Apparatus and method for measuring fluid nanoparticles

Abstract

To provide a measuring apparatus and method for measuring fluid nanoparticles that improves the measurement reliability in nanoparticle measurement. [Solution] The measuring device for flowing nanoparticles includes a flow cell configured to allow a liquid sample containing nanoparticles to flow, a laser generating unit that irradiates the flow cell with a pulsed laser beam, a flow control unit that controls the flow of the liquid sample to the flow cell, and a signal detection unit that detects an optical signal caused by plasma generated in the flow cell by the pulsed laser beam, wherein the signal detection unit includes a spectrometer that analyzes nanoparticle information from the spectrum of the optical signal caused by the plasma.

Description

Technical Field

[0001] (Cross - reference to Related Applications and Claim of Priority) This application claims the benefit of priority based on Korean Patent Application No. 10 - 2024 - 0197306, filed on December 26, 2024, the entire contents of which are incorporated herein by reference.

[0002] (Field of the Invention) The present invention relates to an apparatus and a method for measuring flowing nanoparticles.

Background Art

[0003] Various organic or inorganic chemical substances used in the manufacturing processes of products that require high precision, such as displays and semiconductors, now demand chemicals with higher purity in order to prevent a decrease in manufacturing yield. Also, advanced analytical techniques have been developed and newly applied to confirm the quality of high - purity chemicals.

[0004] The importance of particle analysis is increasing more and more. Nanoscale microparticles may reduce the yield of semiconductor manufacturing processes and affect the high integration of semiconductor manufacturing processes. Therefore, the development of a stable analytical method for quality control is required, and the scalability of the technology must be ensured so that it can interpret the causes of defects that may occur during the process.

[0005] Generally, a substance in which molecules or ions are uniformly dispersed in a liquid is called a solution. In this solution, a state in which microparticles having a diameter of about 1 nm to 1000 nm, which are larger than ordinary molecules or ions, are dispersed without aggregation or precipitation is called a colloidal state, and a substance in this colloidal state is called a colloid.

[0006] Research on fine colloids in solutions focuses on obtaining information about the physicochemical properties of analytes and improving the detection capabilities of separation analyzers. Until recently, the analysis of colloidal particles has been limited to those larger than 100 nm. Therefore, technological development is needed to accurately analyze colloidal particles smaller than 100 nm, which requires high-concentration samples. [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] One aspect of the present invention is to provide a measuring apparatus and method for measuring fluid nanoparticles that improves the measurement reliability in the measurement of nanoparticles. [Means for solving the problem]

[0008] An exemplary embodiment of the present invention provides a measuring apparatus for flowing nanoparticles, comprising: a flow cell configured to allow a liquid sample containing nanoparticles to flow; a laser generating unit that irradiates the flow cell with a pulsed laser beam; a flow control unit that controls the flow of the liquid sample to the flow cell; and a signal detection unit that detects a signal from plasma generated in the flow cell by the pulsed laser beam. The signal detection unit may include a spectrometer that analyzes nanoparticle information from the spectrum of the optical signal from the plasma.

[0009] In an exemplary embodiment, the signal detection unit may include an optical fiber that collects the optical signal generated from the plasma and transmits it to the spectroscopic analyzer.

[0010] In an exemplary embodiment, the signal detection unit includes a focusing unit positioned on the optical path incident to the spectrometer, and the focusing unit may include a condenser, an integrating sphere, and a cosine collector.

[0011] In exemplary embodiments, the signal detection unit may include a microphone and / or a piezoelectric element for detecting shock waves generated from the plasma.

[0012] In the exemplary embodiment, the signal detection unit can be positioned in contact with one surface of the flow cell or spaced apart from the flow cell.

[0013] In an exemplary embodiment, a plurality of piezoelectric elements can be attached to one side of the fluid cell.

[0014] In exemplary embodiments, the measuring device for flowing nanoparticles may include an integrating sphere in which the flow cell is located and which multiple-reflects the optical signal generated from the plasma on its internal surface.

[0015] In exemplary embodiments, a fluid cell holder may be included, which is positioned inside the integrating sphere and on which the fluid cells are detachably stacked.

[0016] In an exemplary embodiment, a first opening communicating with the internal space can be formed on one surface of the integrating sphere so that the pulsed laser beam is incident on it, and a second opening can be formed on the other surface of the integrating sphere so that at least a portion of the pulsed laser beam exits the integrating sphere.

[0017] In exemplary embodiments, the surface of the fluid cell holder may be configured to reflect optical signals generated from the plasma.

[0018] In exemplary embodiments, the inner surface of the integrating sphere and the surface of the fluid cell holder can be configured to reflect light in the wavelength range of 180 to 2500 nm.

[0019] In exemplary embodiments, the inner surface of the integrating sphere and the surface of the fluid cell holder can be configured to reflect light in the wavelength range of 200 to 1100 nm.

[0020] In exemplary embodiments, optical fibers may be included to transmit the optical signals multiple-reflected by the integrating sphere to the spectroscopic analyzer.

[0021] In an exemplary embodiment, the signal detection unit may include a notch filter disposed on an optical path through which an optical signal reflected from an inner surface of the integrating sphere enters the spectroscopic analyzer.

[0022] In an exemplary embodiment, the signal detection unit includes a microphone and / or a piezoelectric element that detects a shock wave generated from the plasma, and at least a part of the signal detection unit can be disposed inside the integrating sphere.

[0023] In an exemplary embodiment, a plurality of piezoelectric elements can be provided so as to be attached to one side of the flow cell holder or the integrating sphere.

[0024] In an exemplary embodiment, the laser generation unit may include an attenuator that adjusts the intensity of the pulsed laser beam.

[0025] A method for measuring flowing nanoparticles according to an exemplary embodiment of the present invention includes a flowing step of flowing a liquid sample containing nanoparticles through a flow cell, an irradiation step of irradiating a pulsed laser beam onto a main flow portion in the flow cell through which the liquid sample flows, a first information acquisition step of detecting an image by an optical signal of plasma generated in the flow cell by the pulsed laser beam, and a second information acquisition step of detecting a spectrum of the optical signal of the plasma.

[0026] In an exemplary embodiment, the flow cell is disposed inside the integrating sphere, and the optical signal of the plasma can be generated inside the integrating sphere.

[0027] In an exemplary embodiment, the first information acquisition step and / or the second information acquisition step can be performed using the optical signal of the plasma reflected from an inner surface of the integrating sphere.

Advantages of the Invention

[0028] The fluid nanoparticle measuring device according to an exemplary embodiment of the present invention can simultaneously analyze shock waves and flashes emitted by an induced plasma using a first detection unit and a second detection unit. This allows for a more accurate understanding of the physical properties and chemical composition of the nanoparticles being measured.

[0029] A fluid nanoparticle measuring device according to an exemplary embodiment of the present invention can accurately analyze the types of nanoparticles in a liquid sample using a spectrometer.

[0030] An exemplary embodiment of the present invention provides a measuring device for flowing nanoparticles. By placing a flow cell inside an integrating sphere, the optical signal emitted from the induced plasma is amplified by multiple reflections of light on the inner surface of the integrating sphere, thereby obtaining a homogenized signal. This enables more precise and accurate analysis of nanoparticle information. [Brief explanation of the drawing]

[0031] [Figure 1] This is a schematic diagram of a measuring device for flowing nanoparticles according to one embodiment of the present invention. [Figure 2] This is a schematic diagram of a measuring device for flowing nanoparticles according to one embodiment of the present invention. [Figure 3] This figure schematically shows the configuration related to the signal detection unit of a measuring device for flowing nanoparticles according to one embodiment of the present invention. [Figure 4] This diagram schematically shows the configuration related to the first detection unit of a measuring device for flowing nanoparticles according to one embodiment of the present invention. [Figure 5] This is a flowchart of a method for measuring fluid nanoparticles according to one embodiment of the present invention. [Modes for carrying out the invention]

[0032] The accompanying drawings are included to provide a further understanding of the present invention, are incorporated into and constitute part of this disclosure, and serve to illustrate embodiments of the present invention and illustrate the principles of the present invention together with the description.

[0033] Embodiments of the present invention are provided to give a more complete explanation of the invention to those who are ordinary skill in the art, and the following embodiments can be modified in various different forms, and the scope of the invention is not limited to the following embodiments.

[0034] For the sake of explanation, some embodiments of the present invention will be described below with reference to illustrative drawings. When assigning reference numerals to components in each drawing, the same reference numerals will be used as much as possible for identical components, even if they are shown in different drawings.

