown. Figure 3A and Figure 3B A flow chamber of a flow nanoparticle measurement apparatus according to an embodiment of the present invention is shown.

[0069] The flow device 20 may be configured to flow a liquid sample.

[0070] The flow chamber 30 may be configured to allow a liquid sample to flow therein. The flow chamber 30 may include a chamber inlet 32 ​​and a chamber outlet 34. The liquid sample is introduced into the chamber inlet 32 ​​and discharged from the chamber outlet 34. The flow chamber 30 may be formed of a material including quartz, but is not limited thereto. For example, the flow chamber 30 may be formed of a material including a polymer material such as acrylic.

[0071] While the flow chamber 30 is described and illustrated as having a rectangular outer shape, this shape is not limited thereto. When the flow chamber 30 is a rectangular chamber, the detector 60 described below may be positioned perpendicular to the outer surface of the rectangular chamber or tilted at a predetermined angle from the outer surface of the rectangular chamber. However, the shape of the flow chamber 30 and the arrangement of the detector 60 based on the shape of the flow chamber 30 are not limited thereto.

[0072] The flow cell 30 may be configured such that the liquid sample flows inside the flow cell 30 . At least a portion of the flow cell 30 may be made of a light-transmitting material so that the first laser beam B1 irradiates the liquid sample in the flow cell 30 .

[0073] The flow chamber 30 may include a flow portion 36 in which the liquid sample flows. The flow portion 36 may be a space formed in the flow chamber 30. A flow path F in a narrow sense may be formed by the flow portion 36. The flow portion 36 may extend from the chamber inlet 32 ​​and lead to the chamber outlet 34. For example, the flow portion 36 may be connected to an opening formed in the chamber inlet 32. For example, the flow portion 36 may be connected to an opening formed in the chamber outlet 34. The chamber outlet 34 may be spaced apart from the chamber inlet 32.

[0074] The flow portion 36 may be formed to extend from the chamber inlet 32, bend, and extend again, and open to the chamber outlet 34. For example, the flow portion 36 may be formed in a curved shape. One end of the flow portion 36 may be connected to the chamber inlet 32, and the other end of the flow portion 36 may open to the chamber outlet 34.

[0075] The inner diameter of the flow portion 36 may be formed within 10 mm, but is not limited thereto. The size and shape of the inner diameter of the flow portion 36 may be variously applied. For example, Figure 3A As shown, the cross section of the flow portion 36 may have a rectangular shape. Alternatively, as shown Figure 3BAs shown, the cross-section of the flow portion 36 may have a circular shape.

[0076] When Figure 3B When the flow portion 36 is formed to have a circular cross section as shown, the distance between the flow portion 36 and the detector 60 can be configured to be the same even if the direction in which the detector 60 is arranged relative to the flow portion 36 is changed. Therefore, the restrictions on the arrangement of the detector 60 can be reduced, and thus the reliability of the detection result can be improved.

[0077] In addition, when Figure 3A When the flow portion 36 is formed to have a rectangular cross section as shown, the first laser beam B1 can irradiate or receive the plasma signal in a direction perpendicular to the flow portion 36. Therefore, distortion such as refraction of the signal can be reduced. With this configuration, more accurate detection results can be obtained.

[0078] In addition, when Figure 3A As shown, when the flow portion 36 is formed into a rectangular cross-section, a larger flow path can be formed for the same width, thereby achieving smoother flow of the liquid sample. However, the shape of the flow portion 36 is not limited. For example, at least a portion of the flow portion 36 can be formed into a curved surface, while the remaining portion of the flow portion 36 can be formed into a flat surface. In other words, the cross-section of the flow portion 36 can be formed into a shape that combines a curved surface and a polygon. When a portion of the flow portion 36 is formed into a curved surface, the detection strength can be maximized, and the generation of bubbles in the liquid sample due to the flow rate can be minimized.

[0079] The size of the inner diameter of the flow portion 36 may be formed uniformly throughout the flow path F, or may vary along the flow path F. More specifically, the flow portion 36 may be divided into a plurality of sections, and each section may have a different inner diameter, or a main flow portion 38 of the flow portion 36 to be described later may have a different inner diameter and a different shape from other sections of the flow portion 36. The size and shape of the inner diameter of the flow portion 36 are not limited.

[0080] The flow portion 36 may include a main flow portion 38 that transmits the first laser beam B1. The main flow portion 38 may form at least a portion of a flow space 37 in which the liquid sample flows. The first laser beam B1 may be irradiated to the main flow portion 38. The flow space 37 may form a flow path through which the liquid sample flows in one direction. The main flow portion 38 may form a portion of the flow space 37. The main flow portion 38 that transmits the first laser beam B1 may be a portion of the flow portion 36 or may be the entire flow portion 36. Figure 3A and Figure 3BAs shown, the portion of the flow portion 36 before it bends may be the main flow portion 38. However, the present invention is not limited thereto. For example, the portion of the flow portion 36 after it bends may be the main flow portion 38, or the entire flow portion 36 may be defined as the main flow portion 38. The position of the main flow portion 38 on the flow portion 36 is not limited.

[0081] For example, Figure 2 As shown, the main flow portion 38 may be formed to extend in one direction from the chamber inlet 32. In another example, the main flow portion 38 may be formed to extend in one direction from the chamber outlet 34.

[0082] The first laser beam B1 may be irradiated to the flow path of the liquid sample passing through the main flow portion 38. More specifically, the first laser beam B1 may be irradiated to the center of the flow path of the liquid sample passing through the main flow portion 38. However, the irradiation position of the pulsed laser beam B1 relative to the main flow portion 38 is not limited thereto.

[0083] The first laser beam B1 can pass through the main flow section 38. In other words, the main flow section 38 can be formed to extend in a single direction and pass through the path of the first laser beam B1. For example, the flow direction F of the liquid sample in the main flow section 38 and the irradiation direction of the first laser beam B1 can be perpendicular to each other. In other words, the extension direction of the main flow section 38 and the incident direction of the first laser beam B1 can be perpendicular to each other. The main flow section 38 can be formed to extend in a single direction from the chamber inlet 32.

[0084] For irradiation with the first laser beam B1 , at least a portion of the flow cell 30 including the main flow portion 38 may include a light-transmitting material.

[0085] However, the present invention is not limited thereto, and the flow direction F of the liquid sample and the irradiation direction of the pulsed laser beam B1 may be adjusted to a predetermined angle. The angle formed by the flow direction F and the irradiation direction of the pulsed laser beam B1 may be applied differently depending on the type of the detector 60 .

[0086] The flow device 20 may include an inlet portion 41 and an outlet portion 42 .

[0087] The liquid sample may pass through the inlet portion 41 and may be introduced into the flow chamber 30. After the liquid sample is discharged from the flow chamber 30, the liquid sample may be discharged to the outside of the flow device 20 through the outlet portion 42.

[0088] The flow device 20 can be connected to a container in which a liquid sample is stored. For example, an inlet portion 41 and an outlet portion 42 can be connected to the container. The liquid sample can be introduced from the container into the flow device 20 through the inlet portion 41. The liquid sample can be introduced from the flow device 20 into the container through the outlet portion 42. However, the present invention is not limited thereto, and the inlet portion 41 and the outlet portion 42 can be connected to separate containers.

[0089] The flow device 20 may include a flow controller 50 .