[0035] The terms and words used herein and in the claims should not be limited to their ordinary or dictionary meanings, but should be interpreted as meanings and concepts consistent with the technical idea of ​​the present invention, based on the principle that inventors can appropriately define the concepts of terms in order to best describe their invention.

[0036] The terms used herein are for illustrative purposes only and are not intended to limit the invention. Where used herein, singular terms include plural forms unless the context clearly indicates otherwise.

[0037] Furthermore, when used to describe and assert this disclosure, the words “comprise,” “include,” “consist of,” and “have” should be interpreted in a non-exclusive manner, meaning that unless otherwise specified, the constituent elements may be inherent, and therefore should be interpreted as including other constituent elements rather than excluding them.

[0038] Furthermore, when describing the components of the embodiments of the present invention, terms such as first, second, A, B, (a), (b), etc., may be used. These terms are intended solely to distinguish a component from other components, and do not limit the nature, order, or sequence of the components.

[0039] When it is stated that one component is “connected” or “joined” to another component, it should be interpreted that while that component may be directly connected or joined to the other component, it may also be that another component is “connected” or “joined” between that component and the other component.

[0040] Spatial terms such as "beneath," "below," "lower," "above," and "upper" are used to facilitate understanding of one element or feature depicted in a drawing and another element or feature. These spatial terms are provided to facilitate understanding of the invention in various process or usage conditions and do not limit the invention. For example, if an element or feature in a drawing is reversed, an element or feature labeled "beneath" or "lower" becomes "above" or "upper." Therefore, "beneath" is a concept that encompasses "above" or "lower."

[0041] The embodiments described herein and the configurations shown in the drawings represent only the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, it should be understood that various equivalents and modifications may exist that can replace them at the time of filing of the present invention. Furthermore, detailed descriptions of known functions and configurations that may unnecessarily obscure the gist of the present invention are omitted.

[0042] This invention relates to a method for analyzing microparticles, which involves generating an induced plasma from minute particles using a laser and detecting the emitted light and shock waves to obtain information such as the size, concentration, distribution, and even composition of nanoparticles.

[0043] The measuring device 1 for flowing nanoparticles can utilize laser-induced breakdown detection (LIBD). Laser-induced breakdown detection is a technique that utilizes the principle of laser-induced plasma generated in the focal region of lens 18 when a pulsed laser beam with a time width of several nanoseconds is incident on it through lens 18. In detail, when a pulsed laser beam is irradiated onto nanoparticles, the energy level of the nanoparticles becomes excited. Subsequently, the excited nanoparticles release energy to return to a stable state, i.e., the ground state. The released energy generates plasma or shock waves from the nanoparticles.

[0044] The phenomenon that generates plasma or shock waves is called a breakdown phenomenon. Energy is required to generate plasma, and the minimum amount of energy required is called the threshold energy. The required ionization energy differs for each substance, and the threshold energy depends on the phase of the substance. When the substance is in a gaseous state, the threshold energy is highest, and as the nanoparticles are in a liquid or solid state, the threshold energy value decreases sequentially.

[0045] The laser beam energy required to generate laser-induced plasma increases sequentially depending on whether the nanoparticles are solid, liquid, or gaseous. Therefore, by using the appropriate laser beam energy, it is possible to destroy only the solid particles in an aqueous solution and create a laser-induced plasma state.

[0046] By utilizing the properties that the particle's breakdown probability varies with particle concentration, and the laser beam threshold energy required for destruction varies with particle size, the concentration or size of nanoparticles can be analyzed. Furthermore, the elemental composition of nanoparticles can be analyzed from the spectrum of the stimulated plasma. This makes it possible to simultaneously understand the physical and chemical properties of the particles.

[0047] Figure 1 is a schematic diagram of a fluid nanoparticle measuring device according to one embodiment of the present invention, and Figure 2 is a schematic diagram of a fluid nanoparticle measuring device including a signal detection unit according to one embodiment of the present invention.

[0048] As shown in Figures 1 and 2, the fluid nanoparticle measuring device 1 may include a laser generator 10 and a fluidizing device 20.

[0049] The laser generation unit 10 may include at least one of the following: a laser generator 12, an optical aperture 13, a mirror 14, a beam splitter 16, a first energy detector 17, a lens 18, and a second energy detector 19.

[0050] The laser generator 12 can generate a pulsed laser beam B. The wavelength of the pulsed laser beam B is not limited to a specific wavelength range. The laser generator 12 can generate the pulsed laser beam B using Q-switching. The laser generator 12 can repeatedly generate the pulsed laser beam B at a constant period. For example, the laser generator 12 can generate the pulsed laser beam B so that it repeatedly turns on and off in the first period. The laser generator 12 can include an Nd:YAG laser that generates a laser beam with a wavelength of 532 nm. However, it is not limited to this, and the type and energy of the pulsed laser beam B emitted from the laser generator 12 can be varied.

[0051] The optical diaphragm 13 is located on one side of the laser generator 12 and can adjust the diameter of the pulsed laser beam B emitted from and incident on the laser generator 12.

[0052] The mirrors 14 are positioned along the path of the pulsed laser beam B, and can alter the path of the pulsed laser beam B. Furthermore, the more mirrors 14 are positioned along the path of the pulsed laser beam B, the more precisely the pulsed laser beam B of the desired wavelength can be delivered to the fluid cell 30.

[0053] The beam splitter 16 can adjust the intensity of the pulsed laser beam B by changing its path or splitting the pulsed laser beam B. The beam splitter 16 can adjust the path of the pulsed laser beam B so that at least a portion of the pulsed laser beam B incident on the beam splitter 16, which is the first pulsed laser beam B1, proceeds to the flow cell 30.

[0054] Furthermore, the second pulsed laser beam B2, which is split and branched from the first pulsed laser beam B1 by the beam splitter 16, is measured by the first energy detector 17, thereby allowing monitoring of the amount of energy of the first pulsed laser beam B1 irradiating the fluid cell 30.

[0055] The first energy detector 17 can detect the second pulsed laser beam B2. By detecting the second pulsed laser beam B2, which is branched off from the pulsed laser beam B at a constant ratio, the first energy detector 17 can detect the energy magnitude of the first pulsed laser beam B1 irradiating the fluid cell 30. In other words, by detecting the energy of the second pulsed laser beam B2 passing through the beam splitter 16, the first energy detector 17 can deduce the energy magnitude of the first pulsed laser beam B1 passing through the beam splitter 16.

[0056] The lens 18 can be adjusted so that the focal point of the first pulsed laser beam B1 incident on the fluid cell 30 is located on the liquid sample within the fluid cell 30. The lens 18 can adjust the irradiation area of ​​the first pulsed laser beam B1 incident on the fluid cell 30. By adjusting the irradiation area of ​​the first pulsed laser beam B1 incident on the fluid cell 30, the lens 18 can improve the detection power of nanoparticles. The focal length of the lens 18 can be adjusted based on the Gaussian distribution of the nanoparticle-induced plasma by the first pulsed laser beam B1. The focal length of the lens 18 can be set to 10-40 mm. However, the focal length of the lens 18 is not limited to this.

[0057] The point where the induced plasma is generated may be the point where the nanoparticles and the first pulsed laser beam B1 meet. For example, the point where the induced plasma is generated may be the focal point of the first pulsed laser beam B1 formed within the fluid cell 30, or adjacent to it. For example, the point where the induced plasma is generated may depend on the refractive index of the liquid sample contained in the fluid cell 30. Therefore, in order to measure various liquid samples, it is necessary to adjust the focal length of the first pulsed laser beam B1.

[0058] The distance between the lens 18 and the fluid cell 30 can be adjusted depending on the type of liquid sample. The distance between the lens 18 and the fluid cell 30 can be adjusted by the control unit 70.

[0059] The second energy detector 19 can detect the first pulsed laser beam B1 that has penetrated the fluidizing device 20. In an exemplary embodiment, the control unit 70 can compare the energy of the second pulsed laser beam B2 detected by the first energy detector 17 with the energy of the first pulsed laser beam B1 detected by the second energy detector 19. This allows the control unit 70 to analyze the energy involved in plasma generation.

[0060] On the other hand, the laser generation unit 10 may further include an attenuator 11 for adjusting the intensity of the pulsed laser beam B. For example, the attenuator 11 can reduce the intensity of the pulsed laser beam B incident on the attenuator 11. For example, the intensity of the pulsed laser beam B incident on the attenuator 11 may be greater than the intensity of the pulsed laser beam B that has passed through the attenuator 11.

[0061] The fluidizing device 20 can be configured to fluidize a liquid sample. The fluidizing device 20 may include a fluidizing cell 30.

[0062] The fluid cell 30 can be configured so that a liquid sample flows through its interior. The fluid cell 30 may include a cell inlet into which the liquid sample flows. The cell inlet may be the portion into which the liquid sample flows into the fluid cell 30.