[0090] The flow controller 50 may be disposed on the path of the liquid sample. The flow controller 50 may control the flow rate and flow rate of the liquid sample passing through the flow chamber 30. The controller 70 may control the flow rate or flow rate of the liquid sample passing through the flow chamber 30 by controlling the flow controller 50.

[0091] like Figure 1 As shown, the flow controller 50 can be located on the path between the flow chamber 30 and the outlet portion 42. That is, since the flow controller 50 is arranged downstream in the flow path of the liquid sample, contamination of the liquid sample to be measured can be minimized. However, the arrangement of the flow controller 50 is not limited.

[0092] For example, the flow controller 50 may be located on a path between the flow chamber 30 and the inlet portion 41. The flow controller 50 is configured to control the flow rate of the liquid sample flowing in the flow chamber 30, and if the flow controller 50 is disposed at a location where the liquid sample is not contaminated, the flow controller 50 can satisfy this requirement.

[0093] The flow controller 50 can control the flow rate so that a predetermined flow rate of the liquid sample is located in the main flow portion 38 in a stationary state. In other words, the flow controller 50 can control the flow rate so that the liquid sample is located in the main flow portion 38 at a predetermined period T2 (see Figure 6 In other words, the flow controller 50 can control the flow rate of the liquid sample so that the liquid sample flows in a second period T2 (see Figure 6 and Figure 7 ) flows in the form of pulse waves.

[0094] The flow controller 50 may be configured to switch the flow state and the flow stop state of the liquid sample at a second cycle T2 (see Figure 6 and Figure 7 The flow state is a state in which the liquid sample flows through the flow portion 36, and the flow stop state may indicate a state in which the liquid sample stops flowing in the flow portion 36.

[0095] like Figure 6As shown, the flow controller 50 can be configured to make the liquid sample flow alternately between the flow state and the flow stop state in the form of pulses. When the flow controller 50 controls the liquid sample to be in the flow state, the liquid sample can flow through the flow portion 36 at a first flow rate V1. For ease of description, Figure 6 The first flow velocity V1 is shown to have a constant speed, but the amplitude and variation of the first flow velocity V1 are not limited thereto. When the flow controller 50 controls the liquid sample to be in a flow stop state, the flow of the liquid sample in the flow portion 36 may stop.

[0096] The flow controller 50 can repeatedly operate between the flow state and the flow stop state based on a signal received from the controller 70, and can also mechanically repeatedly operate between the flow state and the flow stop state. The method for implementing the operation of the flow controller 50 is not limited. This is sufficient if the flow controller 50 controls the flow of the liquid sample.

[0097] The flow operation of the liquid sample through the flow controller 50 may correspond to the irradiation of the first laser beam B1 through the laser generating device 12. For example, the first period T1 of the first laser beam B1 may be the same as the second period T2 of the flow controller 50. For example, the flow controller 50 may control the flow rate of the liquid sample passing through the flow chamber 30 so that the second period T2 of the flow controller 50 is the same as the first period T1 of the first laser beam B1.

[0098] refer to Figure 6 , the time when the flow stop state of the liquid sample begins can be synchronized with the time when the output of the first laser beam B1 changes to the second output P2. Figure 7 , the time when the output of the first laser beam B1 becomes the second output P2 may be later than the time when the flow stop state of the liquid sample begins by the first delay time d1.

[0099] When the flow controller 50 stops the flow of the liquid sample through the main flow portion 38 , the laser generator 10 may generate induced plasma in the nanoparticles in the liquid sample by irradiating the first laser beam B1 to the main flow portion 38 of the flow cell 30 .

[0100] Thereafter, when the flow controller 50 controls the liquid sample to be in a flowing state, the flow controller 50 can cause the liquid sample in which induced plasma is generated by flowing the liquid sample to flow downstream, and can introduce the liquid sample in which induced plasma is not generated into the main flow portion 38. When the liquid sample is flowing, the laser generator 10 can control the output of the first laser beam B1 so that induced plasma is not generated in the liquid sample.

[0101] When the flow controller 50 stops the flow of the liquid sample through the main flow portion 38 , the pulsed laser beam B1 as the second output P2 is irradiated to the main flow portion 38 of the flow chamber 30 by the laser generator 10 , and thus induced plasma can be generated in the nanoparticles of the liquid sample.

[0102] The present invention can measure nanoparticles in a flowing liquid sample and can improve the reliability of nanoparticle measurement by repeating the above process.

[0103] The flow device 20 can be configured so that the flow rate of the liquid sample passing through the main flow portion 38 in the flowing state is equal to or greater than the amount of the liquid sample located in the main flow portion 38 in the flow-stopped state. With this configuration, the liquid sample exposed to the first laser beam B1 of the second output P2 is exposed again to the first laser beam B1 of the second output P2, thereby preventing errors in nanoparticle measurement.

[0104] The flow device 20 may include a separation unit (not shown) for separating nanoparticles in the liquid sample before the liquid sample containing the nanoparticles is introduced into the flow chamber 30. The separation unit may be disposed between the flow chamber 30 and the inlet portion 41 to separate the nanoparticles from the liquid sample introduced into the flow chamber 30. The separation of the nanoparticles may be performed based on the type of the nanoparticles or the size of the nanoparticles.

[0105] Figure 4 An example of a flow controller of a flow nanoparticle measuring apparatus according to an embodiment of the present invention is shown.

[0106] The flow controller 50 may be configured to control the flow of the liquid sample. The flow controller 50 may operate in response to a control signal received from the controller 70.

[0107] The flow controller 50 may include a single piston pump. However, the present invention is not limited thereto. This requirement is satisfied if the flow controller 50 is configured to receive a signal from the controller 70 and control the flow rate of the liquid sample so that the signal corresponds to the pulses of the pulsed laser beam B. As an example, the flow controller 50 may include a magnetic valve for controlling the flow rate and flow rate of the liquid sample.

[0108] The flow controller 50 may include: Figure 1 ) of the first cycle T1 (see Figure 6 and Figure 7) A cam 51 that rotates, a cylinder 54, a piston 52 that is located inside the cylinder 54 and moves, and a connecting rod 53, one end of which is rotatably connected to the cam 51 and the other end of which is rotatably connected to the piston 52, and which transfers the rotational force of the cam 51 to the piston 52. An internal space 55 may indicate a space formed in the cylinder 51. The boundary of the internal space 55 may be determined by the piston 52. The piston 52 may be arranged in the internal space 55. The piston 52 may be coupled to the cylinder 54 to reciprocate in one direction.

[0109] The cam 51 can rotate around the rotation axis 51a. One end of the connecting rod 53 can be rotatably connected to the cam 51 at a position spaced apart from the rotation axis 51a. When the cam 51 rotates, the piston 52 can reciprocate inside the cylinder 54 through the connecting rod 53.

[0110] The flow controller 50 can adjust the flow period of the liquid sample by controlling the rotational speed of the cam 51. In other words, the flow controller 50 can adjust the flow state and the period of the flow cessation state of the liquid sample by controlling the rotational speed of the cam 51. The flow rate of the liquid sample can be controlled by factors such as the rotational speed of the cam 51, the arrangement between the rotating shaft 51a of the cam 51 and the connecting rod 53, and the internal volume of the cylinder 54. For example, the flow rate of the liquid sample can be controlled by adjusting the flow rate of the liquid sample.

[0111] The flow controller 50 may include valves 56a and 56b. In this embodiment, the valves 56a and 56b may include a pair of valves 56a and 56b. One valve 56a of the pair of valves 56a and 56b may be disposed at the liquid sample inlet of the cylinder 54. The other valve 56b of the pair of valves 56a and 56b may be disposed at the liquid sample outlet of the cylinder 54.

[0112] The valve 56a disposed at the liquid sample inlet of the cylinder 54 may be referred to as an inlet valve 56a. The valve 56b disposed at the liquid sample outlet of the cylinder 54 may be referred to as an outlet valve 56b. The inlet valve 56a may be connected to the flow chamber 30 (see Figure 1 ). The outlet valve 56b can be connected to the outlet portion 42 (see Figure 1 ).

[0113] The valves 56a and 56b may include anti-backflow valves. For example, the anti-backflow valves may be check valves. The inlet valve 56a allows the liquid sample to be introduced into the interior space 55 but prevents the liquid sample from being discharged outside the interior space 55. The outlet valve 56b allows the liquid sample to be discharged outside the interior space 55 but prevents the liquid sample from being introduced into the interior space 55.

[0114] The piston 52, the inlet valve 56a, and the outlet valve 56b may be connected to the internal space 55. In other words, the piston 52, the inlet valve 56a, and the outlet valve 56b may form a portion of a boundary of the internal space 55.

[0115] When the piston 52 applies pressure to the interior space 55 of the cylinder 54, the inlet valve 56a can be closed and the outlet valve 56b can be opened. During this process, the liquid sample in the interior space 55 can be discharged to the outside of the flow controller 50 through the outlet valve 56b. When the inlet valve 56a is closed, the flow of the liquid sample located upstream of the flow controller 50 can be stopped. In other words, when the piston 52 applies pressure to the interior space 55 of the cylinder 54, the flow of the liquid sample in the flow chamber 30 can be stopped. When the piston 52 applies pressure to the interior space 55 of the cylinder 54, it can mean that the interior space of the cylinder 54 is reduced by the piston 52.

[0116] Conversely, when the piston 52 operates in the direction opposite to the pressurization direction, the outlet valve 56b may be closed and the inlet valve 56a may be opened. When the piston 52 operates in the direction opposite to the pressurization direction, it may mean that the internal space 55 of the cylinder 54 is enlarged by the piston 52. During this process, the liquid sample outside the cylinder 54 can be introduced into the internal space 55 of the cylinder 54 through the opened inlet valve 56a.

[0117] When the internal space 55 of the cylinder 54 is enlarged by the piston 52, the inlet valve 56a is opened, and the liquid sample can be introduced into the internal space 55 of the cylinder 54 through the inlet valve 56a. When the liquid sample is introduced into the internal space 55 of the cylinder 54 through the inlet valve 56a, the liquid sample in the flow chamber 30 can flow. In other words, when the internal space 55 of the cylinder 54 is enlarged by the piston 52, the liquid sample in the flow chamber 30 can flow.

[0118] The flow chamber 30 is shown and described as being disposed upstream of the flow controller 50 by way of example, but the present invention is not limited thereto. When the flow chamber 30 is disposed downstream of the flow controller 50, the above-described operation may be performed in reverse.

[0119] That is, the movement of the piston 52 in the pressurizing direction allows the liquid sample in the flow chamber 30 to flow, while the movement of the piston 52 in the direction opposite to the pressurizing direction allows the liquid sample in the flow chamber 30 to stop flowing. In other words, for example, the inlet valve 56a may be connected to the inlet portion 41 (see Figure 1 ), and the outlet valve 56b can be connected to the flow chamber 30 (see Figure 1 For example, when the inner space 55 of the cylinder 54 is pressurized by the piston 52, the flow chamber 30 (see Figure 1) can flow. For example, if the piston 52 moves in the direction opposite to the direction in which the cylinder 54 is pressurized, the flow chamber 30 (see Figure 1 ) The liquid sample in the container may not flow.

[0120] Through this process, the flow controller 50 can control the flow of the liquid sample at a predetermined cycle.

[0121] refer to Figures 1 to 4 , the flow nanoparticle measuring device 1 may include a detector 60 .

[0122] Nanoparticles contained in a liquid sample can be placed in a plasma state by first laser beam B1. Detector 60 can detect shock waves or scintillation generated during this process. Detector 60 can detect various signals generated in the plasma. Detector 60 can detect at least one of an element's spectrum, shock waves, an image of the plasma, heat, and sound.

[0123] The detector 60 may include a shock wave detector that measures the laser-induced shock wave associated with the generation of the laser-induced plasma. The detector 60 may include a scintillation detector 60 that detects scintillation associated with the generation of the laser-induced plasma. When the induced plasma is generated in the nanoparticles by the first laser beam B1, the characteristics of the laser-induced plasma may vary depending on the size of the nanoparticles.

[0124] The shock wave detector may include at least one of a piezoelectric element and a microphone.The signal measured by the shock wave detector may be amplified by a lock-in amplifier.

[0125] The scintillation detector may include a CCD camera. The scintillation detector 60 may also include a notch filter arranged on the optical path toward the CCD camera to control measurement errors caused by scattered light. Figure 1 As shown, the shock wave detector and the scintillation detector may be respectively arranged adjacent to the flow cell 30. At least one of the shock wave detector and the scintillation detector may be arranged adjacent to the flow cell 30.

[0126] The detector 60 can obtain information about the nanoparticles by detecting the shock wave or the scintillation. The information about the nanoparticles may include the number and / or size of the nanoparticles.

[0127] The detector 60 may be disposed inside the flow chamber 30 or may be disposed as Figure 1As shown, the detector 60 is arranged outside the flow chamber 30. In addition, a plurality of detectors 60 may be arranged around the flow chamber 30. The controller 70 may correct the detection value based on the distance from the detector 60 to the location where the induced plasma is generated inside the flow chamber 30. The controller 70 may correct the detection value based on the angle between the direction toward the detector 60 at the location where the induced plasma is generated inside the flow chamber 30 and the irradiation direction of the first laser beam B1. The type of the detector 60 is not limited, and the detector 60 may include various detectors, such as a thermal sensor.

[0128] The flow nanoparticle measurement device 1 may include a controller 70 .

[0129] The controller 70 may control the overall operation of the flow nanoparticle measuring apparatus 1. For example, the controller 70 may control the laser generating apparatus 12 and the flow controller 50. The controller 70 may control the laser generating apparatus 12 to control the first period T1 (see Figure 6 and Figure 7 ) and / or the output of the first laser beam B1. In addition, the controller 70 may control the flow controller 50 to control the second period T2 (see Figure 6 and Figure 7 ) or the flow time of a liquid sample.

[0130] The controller 70 may control the laser generating device 12 and the flow controller 50 independently of each other. That is, the controller 70 may control the laser generating device 12 and the flow controller 50 separately.

[0131] The controller 70 may move the lens 18 relative to the flow chamber 30 to adjust the focus of the first laser beam B1 .

[0132] The controller 70 may obtain information about the nanoparticles from the detector 60 .

[0133] The controller 70 can pre-process the signal transmitted from the detector 60. The controller 70 uses a lock-in amplifier to amplify the signal detected by the detector 60 and can use a bandpass filter to remove noise in the low-frequency band less than or equal to 100 Hz. The filtered signal can be converted into a digital signal by a converter. The converted signal can be subjected to a real-time fast Fourier transform (FFT) by extracting the signal values ​​of some segments according to conditions. Through this process, the controller 70 can convert the signal from a function of time to a function of frequency and analyze the frequency component of the shock wave generated by the plasma. The controller 70 can determine the type, size, or number of nanoparticles based on the frequency component and the amplitude converted from the detected shock wave.