[0063] The fluid cell 30 may include a cell outlet from which the liquid sample flows out. The cell outlet may be the part from which the liquid sample flows out of the fluid cell 30.

[0064] The fluid cell 30 can be made from a material containing quartz. However, it is not limited to quartz; polymer materials such as acrylic may be used depending on the type of liquid sample.

[0065] The shape of the flow cell 30 is described assuming that the outer shape of the flow cell 30 is a rectangular cell, but the shape of the flow cell 30 is not limited to a rectangular cell. However, for example, if the flow cell 30 is composed of rectangular cells, the detector can be positioned perpendicular to the outer surface of the rectangular cell, or inclined at a certain angle to the outer surface of the rectangular cell.

[0066] However, the shape of the fluid cell 30 and the arrangement of the detectors according to the shape of the fluid cell 30 are not limited thereto. The fluid cell 30 may be configured so that a liquid sample flows inside the fluid cell 30, and at least a portion of the fluid cell 30 may be made of a light-transmitting material so that the liquid sample located inside the fluid cell 30 is irradiated with the first pulse laser beam B1.

[0067] The fluid cell 30 may include a fluid section in which a liquid sample flows. The fluid section may be formed in the shape of a "┓". The fluid section may be connected to an inlet section 41 and an outlet section 42.

[0068] However, the shape of the fluid section is not limited to the shape of "┓". For example, the fluid section may be configured to connect the inlet section 41 and the outlet section 42, allowing the liquid sample to flow.

[0069] The size and shape of the inner diameter of the fluidized section may vary. For example, the inner diameter of the fluidized section may be 10 mm or less.

[0070] For example, the fluidized section may have a rectangular or circular cross-section.

[0071] In an exemplary embodiment, if the fluid section is formed with a circular cross-section, the distance from the fluid section to the detector can be configured to be the same depending on the direction in which the detector is positioned. This reduces constraints on the placement of the detector and improves the reliability of the detection results.

[0072] In an exemplary embodiment, when the fluid section is formed with a square cross-section, the first pulsed laser beam B1 can be irradiated perpendicular to the cross-section, and the plasma signal can be measured, thereby reducing distortion such as signal refraction. This configuration allows for more accurate detection results. Furthermore, when the fluid section is formed with a square cross-section, a larger flow path can be formed for the same width. This allows the fluid section to guide the smooth flow of the liquid sample.

[0073] However, the aforementioned shape of the fluidized portion is illustrative, and the shape of the fluidized portion is not limited to those described above. For example, the fluidized portion may be formed with at least a part of it as a curved surface and the rest as a flat surface.

[0074] For example, the cross-section of the flow section may be formed as a shape combining curved surfaces and polygons. When a portion of the flow section is formed as a curved surface, the detection intensity can be maximized. In addition, the generation of bubbles in the liquid sample due to the flow velocity can be minimized.

[0075] The inner diameter of the flow section may be constant throughout its entire length. Alternatively, the inner diameter of the flow section may change along the flow direction of the liquid sample. Specifically, the flow section may be divided into multiple sections, with each section having a different inner diameter. The main flow section in the flow section may be configured to have a different inner diameter and shape from the other flow sections.

[0076] The fluid section can form a channel through which the liquid sample flows. The fluid section can be connected to a cell inlet or cell outlet.

[0077] The fluidized section may include a main fluidized section through which the first pulsed laser beam B1 passes. The main fluidized section can form a fluidized space through which the liquid sample flows. The main fluidized section can be configured so that the first pulsed laser beam B1 is irradiated into the fluidized space. The fluidized space of the main fluidized section can form a channel through which the liquid sample flows in one direction.

[0078] The main flow region through which the first pulsed laser beam B1 passes may be a part of the flow region or the entire flow region. For example, the main flow region may be the portion of the flow region before it is bent. However, it is not limited to this, and the main flow region may be the portion of the flow region after it is bent, or the entire flow region may be defined as the main flow region. The position of the main flow region within the flow region is not limited.

[0079] The first pulsed laser beam B1 can irradiate the flow path of the liquid sample passing through the main flow section. Specifically, the first pulsed laser beam B1 can irradiate the center of the flow path of the liquid sample passing through the main flow section. However, the irradiation position of the first pulsed laser beam B1 onto the main flow section is not limited to the flow path or the center of the flow path.

[0080] The flow direction of the liquid sample passing through the main flow section and the irradiation direction of the first pulsed laser beam B1 can be arranged so as to be perpendicular to each other. That is, the flow path of the liquid sample formed inside the main flow section and the first pulsed laser beam B1 incident on the main flow section can be configured to be perpendicular. However, it is not limited to this, and the flow direction of the liquid sample and the irradiation direction of the first pulsed laser beam B1 may be adjusted to form a constant angle that is horizontal, vertical, or non-horizontal. The angle between the flow direction and the irradiation direction of the first pulsed laser beam B1 may be applied differently depending on the type of detector.

[0081] The fluid cell 30 can be configured such that at least a portion of the fluid cell 30, including the main fluid section, contains a light-transmitting material for irradiation with the first pulsed laser beam B1. This allows the first pulsed laser beam B1 to penetrate the fluid cell 30 and irradiate the liquid sample passing through the main fluid section.

[0082] The fluidizing device 20 may include an inlet section 41. The fluidizing device 20 may also include an outlet section 42.

[0083] The liquid sample can flow into the fluid cell 30 via the inlet section 41. The liquid sample contained in the fluid cell 30 can be discharged to the outside of the fluidizer 20 via the outlet section 42.

[0084] The storage tank can store liquid samples. The inlet section 41 and the outlet section 42 can be connected to a single storage tank. This allows liquid samples discharged from the storage tank to the inlet section 41 to flow back into the storage tank via the outlet section 42. However, the design is not limited to this, and the inlet section 41 and the outlet section 42 may each be connected to independent storage tanks.

[0085] The fluidizing device 20 may include a fluidizing control unit 50.

[0086] The flow control unit 50 can be positioned on the flow path of the liquid sample. The flow control unit 50 can be configured to control the flow velocity or flow rate of the liquid sample passing through the flow cell 30. The control unit 70 can control the flow velocity or flow rate of the liquid sample passing through the flow cell 30 by controlling the flow control unit 50.

[0087] In an exemplary embodiment, the flow control unit 50 may be located on the path between the flow cell 30 and the outlet unit 42, as shown in Figure 1. The path between the flow cell 30 and the outlet unit 42 may be downstream in the direction of flow of the liquid sample. This minimizes contamination of the liquid sample being measured. However, the placement of the flow control unit 50 is not limited to between the flow cell 30 and the outlet unit 42.

[0088] For example, the flow control unit 50 can be located on the path between the flow cell 30 and the inlet 41. The flow control unit 50 is configured to control the flow velocity of the liquid sample flowing through the flow cell 30, and the flow control unit 50 can be placed in a location where contamination of the liquid sample does not occur.

[0089] In an exemplary embodiment, the flow control unit 50 can control the liquid sample to flow over the main flow section. In an exemplary embodiment, the flow control unit 50 can control the flow velocity so that a constant flow rate of liquid sample is sequentially positioned in a stationary state over the main flow section. That is, the flow control unit 50 can control the liquid sample to flow repeatedly in pulses of a constant period.

[0090] The flow control unit 50 can operate so that the flow state and the flow stop state of the liquid sample alternate. The flow state may mean that the liquid sample is flowing in the flow section. The flow stop state may mean that the flow of the liquid sample in the flow section has stopped.

[0091] The flow control unit 50 can control the flow of the liquid sample so that it alternates between a flowing state and a flow-stopped state in a pulsed manner. When the flow control unit 50 operates so that the liquid sample flows through the flow section at a constant linear velocity, the liquid sample may be in a flowing state. The linear velocity may be constant, but is not limited to this, and the magnitude and change of the linear velocity may vary. When the flow control unit 50 suppresses the flow of the liquid sample, the liquid sample may be in a flow-stopped state.

[0092] The flow control unit 50 may repeatedly switch between a flowing state and a flow-stopped state based on signals transmitted by the control unit 70, or it may repeatedly switch between a flowing state and a flow-stopped state mechanically. There are various methods for realizing the operation of the flow control unit 50. For example, if the flow of a liquid sample is controlled by the flow control unit 50, this would be a method for realizing the operation of the flow control unit 50. The irradiation of the first pulsed laser beam B1 by the laser generator 12 and the flow operation of the liquid sample by the flow control unit 50 can be configured to correspond to each other. The period of the pulsed laser beam B and the period of the flow control unit 50 can be configured to be the same.