[0134] Under the same output conditions, the size of the induced plasma increases as the particle size increases, and thus the size of the shock wave may also increase. Based on the frequency component and the amplitude of the shock wave, the controller 70 may determine the type, size or number of the nanoparticles.

[0135] The controller 70 may determine the size or number of the nanoparticles based on the number and size of the scintillation detected by the scintillation detector.

[0136] The controller 70 may measure the concentration of the nanoparticles in the liquid sample based on the flow rate of the liquid sample flowed by the flow controller 50 and the information on the nanoparticles detected by the detector 60 .

[0137] The operation of the flow nanoparticle measuring apparatus according to the present invention will be described below.

[0138] Figure 5 is a flowchart illustrating a flowing nanoparticle measurement method ( S100 ) according to an embodiment of the present invention. Figure 6 The time-dependent operation in a flow nanoparticle measurement apparatus according to an embodiment of the present invention is shown.

[0139] exist Figure 5 In the flowchart shown, the method is described by dividing it into multiple steps, but at least some of the steps can be performed in a different order, performed in combination with other steps, omitted, divided into sub-steps, or performed by adding one or more steps not shown.

[0140] exist Figure 6 In the embodiment of the present invention, the second output P2 of the first laser beam B1 may be greater than the first output P1. For example, the first output P1 may be zero. The controller 70 may control the output of the first laser beam B1 over time.

[0141] refer to Figures 1 to 5 The flow nanoparticle measurement device 1 may be configured to measure nanoparticles contained in a flowing liquid sample. The controller 70 may control the laser generating device 12 and the flow controller 50 .

[0142] The flow device 20 can flow a liquid sample containing nanoparticles to the main flow portion 38 of the flow chamber 30. More specifically, the flow device 20 can introduce the liquid sample into the flow chamber 30 through the chamber inlet 32 ​​and discharge the liquid sample to the outside of the flow chamber 30 through the chamber outlet 34. The flow rate of the liquid sample flowing through the flow device 20 can be controlled by the flow controller 50.

[0143] refer to Figures 1 to 6The flow controller 50 may control the flow rate of the liquid sample so that a predetermined flow rate of the liquid sample is located in the main flow portion 38 in a stationary state. That is, the flow controller 50 may be configured to repeatedly flow the liquid sample in a second period T2.

[0144] The pulsed laser beam B generated by the laser generating device 12 may be split into a first laser beam B1 and a second laser beam B2 by the beam splitter 16. The first laser beam B1 may pass through the lens 18 and may be irradiated to the main flow portion 38 of the flow chamber 30. The first laser beam B1 may be repeatedly irradiated with pulses of a first period T1.

[0145] The flowing nanoparticle measurement method S100 according to an embodiment of the present invention may include step S110 of irradiating a pulsed laser beam onto a liquid sample flowing in a flow chamber 30. In step S110, the pulsed laser beam irradiated onto the liquid sample may be a first laser beam B1. In step S110, the controller 70 may control the output of the first laser beam B1 and irradiate the pulsed laser beam onto the liquid sample.

[0146] The first period T1 of the first laser beam B1 can be the same as the period of the pulsed laser beam B. The first period T1 of the first laser beam B1 can be the same as the second period T2 of the flow controller 50. The flow controller 50 can control the flow rate of the liquid sample passing through the flow chamber 30 to correspond to the period of the pulsed laser beam. For example, the start time of the flow stop state of the liquid sample can be synchronized with the time when the output of the first laser beam B1 changes to the second output P2. For example, the start time of the flow state of the liquid sample can be synchronized with the time when the output of the first laser beam B1 changes to the first output P1.

[0147] Thus, when the flow of the liquid sample through the main flow portion 38 is stopped by the flow controller 50 , the first laser beam B1 may be irradiated to the main flow portion 38 of the flow cell 30 to generate plasma in the nanoparticles in the liquid sample.

[0148] The flowing nanoparticle measurement method S100 according to an embodiment of the present invention may include step S120: obtaining a detection signal using a detector. The first laser beam B1 may generate plasma or shock waves in the nanoparticles of the liquid sample stopped by the flow controller 50. The detector 60 may detect the generated plasma or shock waves to generate a detection signal. The detection signal may include information about the shock waves. In step S120, the controller 70 may obtain the detection signal using the detector 60.

[0149] The flow nanoparticle measurement method S100 according to an embodiment of the present invention may include step S130: calculating concentration information of the liquid sample. In step S130, the controller 70 may calculate the concentration information of the nanoparticles contained in the liquid sample based on the flow rate of the liquid sample controlled by the flow controller 50 and the detection signal obtained from the detector 60.

[0150] The controller 70 can be configured to control the flow controller 50 so that the liquid sample repeats the flowing state and the flow stopping state at a predetermined period, and to control the laser generator 10 so that the first laser beam B1 is irradiated at a predetermined period. Therefore, this method can improve the reliability of nanoparticle measurement by measuring nanoparticles in a flowing liquid sample.

[0151] Figure 7 A time-dependent operation in a flow nanoparticle measurement apparatus according to another embodiment of the present invention is shown.

[0152] refer to Figures 1 to 7 , the flow nanoparticle measuring apparatus 1 may be configured to measure nanoparticles contained in a flowing liquid sample.

[0153] The first period T1 of the first laser beam B1 may be the same as the second period T2 of the flow controller 50 .

[0154] Furthermore, the start time of the first period T1 of the first laser beam B1 may be delayed by the first delay time d1 relative to the start time of the second period T2 of the flow controller 50. In other words, the start time of the operation of the first laser beam B1 as the second output P2 may be delayed by the first delay time d1 relative to the start time at which the flow rate of the liquid sample becomes zero. Thus, after the flow of the liquid sample is stopped by the flow controller 50 and after the first delay time d1 has elapsed, the first laser beam B1 may be irradiated to the flow chamber 30.

[0155] The start time when the flow rate of the liquid sample becomes the first flow rate V1 can be delayed by the second delay time d2 from the start time when the first laser beam B1 becomes the first output P1. Thus, after the first laser beam B1 is irradiated to the flow cell 30 and after the second delay time d2 has elapsed, the liquid sample can flow at the first flow rate V1 and can be discharged from the flow cell 30.

[0156] The time during which the flow rate of the liquid sample is maintained at zero during the second period T2 can be greater than the time during which the first laser beam B1 operates as the second output P2 during the first period T1. Therefore, the first laser beam B1 is irradiated to the nanoparticles in which no induced plasma is formed, and the induced plasma can be stably generated.

[0157] Figure 8Schematic illustration of plasma generation by a pulsed laser beam in a flow nanoparticle measurement apparatus according to an embodiment of the present invention.

[0158] refer to Figure 8 , a plurality of detectors 60 may be provided. A plurality of detectors 60a, 60b, and 60c may be arranged at the flow chamber 30. For example, the plurality of detectors 60a, 60b, and 60c may be arranged adjacent to the flow portion 36 and may detect shock waves caused by plasma generated in the flow portion 36.