[0093] In an exemplary embodiment, the flow control unit 50 can control the flow of the liquid sample so that the flow velocity of the liquid sample passing through the flow cell 30 corresponds to the period of the pulsed laser beam B. The operation of the flow control unit 50 to stop the flow and the irradiation of the first pulsed laser beam B1 by the laser generator 12 may be repeated at the same time, or they may be repeated at a time delay.

[0094] For example, when the flow control unit 50 is operating in a flow-stopped state, the flow control unit 50 can stop the flow of the liquid sample in the main flow section. At this time, the laser generator 10 can generate induced plasma for nanoparticles in the liquid sample by irradiating the main flow section of the flow cell 30 with the first pulse laser beam B1.

[0095] Subsequently, when the flow control unit 50 operates in a flow state, it causes the liquid sample into which an induced plasma has been generated to flow downstream, allowing the liquid sample that has not been exposed to the upstream first pulse laser beam B1 to flow into the main flow section. At this time, the laser generator 10 can be controlled so that the first pulse laser beam B1 is not irradiated into the main flow section.

[0096] When the flow control unit 50 operates again in a flow-stopped state, the liquid sample that is not exposed to the first pulsed laser beam B1 located in the main flow area can stop flowing. At the same time, the laser generator 10 irradiates the main flow area of ​​the flow cell 30 with the first pulsed laser beam B1, thereby generating induced plasma for the nanoparticles in the liquid sample.

[0097] In this invention, this process can be repeated. By measuring nanoparticles in a flowing liquid sample according to the process described above, the reliability of nanoparticle measurement can be improved.

[0098] The fluidization device 20 can be configured such that the flow rate of the liquid sample passing through the main fluid section when the fluidization control unit 50 is in a fluid state is equal to or greater than the amount of liquid sample located in the main fluid section when the fluidization control unit 50 is in a stopped state. This configuration prevents the liquid sample that has been exposed to the first pulsed laser beam B1 from being exposed to the first pulsed laser beam B1 again, thereby preventing the occurrence of measurement errors in nanoparticles.

[0099] In an exemplary embodiment, the fluidizer 20 may include a separation unit that separates nanoparticles from a liquid sample before the liquid sample containing nanoparticles flows into the fluid cell 30. For example, the separation unit may be positioned between the fluid cell 30 and the inlet 41 and configured to separate nanoparticles from the liquid sample flowing into the fluid cell 30. The separation of nanoparticles may be performed based on the type or size of the nanoparticles.

[0100] The flow control unit 50 can operate by receiving control signals from the control unit 70.

[0101] The flow control unit 50 can adjust the flow period of the liquid sample. In other words, the flow control unit 50 can adjust the period between the flow state and the flow stop state of the liquid sample.

[0102] If the volume of the internal space of the fluid section through which the liquid sample flows is the same, the fluid control unit 50 can control the flow velocity by adjusting the amount of liquid sample flowing.

[0103] The flow control unit 50 can be operated to stop the flow of the liquid sample in the flow cell 30 located upstream of the flow control unit 50. Alternatively, the flow control unit 50 can be operated to allow the liquid sample in the flow cell 30 located upstream of the flow control unit 50 to flow.

[0104] Although the fluid cell 30 is described as being located upstream of the fluid control unit 50, it is not limited to the fluid control unit 50. For example, if the fluid cell 30 is located downstream of the fluid control unit 50, the above operation may be performed in reverse. That is, movement of the piston in the pressurizing direction causes the liquid sample in the fluid cell 30 to flow, and movement of the piston in the opposite direction to the pressurizing direction can stop the flow of the liquid sample in the fluid cell 30.

[0105] This process allows the flow control unit 50 to control the flow of the liquid sample so that the flow state and the stop flow state of the liquid sample operate in a constant cycle.

[0106] To measure nanoparticles within the fluid cell 30, a method can be used that detects and analyzes the shock waves and flashes of the induced plasma. However, detecting images of the flashes using the camera 112 generally makes it difficult to accurately analyze the component composition of the nanoparticles. In particular, accurate analysis of nanoparticles can be even more difficult when the nanoparticle size is small, the amount of nanoparticles is minute, or the concentration of nanoparticles is low.

[0107] Furthermore, spectral analysis of light requires the acquisition of a light intensity signal of a certain magnitude or greater, but since laser-induced plasma is generally generated at periodic intervals of less than one second, spectral analysis can be difficult.

[0108] Furthermore, when a laser is generally irradiated onto the fluid cell 30, an optical signal S with a specific directionality may be formed with respect to only one side of the fluid cell 30. In this case, the intensity of the optical signal S for analysis may be weak, making spectral analysis difficult.

[0109] Therefore, in one embodiment of the present invention, a measuring device 1 for flowing nanoparticles can be provided that can accurately analyze the component composition of nanoparticles by collecting spectral information of flashes using a spectrophotometer 111.

[0110] Furthermore, in one embodiment of the present invention, a measuring device 1 for flowing nanoparticles can be provided that can supplement the intensity of the optical signal S by using an integrating sphere 113 in which a flow cell 30 is arranged inside.

[0111] The fluid nanoparticle measuring device 1 may include a signal detection unit 100.

[0112] Nanoparticles contained in a liquid sample can be transformed into a laser-induced plasma state by the first pulsed laser beam B1. The signal detection unit 100 can detect shock waves or flashes generated during this process. The signal detection unit 100 can detect various signals generated from the plasma. For example, the signal detection unit 100 can detect signals such as elemental spectra, shock waves, plasma images, heat, and sound.

[0113] In an exemplary embodiment, the signal detection unit 100 can be positioned at a certain distance from the source of the signal to be detected. In an exemplary embodiment, the signal detection unit 100 can be positioned on one side of the integrating sphere 113. For example, the signal detection unit 100 can penetrate the surface of the integrating sphere 113, with at least a portion of the signal detection unit 100 positioned inside the integrating sphere 113.

[0114] Figure 3 is a schematic diagram showing the configuration related to the signal detection unit 100 of the fluid nanoparticle measuring device 1 according to one embodiment of the present invention, and Figure 4 is a schematic diagram showing the configuration related to the first detection unit of the fluid nanoparticle measuring device 1 according to one embodiment of the present invention.

[0115] As shown in Figures 3 and 4, in exemplary embodiments, the signal detection unit 100 may include a first detection unit and a second detection unit that detect different signals.

[0116] The first detection unit can detect the flash generated when a laser-induced plasma is generated. For example, the first detection unit may include a camera 112 and / or a spectrometer 111 for detecting the flash. The first detection unit may also include an integrating sphere 113, a notch filter 115, a light condenser 116, a cosine collector 118, and an optical fiber to improve the reliability of the signal to be detected by the camera 112 and / or the spectrometer 111. The integrating sphere 113, light condenser 116, and cosine collector 118 are for supplementing the intensity of the optical signal S and can be described as a light condenser.

[0117] In an exemplary embodiment, the first detection unit may include a spectrometer 111. The plasma induced by the first pulsed laser beam B1 may emit light of various wavelengths at high temperatures. This may be a phenomenon that occurs when specific atoms or ions in the plasma undergo repeated excitation and de-excitation. The light emitted by the induced plasma may include the intrinsic spectra of the elements constituting the nanoparticles.

[0118] The spectroscopic analyzer 111 can detect and extract information regarding the chemical composition, concentration, or size of nanoparticles by analyzing the spectrum of light emitted when the first pulsed laser beam B1 is irradiated onto the nanoparticles.

[0119] In exemplary embodiments, the first detection unit may include an integrating sphere 113. The integrating sphere 113 may have an internal surface that is perfectly spherical. Alternatively, the internal surface of the integrating sphere 113 may be coated with a material having high reflectivity, so that light is not absorbed but instead undergoes multiple reflections.

[0120] For example, at least some of the light directed toward the inner surface of the integrating sphere 113 may be reflected by the inner surface of the integrating sphere 113. The light traveling through the interior of the integrating sphere 113 may include at least one of visible light, infrared light, ultraviolet light, and microwaves.

[0121] For example, a space may be formed inside the integrating sphere 113. For example, the integrating sphere 113 can form a hollow portion. The internal surface of the integrating sphere 113 can face the hollow portion of the integrating sphere 113. For example, the internal surface of the integrating sphere 113 can define the hollow portion of the integrating sphere 113.

[0122] At least a portion of the internal surface of the integrating sphere 113 may form a curved surface. For example, at least a portion of the internal surface of the integrating sphere 113 may be spherical. For example, the cross-section of at least a portion of the internal surface of the integrating sphere 113 may be a circular arc.

[0123] For example, at least a portion of the inner surface of the integrating sphere 113 may form an ellipsoid shape. For example, at least a portion of the cross-section of the inner surface of the integrating sphere 113 may form an ellipse shape.

[0124] For example, at least a portion of the inner surface of the integrating sphere 113 may form a paraboloid shape. For example, at least a portion of the cross-section of the inner surface of the integrating sphere 113 may form a parabola shape. The first opening 113a may be an opening formed in the integrating sphere 113.

[0125] The second opening 113b may be an opening formed in the integrating sphere 113. The first opening 113a and the second opening 113b can be located opposite each other. For example, the first opening 113a and the second opening 113b can be located antipodally to each other.

[0126] The openings 113a and 113b may mean that at least one of the first opening 113a and the second opening 113b is included. Windows may be joined or connected to the openings 113a and 113b. The windows located in the openings 113a and 113b may be formed of a light-transmitting material.

[0127] In exemplary embodiments, a flow cell 30 can be placed inside the integrating sphere 113. For example, the center of the integrating sphere 113 can be located in the flow cell 30. The flow cell 30 can be located between a first opening 113a and a second opening 113b. For example, a hypothetical line connecting the first opening 113a and the second opening 113b can pass through the flow cell 30. A flow cell holder 114 can be placed inside the integrating sphere 113 to which the flow cell 30 can be fixed. The flow cell 30 can be detachably coupled to the flow cell holder 114 inside the integrating sphere 113. The flow cell 30 can be detachably stacked on the flow cell holder 114. The flow cell 30 can be positioned in the center of the integrating sphere 113 by the flow cell holder 114.

[0128] In other words, the flow channels through which the liquid sample containing nanoparticles flows can be located inside the integrating sphere 113. For example, the inlet portion 41 and outlet portion 42 of the flow cell 30 can be arranged to communicate with the first opening 113a and the second opening 113b of the integrating sphere 113, respectively.

[0129] For example, the flow cell 30 can extend from the inlet portion 41 to the outlet portion 42. The direction in which the flow cell 30 extends may be the longitudinal direction of the flow cell 30. The longitudinal direction of the flow cell 30 may be parallel to the direction from the inlet portion 41 to the outlet portion 42, for example.

[0130] The first pulsed laser beam B1 can be irradiated onto the fluid cell 30. The first pulsed laser beam B1 can intersect with the fluid cell 30. The direction of propagation of the first pulsed laser beam B1 may be, for example, from the first aperture 113a toward the second aperture 113b.

[0131] However, the arrangement structure of the inlet portion 41 and outlet portion 42 of the flow cell 30 is not limited to this. For example, the inlet portion 41 and outlet portion 42 of the flow cell 30 can each be arranged at different positions on the integrating sphere 113.

[0132] For example, the surface of the fluid cell holder 114 can be coated with a material having high reflectivity so that light can be reflected multiple times without being absorbed, similar to the inner surface of the integrating sphere 113.

[0133] The inner surface of the integrating sphere 113 and the surface of the fluid cell holder 114 can be configured to reflect light of a predetermined wavelength. For example, the inner surface of the integrating sphere 113 and the surface of the fluid cell holder 114 can reflect light in the wavelength range of 180 to 2500 nm.

[0134] Alternatively, the internal surface of the integrating sphere 113 and the surface of the fluid cell holder 114 can be configured to reflect light in the wavelength range of 200 to 1100 nm. However, this range of reflected wavelengths is illustrative and not limited to it.

[0135] For example, the inner surface of the integrating sphere 113 and the surface of the fluid cell holder 114 can be configured to reflect light of various wavelengths, such as ultraviolet light, visible light, and infrared light, depending on the light source being irradiated.

[0136] In an exemplary embodiment, at least a portion of the first pulsed laser beam B1 that enters the interior of the integrating sphere 113 through the first aperture 113a can enter the flow cell 30. At least a portion of the first pulsed laser beam B1 that has passed through the flow cell 30 can be discharged through the second aperture 113b.

[0137] When the first pulsed laser beam B1 is irradiated onto the liquid sample in the fluid cell 30, at least some of the nanoparticles in the liquid sample receive energy from the first pulsed laser beam B1, thereby generating induced plasma. At this time, the light emitted by the induced plasma can be multiple-reflected on the internal surface of the integrating sphere 113 and uniformly dispersed inside.

[0138] Light generated from the induced plasma can form an optical signal S. For example, in this invention, the light reflected from the inner surface of the integrating sphere 113 is uniformly mixed, thereby generating an overall uniform optical signal S.

[0139] The spectrometer 111 of the first detection unit can be positioned in the integrating sphere 113. For example, the spectrometer 111 may be spaced apart from the apertures 113a, 113b and the flow cell 30. The spectrometer 111 can receive and detect light. For example, the spectrometer 111 can detect at least a portion of the light incident on it. The spectrometer 111 of the first detection unit can detect an optical signal S that has been reflected and homogenized by the inner surface of the integrating sphere 113.

[0140] In the above description, the fluid cell 30 is arranged inside the integrating sphere 113, but this is an exemplary embodiment of the present invention, and the arrangement structure of the fluid cell 30 is not limited thereto.

[0141] In exemplary embodiments, the flow cell 30 may also be located outside the integrating sphere 113. For example, the flow cell 30 may be located outside the integrating sphere 113, adjacent to the integrating sphere 113.

[0142] In this case, when the first pulsed laser beam B1 irradiated onto the fluid cell 30 generates an induced plasma, the optical signal S from the induced plasma is incident inside the integrating sphere 113 and can be multiple-reflected from its internal surface.

[0143] In the present invention, the spectrometer 111 can detect the optical signal S that has been multiple-reflected by the integrating sphere 113. At this time, the optical signal S that has been multiple-reflected by the integrating sphere 113 can be transmitted to the spectrometer 111 via an optical fiber.

[0144] In an exemplary embodiment, the first detection unit may include a notch filter 115. The notch filter 115 can be positioned on the optical path through which the optical signal S is incident on the camera 112 and / or the spectrometer 111. For example, the notch filter 115 can be positioned on the optical path through which the optical signal S, reflected from the inner surface of the integrating sphere 113, is incident on the spectrometer 111.

[0145] The notch filter 115 can block light of a specific, preset wavelength while allowing light of the remaining wavelengths to pass through. For example, the notch filter 115 can block light in the 532 nm wavelength band. For example, the notch filter 115 can block light from the first pulsed laser beam B1 while allowing flashes of light emitted by the stimulated plasma to pass through.

[0146] When the camera 112 and / or spectrometer 111 analyze the emission flash from the stimulated plasma, noise may be generated by the first pulsed laser beam B1 if the intensity of the first pulsed laser beam B1 is stronger than the intensity of the plasma emission flash. Therefore, the notch filter 115 of the present invention can be placed on the optical path incident on the camera 112 and / or spectrometer 111. This prevents light from the first pulsed laser beam B1 from entering the camera 112 and / or spectrometer 111, thereby minimizing noise that may occur during analysis.

[0147] In an exemplary embodiment, the first detection unit may include a light condenser 116.

[0148] For example, the light concentrator 116 can be positioned adjacent to the induction plasma generation site to collect the flash emitted by the induction plasma. The light concentrator 116 can be positioned so that the light emitted from the induction plasma is aligned along the optical axis. For example, the light collected and amplified by the light concentrator 116 can be transmitted to the camera 112 and / or spectrometer 111 via an optical fiber or an integrating sphere 113.

[0149] For example, the light concentrator 116 can collect an optical signal S at a specific location when light emitted by the stimulated plasma is reflected inside the integrating sphere 113 and diffuses in various directions, and transmit it to the camera 112 and / or spectrometer 111. The light concentrator 116 can focus the multi-directional light reflected inside the integrating sphere 113, minimizing light loss.

[0150] Furthermore, the light concentrator 116 can increase the intensity of light for analysis by reducing the diffusion of light emitted by the stimulated plasma and focusing the light to a focal point. By increasing the intensity of light for analysis, the light concentrator 116 can improve the signal-to-noise ratio.

[0151] For example, the light condenser 116 may include a focusing lens. However, this is illustrative and not limited to this, and it should be understood that anything capable of collecting an optical signal is applicable, as long as it does not deviate from the scope of the present invention.

[0152] In exemplary embodiments, the first detection unit may include an optical fiber. The optical fiber can transmit the optical signal S from the induced plasma to the spectrometer 111. For example, the optical fiber may be configured to transmit the optical signal S, which has been multiple-reflected on the inner surface of the integrating sphere 113, to the spectrometer 111.