[0159] The arrangement of the plurality of detectors 60a, 60b, and 60c relative to the flow portion 36 is not limited to Figure 8 For example, at least a portion of the plurality of detectors 60a, 60b, and 60c may be arranged to be exposed to the flow space 37 of the flow portion 36, or may be arranged in the flow chamber 30 to be spaced apart from the flow portion 36 by a predetermined distance.

[0160] The shock wave signal may be generated by detecting the shock wave by the detectors 60a, 60b, and 60c. The shock wave signal (or information) may be converted into a signal regarding amplitude and frequency by the shock wave analysis unit 180.

[0161] The plurality of detectors 60a, 60b, and 60c may be arranged to be spaced apart from one another along the liquid sample flow direction F. When the plurality of detectors 60a, 60b, and 60c are arranged to be spaced apart from one another by a predetermined distance, the plurality of detectors 60a, 60b, and 60c may detect shock waves caused by the generation of plasma by varying the magnitude of the amplitude.

[0162] Figure 8 The arrangement of three detectors is shown by way of example. However, the present invention is not limited thereto. This requirement can be satisfied by arranging at least two detectors. For ease of description, the multiple detectors 60a, 60b, and 60c may include a first detector 60a, a second detector 60b arranged further downstream than the first detector 60a in the flow direction F of the liquid sample, and a third detector 60c arranged further downstream than the second detector 60b in the flow direction F.

[0163] The first detector 60a may be disposed adjacent to a position S where plasma is generated by irradiation of the first laser beam B1. The position S where plasma is generated may be set by an irradiation direction of the first laser beam B1 with respect to the flow portion 36.

[0164] The first detector 60a can be arranged radially relative to the location S where plasma is generated. However, the location of the first detector 60a is not limited. For example, if the first detector 60a is arranged adjacent to the location S where plasma is generated, this is sufficient. The multiple detectors 60a, 60b, and 60c are arranged at predetermined distances along the flow direction F of the liquid sample, and can accurately detect the shock wave caused by the generation of plasma by changing the position and / or angle from the location where plasma is generated. The multiple detectors 60a, 60b, and 60c can also minimize distortion of the detection results caused by the generation of noise.

[0165] When the distance between the plasma generation location S and the detectors 60a, 60b, and 60c is short, bubbles may be generated for a long time during detection. These bubbles may prevent the detection element from detecting the shock wave. In addition, when the distance between the plasma generation location S and the detectors 60a, 60b, and 60c is long, reflected waves generated by the outer surface of the flow portion 36 or the surface of the liquid sample may be detected, resulting in distortion of the detection results.

[0166] The plurality of detectors 60a, 60b, and 60c may include piezoelectric elements each having a width, length, and height of 2 mm. The arrangement of the plurality of detectors 60a, 60b, and 60c may be adjusted at the nanometer level, and thus may detect shock waves with high resolution in consideration of the plasma generation position S.

[0167] Figure 9 is a block diagram illustrating a controller of a flow nanoparticle measuring apparatus according to an embodiment of the present invention. Figure 10 (a) and (b) are graphs showing the frequency and amplitude of shock waves detected by a plurality of detectors, which is one configuration of a flow nanoparticle measurement apparatus according to an embodiment of the present invention.

[0168] Although three or more detectors may be arranged as described above, for convenience of description, an embodiment including the first detector 60a and the second detector 60b will be described. The detector 60 may include a third detector 60c and more detectors.

[0169] refer to Figure 9 and Figure 10 , the controller 170 may analyze the nanoparticles based on the shock waves detected by the plurality of detectors 60a and 60b.

[0170] The controller 170 may include a shock wave analysis unit 180 .

[0171] The shock wave analysis unit 180 may analyze the shock waves detected by the plurality of detectors 60a and 60b. The shock wave analysis unit 180 may convert the signals transmitted from the detectors 60 into signals such as Figure 10 The functions shown are related to frequency and amplitude. Figure 10 , (a) shows that the shock wave detected by the first detector 60a is converted into parameters related to frequency and amplitude, and (b) shows that the shock wave detected by the second detector 60b is converted into parameters related to frequency and amplitude.

[0172] The shock wave analysis unit 180 may include a frequency measurement unit 182 that measures a natural frequency and an amplitude measurement unit 184 that measures an amplitude.

[0173] Frequency measurement unit 182 can measure the frequency at which the amplitude occurs. In other words, frequency measurement unit 182 can specify a frequency corresponding to a specific amplitude. One of the multiple frequencies specified by frequency measurement unit 182 can be defined as a natural frequency. For example, a natural frequency can indicate a frequency corresponding to a local peak amplitude.

[0174] The frequency measurement unit 182 may specify at least one natural frequency from the shock wave signal detected by each of the plurality of detectors 60a and 60b. The frequency measurement unit 182 may define overlapping frequencies f1 and f2 as natural frequencies among the frequencies specified by the plurality of detectors 60a and 60b to remove noise generated during the plasma generation process.

[0175] The amplitude measuring unit 184 may measure the amplitude at the natural frequency measured by the frequency measuring unit 182 .

[0176] The controller 170 may include an amplitude ratio calculator 186 and a nanoparticle determination unit 188 .

[0177] The amplitude ratio calculator 186 may calculate the amplitude ratio at the natural frequency. For example, the amplitude ratio calculator 186 may calculate the amplitude ratio of the natural frequency of each of the plurality of detectors 60a and 60b.

[0178] The amplitude ratio calculator 186 may calculate the amplitude ratio of the natural frequency of each of the plurality of detectors 60a and 60b. If there are multiple natural frequencies of the nanoparticle, the amplitude measured by the amplitude measurement unit 184 may be different for each natural frequency.

[0179] Amplitude ratio calculator 186 can calculate a first amplitude ratio and a second amplitude ratio, where the first amplitude ratio is the ratio of the amplitude magnitudes A1a and A2a at the multiple natural frequencies f1 and f2 measured by first detector 60a, and the second amplitude ratio is the ratio of the amplitude magnitudes A1b and A2b at the multiple natural frequencies f1 and f2 measured by second detector 60b. For example, the first amplitude ratio can be the ratio of the amplitude magnitude A1a at the first natural frequency f1 to the amplitude magnitude A2a at the second natural frequency f2 in first detector 60a. For example, the second amplitude ratio can be the ratio of the amplitude magnitude A1b at the first natural frequency f1 to the amplitude magnitude A2b at the second natural frequency f2 in second detector 60b. Amplitude magnitude can indicate the magnitude of the amplitude.

[0180] The nanoparticle determination unit 188 may determine the type and size of the nanoparticles based on the natural frequency measured by the frequency measurement unit 182 and the amplitude ratio calculated by the amplitude ratio calculator 186 .

[0181] The nanoparticle determination unit 188 may specify the type of the nanoparticle based on the natural frequency measured by the frequency measurement unit 182. In addition, the nanoparticle determination unit 188 may determine the size of the specified nanoparticle based on the change in the amplitude ratio.

[0182] That is, the nanoparticle determination unit 188 can compare the data of the natural frequency of each nanoparticle pre-stored in the controller 170 with the natural frequency calculated by the frequency measurement unit 182 to specify the type of the nanoparticle. The nanoparticle determination unit 188 can compare the data of the first amplitude ratio and the second amplitude ratio of each nanoparticle pre-stored in the controller 170 with the first amplitude ratio and the second amplitude ratio calculated by the amplitude ratio calculator 186 to determine the size of the matched nanoparticle. Thus, the nanoparticle determination unit 188 can determine the type and size of the nanoparticle.