[0153] For example, an optical fiber can provide a path for the light collected by the light collector 116. For example, an optical fiber can be placed between the light collector 116 and the spectrometer 111 to transmit the light collected by the light collector 116 to the spectrometer 111.

[0154] Optical fibers minimize optical loss through internal total internal reflection and can provide a flexible optical path toward the camera 112 and / or spectrometer 111. Optical fibers can also minimize signal distortion and enhance stability by protecting the transmitted light from external electromagnetic interference (EMI).

[0155] In exemplary embodiments, the first detection unit may further include a cosine corrector 118. For example, the cosine corrector 118 may be positioned between the light concentrator 116 and the spectrometer 111, and can remove or correct the directionality of the light incident on the spectrometer 111. The cosine corrector 118 can also ensure a uniform optical signal at all angles.

[0156] Light emitted by the stimulated plasma is reflected off the internal surface of the integrating sphere 113 and diffuses in multiple directions. That is, even if the light is focused by the concentrator 116, the light generated inside the integrating sphere 113 may still have multiple directions. The cosine collector 118 can correct the residual asymmetry problem of the mixed light inside the integrating sphere 113. This allows the cosine collector 118 to ensure that the signal transmitted to the spectrometer 111 is reliable, enabling the spectrometer 111 to collect spectral data more precisely.

[0157] The fluid nanoparticle measuring device 1 of the present invention can analyze the characteristics of particles derived from the absorption, scattering, or emission of light while the nanoparticles flow through the fluid cell 30 in real time. In particular, the present invention can improve the accuracy of estimating the type and size of nanoparticles flowing through the fluid cell 30 by using the spectrometer 111 of the signal detection unit 100. Furthermore, according to one embodiment of the present invention, since the light generated by the induced plasma is reflected multiple times on the inner surface of the integrating sphere 113, even when the concentration of nanoparticles is low, the light is amplified by multiple reflections and a strong signal can be obtained.

[0158] On the other hand, the first detection unit may include a camera 112 capable of detecting the size of nanoparticles. For example, the camera 112 may be a high-sensitivity CCD camera 112 or a CMOS camera 112. For example, the camera 112 may be positioned on one side of the integrating sphere 113 and be able to detect light homogenized by the inner surface of the integrating sphere 113. For example, the camera 112 may be positioned inside the integrating sphere 113 and be able to detect the intensity distribution or pattern of scattered light, thereby estimating the average particle size of the nanoparticles.

[0159] Since the stimulated plasma is generated inside the integrating sphere 113, the emitted light from the asymmetrically distributed stimulated plasma can be homogenized by the integrating sphere 113 and converted to facilitate signal analysis. This allows for reliable data even when the concentration and distribution of nanoparticles are non-uniform.

[0160] Light emitted by an stimulated plasma may be strongly emitted in a particular direction or distributed asymmetrically. In this invention, the asymmetry is eliminated by multiple reflections of the light inside the integrating sphere 113, allowing the signal intensity to be distributed uniformly. Furthermore, since the light is dispersed into multiple paths during the multiple reflection process and reaches specific locations again, the signal can be efficiently reused. As a result, even weak signals can be transmitted to the spectrometer 111 and / or camera 112 by being reflected multiple times without being lost in a single path.

[0161] Furthermore, in this invention, when the signal generated from nanoparticles is weak, the integrating sphere 113 has the effect of amplifying the signal through multiple reflections, and this effect enables the detection of the signal even when the concentration of the liquid sample is low. In other words, the integrating sphere 113 of this invention can spatially diffuse weak signals and substantially increase the amount of light transmitted to the spectrometer 111 and / or camera 112.

[0162] Furthermore, in this invention, the integrating sphere 113 automatically mixes signals internally, reducing the complexity of optical path design and alignment, eliminating the need to selectively adjust signals in a specific direction, and enabling stable measurement of the average value of the entire signal.

[0163] The second detection unit can measure the laser-induced shock wave (SCR) generated when laser-induced plasma is produced. When SCR is generated from nanoparticles by the first pulsed laser beam B1, the size and intensity of the generated plasma may differ depending on the size of the nanoparticles. The shock wave detector can detect the shock wave generated when SCR is produced.

[0164] In exemplary embodiments, the second detection unit may include a piezoelectric element 122 and a microphone 121. The signal measured by the second detection unit can be amplified by an amplifier (e.g., a lock-in amplifier).

[0165] In this invention, the signal detection unit 100 can obtain information about nanoparticles by detecting shock waves or flashes of light. The information about nanoparticles may include the number or size of the nanoparticles.

[0166] In exemplary embodiments, the first detection unit and the second detection unit can be positioned at different locations on the surface of the integrating sphere 113. For example, the first detection unit and the second detection unit can be positioned so as to penetrate the surface of the integrating sphere 113. Thus, at least a portion of the first detection unit and at least a portion of the second detection unit can be located inside the integrating sphere 113.

[0167] In exemplary embodiments, the first detection unit and the second detection unit can be arranged adjacent to the flow cell 30. For example, the first detection unit and the second detection unit may be arranged inside the flow cell 30 or outside the flow cell 30. For example, the first detection unit and the second detection unit may be arranged so that at least a portion of them is in contact with the flow cell 30, or they may be arranged at a distance from the flow cell 30.

[0168] Furthermore, multiple first and second detection units can be arranged around the flow cell 30. For example, at least one or more piezoelectric elements 122 can be provided in the second detection unit to detect pressure changes due to shock waves of the induced plasma. For example, at least some of the multiple piezoelectric elements 122 may be attached to the surface of the flow cell 30. Alternatively, at least some of the multiple piezoelectric elements 122 may be attached to the surface of the flow cell holder 114. Alternatively, at least some of the multiple piezoelectric elements 122 may be attached to the surface of the integrating sphere 113.

[0169] In the present invention, the type of signal detection unit 100 is not limited, and various detectors corresponding to the detected signal can be applied.

[0170] The fluid nanoparticle measuring device 1 may include a control unit 70.

[0171] The control unit 70 can control the overall operation of the fluid nanoparticle measuring device 1. For example, the control unit 70 can control the laser generator 12 or the fluid control unit 50.

[0172] The control unit 70 can control the generation of the pulsed laser beam B by the laser generator 12. For example, the control unit 70 can control the first cycle or generation time of the first pulsed laser beam B1 by controlling the laser generator 12. Furthermore, the control unit 70 can control the second cycle or flow time of the liquid sample by controlling the flow control unit 50. The control of the laser generator 12 and the flow control unit 50 by the control unit 70 can be performed independently. That is, the control unit 70 can control the laser generator 12 and the flow control unit 50, respectively.

[0173] The control unit 70 can correct the detected value based on the distance between the point where the induced plasma is generated in the flow cell 30 and the signal detection unit 100, and the angle between the flow cell 30 and the signal detection unit 100.

[0174] Furthermore, the control unit 70 can move the lens 18 relative to the fluid cell 30 in order to adjust the focal length or focus.

[0175] The control unit 70 can obtain information about nanoparticles from the signal detection unit 100. The control unit 70 can analyze the signals detected by the signal detection unit 100. The control unit 70 can determine information about the composition and size of nanoparticles from the signals of the induced plasma detected by the first detection unit and the second detection unit.

[0176] The control unit 70 processes the signal transmitted from the first detection unit to determine the type, size, and concentration of nanoparticles based on the light generated from the induced plasma. For example, the control unit 70 can detect the intensity and spectral data of the signal incident on the camera 112 and / or spectrometer 111 in real time. For example, the control unit 70 can classify the type of nanoparticles in real time based on the analyzed spectral data, or it can automatically classify them by comparing the spectral data with existing data using machine learning or database-based algorithms.

[0177] For example, the control unit 70 can adjust the state of each optical component or issue an alarm based on the output data from the camera 112 and the spectrometer 111.

[0178] In an exemplary embodiment, the control unit 70 can monitor the position of the notch filter 115 and whether it is functioning correctly. The control unit 70 can adjust the position of the notch filter 115, set a cutoff band, and issue an alarm.

[0179] In an exemplary embodiment, the control unit 70 can fine-tune the focal length of the light condenser 116. This allows the control unit 70 to control the focus of the plasma emission light to reach the entrance of the optical fiber or the first detection unit. For example, the control unit 70 can control the alignment so that the positions of the light condenser 116 and the plasma emission light are located on the same optical axis. Alternatively, the control unit 70 can detect the alignment of the light condenser 116 and issue an alarm. Alternatively, the control unit 70 can issue an alarm to switch to a preset lens depending on the signal strength.

[0180] In an exemplary embodiment, the control unit 70 can periodically detect the signal transmission efficiency of the optical fiber and issue alarms regarding damage and contamination of the optical fiber.