[0183] Figure 11 is a flow chart illustrating a method S200 for determining the type and size of nanoparticles according to an embodiment of the present invention.

[0184] refer to Figures 1 to 11 , plasma is generated in the nanoparticles by the first laser beam B1, and a shock wave is generated in the process.

[0185] Since the plurality of detectors 60a and 60b are spaced apart from each other along the flow direction F of the liquid sample, the same shock wave can be detected by changing the distances between the plurality of detectors 60a and 60b and the shock wave generation positions.

[0186] The shock wave analysis unit 180 may analyze the electrical signals of the shock waves detected by the plurality of detectors 60a and 60b and may convert the electrical signals of the shock waves into parameters related to frequency and amplitude.

[0187] The frequency measuring unit 182 of the shock wave analyzing unit 180 can measure the common natural frequencies f1 and f2 in the first detector 60a and the second detector 60b. Figure 10 In (a) and (b), the frequency measuring unit 182 may define the first natural frequency f1 as 8 kHz and the second natural frequency f2 as 22 kHz based on the shock waves detected by the first detector 60 a and the second detector 60 b .

[0188] The method S200 for determining the type and size of nanoparticles according to an embodiment of the present invention may include step S210: measuring the amplitude and frequency of the shock wave. In step S210, the controller 70 may measure the amplitude and frequency of the shock wave based on the detection signal. In other words, in step S210, the controller 70 may generate spectrum information of the amplitude based on the frequency of the detection signal.

[0189] In step S210, the amplitude measurement unit 184 of the shock wave analysis unit 180 may measure the magnitude of the amplitude at the natural frequencies f1 and f2. Figure 10 As shown in (a), the amplitude measurement unit 184 can measure the amplitude A1a at the first natural frequency f1 to be 0.015 and the amplitude A2a at the second natural frequency f2 to be 0.16. Figure 10 As shown in (b), the amplitude measurement unit 184 can measure the amplitude A1b at the first natural frequency f1 as 0.012 and the amplitude A2b at the second natural frequency f2 as 0.004.

[0190] The method S200 for determining the type and size of nanoparticles according to an embodiment of the present invention may include step S220 of calculating an amplitude ratio of each of the plurality of detectors at a natural frequency based on the measured amplitude and natural frequency.

[0191] In step S220, the amplitude ratio calculator 186 may calculate the first detector amplitude ratio and the second detector amplitude ratio based on the analysis result of the shock wave analysis unit 180. For example, referring to Figure 10 , the amplitude ratio calculator 186 may calculate the first detector amplitude ratio as 0.015:0.16 and the second detector amplitude ratio as 0.012:0.004 based on the magnitude of the amplitude measured by the amplitude measurement unit 184. The detector amplitude ratio may indicate at least one of the first detector amplitude ratio and the second detector amplitude ratio. The "amplitude ratio of each detector" may indicate the detector amplitude ratio.

[0192] The method S200 for determining the type and size of nanoparticles according to an embodiment of the present invention may include step S230 of specifying the type of nanoparticles according to the measured natural frequency and determining the size of the nanoparticles based on the amplitude ratio of each detector.

[0193] In step S230, the nanoparticle determination unit 188 may determine the type and size of the nanoparticles. The nanoparticle determination unit 188 may specify the type of the nanoparticles based on the measured natural frequencies f1 and f2.

[0194] In step S230, the nanoparticle determination unit 188 may determine the size of the nanoparticle based on the amplitude ratio of the specified nanoparticle calculated by the amplitude ratio calculator 186. That is, the nanoparticle determination unit 188 may specify the type of nanoparticle based on the measured natural frequency, and compare the amplitude ratio of the first detector and the second detector calculated by the amplitude ratio calculator 186 with pre-stored data of the amplitude ratio of the first detector and the second detector for each type of nanoparticle to determine the size of the specified nanoparticle.

[0195] The present invention can more accurately determine the type and size of nanoparticles by varying the distances between multiple detectors and shock waves, and by determining the nanoparticles based on changes in the amplitude ratio of each of the multiple detectors. The present invention can also improve the reliability of the determination results by using the detection results from multiple detectors.

[0196] The controller 170 includes a shock wave analysis unit 180 , and the shock wave analysis unit 180 may include a frequency measurement unit 182 that measures a natural frequency and an amplitude measurement unit 184 that measures an amplitude.

[0197] The controller 170 may include an amplitude ratio calculator 186 and a nanoparticle determination unit 188 .

[0198] The amplitude ratio calculator 186 may calculate the ratio of the magnitudes of the amplitudes. The amplitude ratio calculator 186 may calculate the amplitude ratio of each natural frequency in the plurality of detectors 60a and 60b.

[0199] The amplitude ratio calculator 186 may calculate the amplitude ratio of each natural frequency f1 and f2 in the plurality of detectors 60a and 60b. When the natural frequency of the nanoparticle is one or more, the magnitude of the amplitude measured by the amplitude measuring unit 184 may be detected for each natural frequency.

[0200] The amplitude ratio calculator 186 can calculate an amplitude ratio for each of the natural frequencies f1 and f2. That is, the amplitude ratio at the first natural frequency can indicate the ratio of the amplitude magnitude A1a at the first natural frequency f1 measured by the first detector 60a to the amplitude magnitude A1b at the first natural frequency f1 measured by the second detector 60b. Furthermore, the amplitude ratio at the second natural frequency can indicate the ratio of the amplitude magnitude A2a at the second natural frequency f2 measured by the first detector 60a to the amplitude magnitude A2b at the second natural frequency f2 measured by the second detector 60b. The amplitude ratio at the natural frequency can indicate at least one of the first natural frequency amplitude ratio and the second natural frequency amplitude ratio.

[0201] Since the natural frequency amplitude ratio is calculated for each natural frequency, if there are multiple natural frequencies, multiple amplitude ratios can be calculated. In addition, if there is one natural frequency, one natural frequency amplitude ratio can be calculated.

[0202] The nanoparticle determination unit 188 may determine the type and size of the nanoparticles based on the natural frequency measured by the frequency measurement unit 182 and the amplitude ratio calculated by the amplitude ratio calculator 186 .

[0203] The nanoparticle determination unit 188 can specify the type of nanoparticle based on the natural frequency measured by the frequency measurement unit 182. The nanoparticle determination unit 188 can also specify the size of the nanoparticle that matches the amplitude ratio calculated by the amplitude ratio calculator 186 based on the change of the pre-stored amplitude ratio of each natural frequency. That is, the nanoparticle determination unit 188 can compare the pre-stored data of the natural frequency for each nanoparticle with the natural frequency calculated by the frequency measurement unit to specify the type of nanoparticle, and can compare the pre-stored data of the amplitude ratio for each natural frequency with the amplitude ratio calculated by the amplitude ratio calculator 186 to determine the size of the matched nanoparticle.

[0204] When a nanoparticle has multiple natural frequencies, the nanoparticle determination unit 188 can compare the amplitude ratio of each of the multiple natural frequencies with pre-stored data to determine the size of the matched nanoparticle. In this way, the nanoparticle determination unit 188 can determine the type and size of the nanoparticle.

[0205] Figure 12 FIG. 4 is a flow chart illustrating a method S300 for determining the type and size of nanoparticles according to another embodiment of the present invention.

[0206] Plasma is generated from the nanoparticles contained in the liquid sample by the pulse laser beam B1, and a shock wave is generated in the process.

[0207] The plurality of detectors 60a and 60b are spaced apart from each other along the flow direction F of the liquid sample and thus can detect the same shock wave by varying the distance from the shock wave generation position.

[0208] The shock wave analysis unit 180 may analyze the electrical signals of the shock waves detected by the plurality of detectors 60a and 60b and may convert the electrical signals of the shock waves into parameters related to frequency and amplitude.

[0209] The frequency measuring unit 182 of the shock wave analyzing unit 180 can measure the common natural frequencies f1 and f2 in the first detector 60a and the second detector 60b. Figure 10 In (a) and (b), the frequency measuring unit 182 may define common natural frequencies as 8 kHz and 22 kHz based on the shock waves detected by the first detector 60 a and the second detector 60 b .

[0210] refer to Figures 1 to 10 and Figure 12 According to another embodiment of the present invention, a method for determining the type and size of nanoparticles ( S300 ) may include step S310 of measuring the amplitude and natural frequency of a shock wave. In step S310 , the controller 70 may measure the amplitude and frequency of the shock wave based on the detection signal. In other words, in step S310 , the controller 70 may generate spectrum information of the amplitude based on the frequency of the detection signal.

[0211] In step S310, the amplitude measurement unit 184 of the shock wave analysis unit 180 may measure the magnitude of the amplitude at the natural frequencies f1 and f2. Figure 10 As shown in (a), the amplitude measurement unit 184 can measure the amplitude A1a of the first natural frequency f1 in the first detector 60a as 0.015 and the amplitude A2a of the second natural frequency f2 as 0.16. Figure 10 As shown in (b), the amplitude measurement unit 184 can measure the amplitude A1b of the first natural frequency f1 in the second detector 60b as 0.012 and the amplitude A2b of the second natural frequency f2 as 0.004.

[0212] The method S300 for determining the type and size of nanoparticles according to another embodiment of the present invention may include step S320 of calculating an amplitude ratio of each natural frequency in a plurality of detectors based on the measured amplitude and natural frequency.

[0213] In step S320, the amplitude ratio calculator 186 may calculate the amplitude ratio of each natural frequency based on the analysis result of the shock wave analysis unit 180. For example, the amplitude ratio calculator 186 may calculate a first natural frequency amplitude ratio and a second natural frequency amplitude ratio based on the amplitude measured by the amplitude measurement unit 184. The natural frequency amplitude ratio may indicate at least one of the first natural frequency amplitude ratio and the second natural frequency amplitude ratio. The "amplitude ratio of each natural frequency" may indicate the natural frequency amplitude ratio.

[0214] The first natural frequency amplitude ratio may refer to a ratio of the amplitude A1a measured by the first detector 60a to the amplitude A1b measured by the second detector 60b at the first natural frequency f1. For example, the first natural frequency amplitude ratio may be 0.015:0.012.

[0215] The second natural frequency amplitude ratio may refer to a ratio of the amplitude A2a measured by the first detector 60a to the amplitude A2b measured by the second detector 60b at the second natural frequency f2. For example, the second natural frequency amplitude ratio may be 0.16:0.004.

[0216] The method S300 for determining the type and size of nanoparticles according to another embodiment of the present invention may include step S330 of specifying the type of nanoparticles according to the measured natural frequencies and determining the size of the nanoparticles based on the amplitude ratio of each natural frequency.

[0217] In step S330, the nanoparticle determination unit 188 may determine the type and size of the nanoparticles. The nanoparticle determination unit 188 may specify the type of the nanoparticles based on the measured natural frequencies f1 and f2. In addition, the nanoparticle determination unit 188 may determine the size of the nanoparticles based on the amplitude ratio of each natural frequency of the specified nanoparticles calculated by the amplitude ratio calculator 186. That is, the nanoparticle determination unit 188 may specify the type of the nanoparticles based on the measured natural frequencies, and compare the first natural frequency amplitude ratio and the second natural frequency amplitude ratio calculated by the amplitude ratio calculator 186 with the first natural frequency amplitude ratio and the second natural frequency amplitude ratio data pre-stored for each type of nanoparticle to determine the size of the nanoparticles.

[0218] refer to Figures 1 to 12 , the “amplitude ratio” may indicate at least one of a “detector amplitude ratio” and a “natural frequency amplitude ratio”.

[0219] Step S220 and step S320 of calculating the amplitude ratio may indicate at least one of step S220 of calculating the amplitude ratio of each of the plurality of detectors at a natural frequency and step S320 of calculating the amplitude ratio of each natural frequency in the plurality of detectors.

[0220] Steps S230 and S330 of specifying the type of nanoparticles according to the measured natural frequency and determining the size of the nanoparticles based on the calculated amplitude ratio may indicate at least one of steps S230 and S330, wherein step S230 is to indicate the type of nanoparticles according to the measured natural frequency and determine the size of the nanoparticles based on the amplitude ratio of each detector, and step S330 is to specify the type of nanoparticles according to the measured natural frequency and determine the size of the nanoparticles based on the amplitude ratio of each natural frequency.

[0221] The present invention can more accurately determine the type and size of nanoparticles by changing the distance between multiple detectors and shock waves and determining the nanoparticles based on the change in the amplitude ratio of each natural frequency through this operation. The present invention can also improve the reliability of the determination result by using the detection results from multiple detectors.

[0222] Although embodiments have been described with reference to several illustrative embodiments of the present invention, those skilled in the art may devise many other variations and other embodiments that fall within the scope of the principles of the present invention. In particular, various variations and modifications of the arrangement of component parts and / or subject combinations within the scope of this specification, the drawings, and the appended claims are possible. In addition to variations and modifications of component parts and / or arrangements, alternative uses will also be apparent to those skilled in the art. The scope of the present invention should be determined by a reasonable interpretation of the appended claims, and all modifications within the scope of the invention are included within the scope of the invention.

Claims

1. A flow nanoparticle measurement device comprising: a flow chamber configured to form a flow path through which a liquid sample flows; a laser generator configured to generate a first laser beam and irradiate the first laser beam to the flow chamber; a plurality of detectors disposed at the flow chamber and configured to detect shock waves of the plasma induced by the first laser beam in the flow chamber and to generate detection signals; as well as a controller configured to obtain the detection signals from the plurality of detectors and determine the type and size of the nanoparticles contained in the liquid sample based on the detection signals, Wherein, the controller includes: an amplitude measuring unit configured to measure the amplitude of the shock wave based on the detection signal; and a frequency measuring unit configured to measure a natural frequency of the shock wave based on the detection signal, wherein the plurality of detectors include a first detector and a second detector arranged to be spaced apart from each other along the flow path, wherein the second detector is arranged at a position further downstream in the flow path than the first detector, and Wherein, the controller includes: an amplitude ratio calculator configured to extract at least one common natural frequency measured by the first detector and the second detector, and calculate a natural frequency amplitude ratio, the natural frequency amplitude ratio being a ratio of an amplitude corresponding to the common natural frequency in the first detector to an amplitude corresponding to the common natural frequency in the second detector; and A nanoparticle determination unit is configured to specify the type of the nanoparticle based on data pre-stored in the controller and the common natural frequency, and to determine the size of the nanoparticle based on the data and the natural frequency amplitude ratio.

2. The flow nanoparticle measurement device according to claim 1, wherein: The plurality of detectors are arranged to be spaced apart from each other along the flow path.