[0181] In an exemplary embodiment, the control unit 70 can adjust the position of the cosine collector 118 to ensure that the optical signal is uniformly transmitted to the input of the first detection unit. For example, the control unit 70 can detect the uniformity of the signal and confirm the operating state of the cosine collector 118.

[0182] The control unit 70 can determine the type, size, and concentration of nanoparticles from the shock wave signal of the induced plasma detected by the second detection unit.

[0183] The control unit 70 can comprehensively analyze the signals detected by the first detection unit and the second detection unit to further improve the accuracy of determining information such as the type, size, and concentration of nanoparticles.

[0184] In an exemplary embodiment, the control unit 70 can preprocess the signal transmitted from the signal detection unit 100. The preprocessing allows the control unit 70 to amplify the signal detected from the second detection unit, such as the piezoelectric element 122 or the microphone 121, using a signal amplifier (e.g., a lock-in amplifier).

[0185] The control unit 70 can remove noise in the low-frequency range below 100 Hz using a bandpass filter. The filtered signal can be converted into a digital signal by a converter. Depending on the conditions, the converted signal can have signal values ​​for certain intervals extracted and perform a Fast Fourier Transform (FFT) in real time. Through this process, the control unit 70 can convert the time function into a frequency function and analyze the frequency components of the shock wave generated by the plasma. Based on the frequency components or amplitude magnitudes converted from the detected shock wave, the control unit 70 can determine the type, size, or number of nanoparticles.

[0186] Under the same energy conditions, as the size of the nanoparticles increases, the size of the generated plasma also increases, and the magnitude of the shock wave can also increase. The control unit 70 can determine the type, size, or number of nanoparticles based on the frequency components and amplitude of the shock wave.

[0187] The control unit 70 can measure the concentration of nanoparticles in the liquid sample based on the flow rate of the liquid sample flowing by the flow control unit 50 and the information on nanoparticles detected from the signal detection unit 100.

[0188] On the other hand, the fluid nanoparticle measuring device 1 according to an exemplary embodiment of the present invention may further include a data storage unit capable of storing signals detected by the signal detection unit 100 and / or information analyzed by the control unit 70.

[0189] The operation of the fluid nanoparticle measuring device 1 of the present invention will be described below.

[0190] Figure 5 is a flowchart of a method for measuring fluid nanoparticles according to one embodiment of the present invention.

[0191] In an exemplary embodiment, the output of the first pulsed laser beam B1 can be controlled by the control unit 70. When the control unit 70 transmits a high signal to the laser generator 10, the first pulsed laser beam B1 may be generated. When the control unit 70 transmits a low signal to the laser generator 10, the first pulsed laser beam B1 may not be generated. However, the embodiment is not limited thereto.

[0192] The fluid nanoparticle measuring device 1 can be operated to measure nanoparticles contained in a fluid liquid sample. The control unit 70 can control the laser generator 12, the fluid control unit 50, and the signal detection unit 100.

[0193] As shown in Figure 5, a method for measuring flowing nanoparticles according to an exemplary embodiment of the present invention may include a flow step S910 in which a liquid sample containing nanoparticles is flowed into a flow cell 30. In this step S910, the flowing device 20 can flow the liquid sample containing nanoparticles into the main flow section of the flow cell 30 located in the integrating sphere 113. Specifically, the flowing device 20 can introduce the liquid sample into the cell inlet of the flow cell 30, cause it to flow through the internal flow section, and discharge it through the cell outlet. The flow velocity of the liquid sample flowing through the flowing device 20 can be controlled by the flow control unit 50.

[0194] The flow control unit 50 can control the flow velocity so that a liquid sample at a constant flow rate is positioned in the main flow section in a state of stopped flow. For example, the flow control unit 50 can operate so that the liquid sample flows repeatedly at a constant cycle. The flow control unit 50 can operate so that the flow state and the stopped flow state of the liquid sample alternate at a constant cycle.

[0195] A method for measuring flowing nanoparticles according to an exemplary embodiment of the present invention may include an irradiation step S920 in which a first pulse laser beam B1 is irradiated onto the main flow portion in the flow cell 30.

[0196] In step S920, the first pulsed laser beam B1 can pass through the mirror 14, beam splitter 16, and lens 18 to irradiate the main fluid portion of the fluid cell 30.

[0197] In an exemplary embodiment, when the fluid cell 30 is located inside the integrating sphere 113, the first pulsed laser beam B1 generated from the laser generator 12 can be irradiated into the interior of the integrating sphere 113 through the first aperture 113a of the integrating sphere 113. For example, a mirror 14, a beam splitter 16, a lens 18, etc., can be located inside the integrating sphere 113, but the internal arrangement structure of the integrating sphere 113 is not limited and may be located outside the integrating sphere 113.

[0198] For example, the first pulsed laser beam B1 can be irradiated in a manner that repeats with pulses of a constant period. The first pulsed laser beam B1 can be irradiated perpendicular to the flow direction of the liquid sample flowing in the main flow section. The period of the first pulsed laser beam B1 and the constant period of the flow control unit 50 can be configured to be the same. Through this operation, the flow control unit 50 can control the flow velocity of the liquid sample passing through the flow cell 30 to correspond to the period of the first pulsed laser beam B1. As a result, when the flow of the liquid sample passing through the main flow section is stopped by the flow control unit 50, the first pulsed laser beam B1 is irradiated into the main flow section of the flow cell 30, thereby generating induced plasma for nanoparticles in the liquid sample. The first pulsed laser beam B1 can generate plasma-induced shock waves and flashes from the nanoparticles in the liquid sample that have been stopped by the flow control unit 50.

[0199] A method for measuring flowing nanoparticles according to an exemplary embodiment of the present invention may include a first information acquisition step S930 for detecting an image of the optical signal S of the plasma generated in the flow cell 30 by a first pulsed laser beam B1.

[0200] For example, the image generated by the optical signal S can be detected by the camera 112 of the first detection unit described above. In addition, the first information acquisition step S930 can also detect the shock wave generated by the plasma.

[0201] For example, in the first information acquisition step S930, the camera 112 of the first detection unit and the second detection unit detect flashes and shock waves caused by the plasma, and information about nanoparticles can be obtained. More specifically, in the first information acquisition step S930, an image of the flash can be detected along with the shock wave caused by the plasma.

[0202] When an induced plasma is generated by the previous irradiation step S920, the rapid pressure change caused by the plasma expansion generates a shock wave. For example, in step S930, the shock wave can be detected by the second detection unit, and the intensity and propagation speed (time delay) of the shock wave can be collected. Based on the information obtained in step S930, the concentration and density of nanoparticles can be analyzed from the intensity and duration of the shock wave, and the average size and energy distribution of nanoparticles can be estimated by relating the propagation speed and intensity of the shock wave to the plasma energy.

[0203] Furthermore, in the first information acquisition step S930, the camera 112 of the first detection unit can also detect flashes caused by the induced plasma. For example, in this step S930, the camera 112 can rapidly capture images of the spatial shape and intensity distribution of the plasma, allowing for the analysis of the nanoparticle density distribution and energy transfer characteristics.

[0204] Furthermore, in the first information acquisition step S930, the camera 112 can detect the emission intensity and color distribution of the plasma. Since certain elements exhibit unique color characteristics in high-temperature plasma, the component composition of the nanoparticles can be estimated based on this. In addition, the intensity and velocity of the shock wave detected by the first detection unit are related to the energy density of the plasma, which is influenced by the composition of the nanoparticles. Therefore, the composition of the nanoparticles can also be estimated by interpreting the velocity, intensity, and duration of the shock wave. In other words, by combining the detection results of the plasma flash and shock wave obtained in this step S930, the composition, size, and concentration of the nanoparticles can be comprehensively analyzed.

[0205] However, it is difficult to analyze the composition of nanoparticles in complex materials such as alloys and mixtures using only the information obtained in the first information acquisition step S930, and the accuracy of the analysis may decrease, especially for trace elements.

[0206] A method for measuring flowing nanoparticles according to an exemplary embodiment of the present invention may include a second information acquisition step S940 for detecting the spectrum of the optical signal S of the plasma. For example, in the second information acquisition step S940, information about nanoparticles can be extracted by detecting the spectrum of the optical signal S from the plasma using the spectrophotometer 111 of the first detection unit.

[0207] In the second information acquisition step S940, the spectrometer 111 of the first detection unit detects the flash of the induced plasma, and the spectral information can be precisely analyzed to extract the unique properties of the nanoparticles. For example, in this step S940, the elemental composition in the nanoparticles can be confirmed by analyzing the emission lines at specific wavelengths of the spectrum using the spectrometer 111, the average size of the nanoparticles can be analyzed from linewidth analysis (e.g., Full Width at Half Maximum) and intensity ratio, and the concentration of nanoparticles can be estimated based on the intensity of the emitted light.