3. The flow nanoparticle measurement device according to claim 1, wherein: The shock wave is generated at a set location in the flow chamber, and The plurality of detectors are arranged to have varying distances from the set position.

4. The flow nanoparticle measurement device according to claim 1, wherein: The controller determines the type and size of the nanoparticles based on the amplitude and frequency of the shock wave.

5. The flow nanoparticle measurement device according to claim 1, wherein: The laser generator comprises: a laser generating device configured to generate a pulsed laser beam; a beam splitter configured to split the pulsed laser beam into the first laser beam and a second laser beam; and a lens disposed between the beam splitter and the flow chamber and configured to adjust a focus of the first laser beam, The focal length is the distance between the focus of the first laser beam and the lens.

6. The flow nanoparticle measurement device according to claim 5, wherein: The laser generator further includes an energy detector facing the beam splitter and configured to measure the power of the second laser beam, and The second laser beam travels at an angle to the first laser beam and is incident on the energy detector.

7. The flow nanoparticle measurement device according to claim 5, wherein: The laser generator further includes a beam stop facing the flow chamber and configured to stop the first laser beam from passing through the flow chamber, and The flow chamber is located between the lens and the beam blocking member.

8. The flow nanoparticle measurement device according to claim 1, wherein: The flow chamber comprises: a flow portion, the flow portion being a space formed inside the flow chamber; a chamber inlet connected to the flow portion, the chamber inlet being an opening formed in the flow chamber, and the liquid sample being injected into the flow portion through the chamber inlet; and A chamber outlet is connected to the flow portion and spaced apart from the chamber inlet. The chamber outlet is an opening formed in the flow chamber, and the liquid sample is discharged from the flow portion through the chamber outlet.

9. The flow nanoparticle measurement device according to claim 8, wherein: The flow portion includes a main flow portion formed inside the flow chamber, and The main flow portion extends in one direction and passes through a path of the first laser beam.

10. The flow nanoparticle measurement device according to claim 1, further comprising: A flow controller is connected to the flow chamber, disposed on a path of the liquid sample, and configured to control a flow rate of the liquid sample.

11. The flow nanoparticle measurement device according to claim 10, wherein: The flow controller comprises: a cylinder forming an internal space, the cylinder including an inlet member and an outlet member, the liquid sample being introduced into the internal space through the inlet member and the liquid sample being discharged from the internal space through the outlet member, a piston disposed in the inner space and coupled to the cylinder such that the piston can reciprocate parallel to one direction; an inlet valve located at the inlet member and configured to allow introduction of the liquid sample and inhibit discharge of the liquid sample; and An outlet valve is located at the outlet member and is configured to allow discharge of the liquid sample and inhibit introduction of the liquid sample.

12. The flow nanoparticle measurement device according to claim 11, wherein: When the piston moves in the one direction and the internal space is pressurized, the inlet valve closes and the outlet valve opens, and When the piston moves in another direction opposite to the one direction, the inlet valve opens and the outlet valve closes.

13. The flow nanoparticle measurement device according to claim 12, wherein: The flow controller further comprises: a cam spaced apart from the cylinder and forming a rotation axis; and a connecting rod having one end and the other end, wherein the one end is rotatably connected to the cam at a position spaced apart from the rotation axis, and the other end is rotatably connected to the piston, When the cam rotates, the piston reciprocates in the inner space.

14. A flow nanoparticle measurement device comprising: a flow chamber configured to form a flow path through which a liquid sample flows; a laser generator configured to generate a first laser beam and irradiate the first laser beam to the flow chamber; a plurality of detectors disposed at the flow chamber and configured to detect shock waves of the plasma induced by the first laser beam in the flow chamber and to generate detection signals; as well as a controller configured to obtain the detection signals from the plurality of detectors and determine the type and size of the nanoparticles contained in the liquid sample based on the detection signals, Wherein, the controller includes: an amplitude measuring unit configured to measure the amplitude of the shock wave based on the detection signal; and a frequency measuring unit configured to measure a natural frequency of the shock wave based on the detection signal, wherein the plurality of detectors include a first detector and a second detector arranged to be spaced apart from each other along the flow path, wherein the second detector is arranged at a position further downstream in the flow path than the first detector, and Wherein, the controller includes: an amplitude ratio calculator configured to extract a plurality of common natural frequencies shared by the first detector and the second detector from the plurality of natural frequencies when the first detector and the second detector measure the plurality of natural frequencies, calculate a first detector amplitude ratio, and calculate a second detector amplitude ratio, wherein the first detector amplitude ratio is a ratio of amplitudes at the plurality of common natural frequencies in the first detector, and the second detector amplitude ratio is a ratio of amplitudes at the plurality of common natural frequencies in the second detector; and A nanoparticle determination unit is configured to specify the type of the nanoparticle based on data pre-stored in the controller and the plurality of common natural frequencies, and to determine the size of the nanoparticle based on the data and the first and second detector amplitude ratios.

15. A method (S200, S300) for measuring flowing nanoparticles using a flowing nanoparticle measuring device, the flowing nanoparticle measuring device comprising: a flow chamber, the flow chamber forming a flow path through which the liquid sample flows; a laser generator that generates a pulsed laser beam and irradiates a first laser beam split from the pulsed laser beam to the flow chamber; and a plurality of detectors arranged along the flow path and detecting shock waves of the plasma generated in the flow chamber to generate detection signals. The flow nanoparticle measurement method (S200, S300) includes: a step of measuring the amplitudes of the shock wave at multiple frequencies based on the detection signal ( S210 , S310 ); a step of calculating an amplitude ratio based on the amplitude and the natural frequencies of the plurality of detectors (S220, S320); and the steps of specifying the type of nanoparticles contained in the liquid sample according to the natural frequency and determining the size of the nanoparticles based on the amplitude ratio (S230, S330), The step of calculating the amplitude ratio (S220, S320) includes: a step (S320) of calculating an amplitude ratio of each natural frequency at said plurality of detectors, The amplitude ratio of each natural frequency is the ratio of the amplitudes of the multiple detectors at the natural frequency.

16. A method (S200, S300) for measuring flowing nanoparticles using a flowing nanoparticle measuring device, the flowing nanoparticle measuring device comprising: a flow chamber, the flow chamber forming a flow path through which the liquid sample flows; a laser generator that generates a pulsed laser beam and irradiates a first laser beam split from the pulsed laser beam to the flow chamber; and a plurality of detectors arranged along the flow path and detecting shock waves of the plasma generated in the flow chamber to generate detection signals. The flow nanoparticle measurement method (S200, S300) includes: a step of measuring the amplitudes of the shock wave at multiple frequencies based on the detection signal ( S210 , S310 ); a step of calculating an amplitude ratio based on the amplitude and the natural frequencies of the plurality of detectors (S220, S320); and the steps of specifying the type of nanoparticles contained in the liquid sample according to the natural frequency and determining the size of the nanoparticles based on the amplitude ratio (S230, S330), The step of calculating the amplitude ratio (S220, S320) includes: When the natural frequency includes a plurality of natural frequencies, a step (S220) of calculating an amplitude ratio of each of the plurality of detectors at the plurality of natural frequencies based on the amplitude and the plurality of natural frequencies, The amplitude ratio of each detector in the plurality of detectors at the plurality of natural frequencies is a ratio of the amplitudes of each detector in the plurality of detectors at the plurality of natural frequencies.

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