[0208] In exemplary embodiments, the second information acquisition step S940 may be performed additionally based on the analysis results of the first information acquisition step S930 if the amount of nanoparticles is trace or if the size of the nanoparticles is small and below a certain size.

[0209] Furthermore, although the first information acquisition step S930 is explained here before the second information acquisition step S940, this is merely a sequential explanation to aid in understanding the invention, and the first information acquisition step S930 and the second information acquisition step S940 do not necessarily need to be performed sequentially.

[0210] For example, in the present invention, the first information acquisition step S930 and the second information acquisition step S940 may be performed sequentially or in reverse order, and both steps S930 and S940 may be performed simultaneously.

[0211] A method for measuring flowing nanoparticles according to an exemplary embodiment of the present invention may include an analysis step of analyzing information about nanoparticles in a liquid sample based on information about the shock waves and flashes of the induced plasma obtained in the first information acquisition step S930 and the second information acquisition step S940.

[0212] In the analysis step, information such as the dynamic characteristics of the plasma and nanoparticle density information extracted by the microphone 121 and / or piezoelectric element 122 of the first detection unit, the spatial distribution and intensity of the plasma flash extracted by the camera 112 of the second detection unit, and the emission lines and linewidths of specific wavelengths obtained by the spectrophotometer 111 of the second detection unit can be combined to derive comprehensive analysis results. In this step, by utilizing the complementary information obtained by each detector, the accuracy and precision of the analysis regarding the composition, size, and concentration of nanoparticles can be improved.

[0213] The aforementioned measuring device 1 for fluid nanoparticles of the present invention can more accurately determine the physical properties and chemical composition of the nanoparticles to be measured by simultaneously analyzing the shock waves and flashes emitted by the induced plasma using the first detection unit and the second detection unit.

[0214] The fluid nanoparticle measuring device 1 according to one embodiment of the present invention can accurately analyze the type of nanoparticles in a liquid sample using the spectroscopic analyzer 111 of the second detection unit.

[0215] Furthermore, in this invention, by arranging the fluid cell 30 inside the integrating sphere 113, the optical signal S emitted from the induced plasma is amplified by multiple reflections of light on the internal surface of the integrating sphere 113, thereby obtaining a uniform signal. This makes it possible to analyze nanoparticle information more precisely and accurately.

[0216] Although the embodiments of the present invention have been described above as operating as a single unit or in combination, the present invention is not necessarily limited to such embodiments. That is, within the scope of the object of the present invention, one or more components may be selectively combined and operated. All terms, including technical or scientific terms, have the same meaning as generally understood by a person of ordinary skill in the art to which the present invention pertains, unless otherwise specifically defined. Commonly used terms, such as those defined in dictionaries, should be interpreted in accordance with their meaning in the context of the relevant art, and should not be interpreted in an ideal or overly formal sense unless expressly defined in the present invention.

[0217] The above description is merely illustrative of the technical concept of the present invention, and a person with ordinary skill in the art to which the present invention pertains will understand that various modifications and variations are possible without departing from the essential features of the present invention. Accordingly, the embodiments disclosed herein are not limiting, but rather illustrating, the scope of the technical concept of the present invention is not limited to these embodiments. The scope of protection of the present invention should be interpreted by the following claims, and all technical concepts within an equivalent scope should be interpreted as being included within the scope of the rights of the present invention. [Explanation of Symbols]

[0218] 1: Measurement device for fluid nanoparticles 10: Laser generation unit 12: Laser generator 14: Mirror 16: Beam Splitter 17: First Energy Detector 18: Lens 19: Second Energy Detector 20: Flow apparatus 30: Flow Cell 41: Inlet section 42: Outlet Section 50: Flow Control Unit 70: Control Unit 100: Signal detection unit 111: Spectroscopic analyzer 112: Camera 113: Integrating sphere 113a: 1st opening 113b:Second opening 114: Flow cell holder 115: Notch filter 116: Light concentrator 118: Cosine Collector 121: Microphone 122: Piezoelectric element

Claims

1. A fluid cell configured to allow a liquid sample containing nanoparticles to flow, A laser generating unit that irradiates the aforementioned fluid cell with a pulsed laser beam, A flow control unit that controls the flow of a liquid sample in the flow cell, It includes a signal detection unit that detects a signal caused by plasma generated in the fluid cell by the pulsed laser beam, The signal detection unit is a measuring device for flowing nanoparticles, which includes a spectrometer that analyzes nanoparticle information from the spectrum of the optical signal generated by the plasma.

2. The apparatus for measuring flow nanoparticles according to claim 1, wherein the signal detection unit includes an optical fiber that collects the optical signal and transmits it to the spectroscopic analyzer.

3. The signal detection unit includes a light-collecting unit positioned on the path of the optical signal incident on the spectrometer, The measuring apparatus for flowing nanoparticles according to claim 1, wherein the light-gathering section includes a light-gatherer, an integrating sphere, and a cosine collector.

4. The apparatus for measuring flow nanoparticles according to claim 1, wherein the signal detection unit includes a microphone and / or a piezoelectric element for detecting shock waves generated from the plasma.

5. The apparatus for measuring flow nanoparticles according to claim 4, wherein the piezoelectric element is in contact with one surface of the flow cell, and the microphone is positioned at a distance from the flow cell.

6. Multiple piezoelectric elements are provided, The apparatus for measuring flow nanoparticles according to claim 4, wherein the plurality of piezoelectric elements are attached to one side of the flow cell.

7. The apparatus for measuring fluid nanoparticles according to claim 1, further comprising an integrating sphere in which the fluid cell is disposed and on the internal surface of which optical signals generated from the plasma are multiple reflections.

8. The apparatus for measuring fluid nanoparticles according to claim 7, comprising a fluid cell holder disposed inside the integrating sphere and on which the fluid cells are detachably stacked.

9. The apparatus for measuring flowing nanoparticles according to claim 7, wherein a first opening is formed on one side of the integrating sphere through which the pulsed laser beam enters the interior of the integrating sphere, and a second opening is formed on the other side of the integrating sphere through which at least a portion of the pulsed laser beam exits the integrating sphere.

10. The apparatus for measuring flow nanoparticles according to claim 8, wherein the surface of the flow cell holder is configured to reflect the light signal.

11. The apparatus for measuring flow nanoparticles according to claim 10, wherein the inner surface of the integrating sphere and the surface of the flow cell holder are configured to reflect light in the wavelength range of 180 to 2500 nm.

12. The apparatus for measuring flow nanoparticles according to claim 11, wherein the inner surface of the integrating sphere and the surface of the flow cell holder are configured to reflect light in the wavelength range of 200 to 1100 nm.

13. The apparatus for measuring flow nanoparticles according to claim 7, further comprising an optical fiber for transmitting the optical signal, which has been multiple-reflected inside the integrating sphere, to the spectroscopic analyzer.

14. The apparatus for measuring flowing nanoparticles according to claim 7, wherein the signal detection unit includes a notch filter positioned on the path through which the light signal reflected from the inner surface of the integrating sphere is incident to the spectroscopic analyzer.

15. The signal detection unit includes a microphone and / or a piezoelectric element for detecting shock waves generated from the plasma. The apparatus for measuring flow nanoparticles according to claim 8, wherein at least a portion of the signal detection unit is arranged inside the integrating sphere.

16. Multiple piezoelectric elements are provided, The apparatus for measuring flow nanoparticles according to claim 15, wherein the plurality of piezoelectric elements are attached to the flow cell holder or the integrating sphere.

17. The apparatus for measuring flow nanoparticles according to claim 1, wherein the laser generation unit includes an attenuator for adjusting the intensity of the pulsed laser beam.

18. A fluidization step in which a liquid sample containing nanoparticles is flowed into a fluid cell, An irradiation step in which a pulsed laser beam is irradiated onto the main flow portion in the flow cell in which the liquid sample is flowing, A first information acquisition step involves detecting an image of the optical signal of the plasma generated in the flow cell by the pulsed laser beam, A method for measuring flowing nanoparticles, comprising a second information acquisition step of detecting the spectrum of the optical signal of the plasma.

19. The aforementioned flow cell is placed inside the integrating sphere, The method for measuring flow nanoparticles according to claim 18, wherein the optical signal of the plasma is generated inside the integrating sphere.

20. The method for measuring flowing nanoparticles according to claim 19, wherein the first information acquisition step and / or the second information acquisition step are performed using the optical signal of the plasma reflected from the inner surface of the integrating sphere.

Images