WO2018070324A1 - Nanoparticle evaluation method and nanoparticle observation device - Google Patents

Nanoparticle evaluation method and nanoparticle observation device Download PDF

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WO2018070324A1
WO2018070324A1 PCT/JP2017/036174 JP2017036174W WO2018070324A1 WO 2018070324 A1 WO2018070324 A1 WO 2018070324A1 JP 2017036174 W JP2017036174 W JP 2017036174W WO 2018070324 A1 WO2018070324 A1 WO 2018070324A1
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light
intensity
nanoparticles
sample
nanoparticle
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PCT/JP2017/036174
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French (fr)
Japanese (ja)
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時崎 高志
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国立研究開発法人産業技術総合研究所
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Priority to JP2018544975A priority Critical patent/JP6659062B2/en
Publication of WO2018070324A1 publication Critical patent/WO2018070324A1/en

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01QSCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q30/00Auxiliary means serving to assist or improve the scanning probe techniques or apparatus, e.g. display or data processing devices
    • G01Q30/02Non-SPM analysing devices, e.g. SEM [Scanning Electron Microscope], spectrometer or optical microscope
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/27Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/47Scattering, i.e. diffuse reflection
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/02Details
    • H01J37/20Means for supporting or positioning the object or the material; Means for adjusting diaphragms or lenses associated with the support

Definitions

  • the present invention relates to a method for evaluating the dispersion state of nanoparticles and an apparatus for observing the shape of the nanoparticles.
  • TEM electron microscope
  • AFM atomic force microscope
  • a sample having non-uniformly dispersed nanoparticles includes a part where the particles are aggregated and stacked, and a part where the particles are not present. Therefore, in a sample having nanoparticles dispersed unevenly, it is not easy to know which part should be observed with a TEM or the like.
  • various parts of the sample were viewed, and the optimal observation part in which the nanoparticles were uniformly dispersed was selected.
  • the optical microscope since the optical microscope has a wide field of view, it is possible to specify a portion that is clearly unsuitable for observation, such as a portion where nanoparticles overlap. However, due to the diffraction limit of light, it is difficult to directly observe the dispersion state of particles having a diameter of 1 ⁇ m or less. It is desirable that a portion to be observed with a TEM or the like can be selected in a short time from a wide region of several hundred ⁇ m square of the sample by a single observation using an optical microscope. Since the field of precision measurement using TEM etc.
  • the dispersion state of nanoparticles in the part of several ⁇ m square of the sample is measured using an optical microscope at the stage before precise measurement of nanoparticles using TEM etc. If it can be evaluated, accurate measurement of nanoparticles can be performed efficiently.
  • the present invention has been made in view of the above circumstances, and an object thereof is to select a portion of a sample for which a nanoparticle should be observed quantitatively and precisely with a TEM, an AFM, or the like by a simple technique using an optical microscope or the like. To do.
  • the nanoparticle evaluation method of the present invention includes an irradiation step of irradiating a nanoparticle of a sample containing dispersed nanoparticles with light containing three primary colors, and a measurement step of measuring the wavelength and intensity of light scattered by the nanoparticle.
  • the total scattered light intensity which is the sum of the intensity of the three primary colors
  • the blue light intensity which is the intensity of the blue light
  • the blue light relative to the total scattered light intensity A calculation step of calculating a blue light ratio, which is a ratio of intensity, in a predetermined region of the sample, and an evaluation step of evaluating the dispersion state of the nanoparticles for each predetermined portion in the region using the blue light ratio as an index.
  • the nanoparticle observation apparatus of the present invention includes a stage for placing a sample containing dispersed nanoparticles, and the three primary colors of the nanoparticles from an oblique direction with respect to the upper surface of the stage in a state where the sample is placed.
  • a digital device that records the wavelength and intensity of scattered light in a predetermined region of the sample as digital data out of the light source provided to irradiate light including the light, and the light scattered by the nanoparticles of the light emitted from the light source
  • a digital processing device that calculates a blue light intensity that is the intensity of blue light and a total scattered light intensity that is a sum of the light intensity of the three primary colors based on digital data recorded by the digital device, and an upper surface of the stage
  • a scanning probe microscope including a stage control device that moves the stage in three dimensions.
  • Another nanoparticle observation apparatus includes a stage for placing a sample containing dispersed nanoparticles, and a nanoparticle from an oblique direction with respect to the upper surface of the stage in a state where the sample is placed.
  • the light source provided to irradiate light including the three primary colors and the wavelength and intensity of the scattered light in a predetermined region of the sample among the light scattered by the nanoparticles of the light emitted from the light source are recorded as digital data
  • a digital device, a digital processing device for calculating a blue light intensity that is an intensity of blue light and a total scattered light intensity that is a sum of the intensity of three primary colors based on digital data recorded by the digital device, and a stage An electron microscope provided with an electron gun provided so as to face the upper surface and a stage control device for moving the stage in three dimensions.
  • the present invention it is possible to select a portion of a sample where the nanoparticles should be observed quantitatively and precisely with a TEM, an AFM, or the like by a simple method using an optical microscope or the like.
  • the schematic diagram of the nanoparticle observation apparatus which concerns on embodiment of this invention.
  • the graph which shows the particle diameter dependence of a blue light ratio.
  • the image when the scattered light from the sample of an Example is image
  • the drawings schematically show the nanoparticle observation device, the constituent members of the nanoparticle observation device, and the peripheral members of the nanoparticle observation device.
  • the dimensions and size ratios of these objects are the dimensions and dimensions on the drawings. It is not necessarily consistent with the ratio. A duplicate description will be omitted as appropriate.
  • a numerical range is indicated by describing “ ⁇ ” between two numerical values, the two numerical values are also included in the numerical range.
  • FIG. 1 schematically shows a nanoparticle observation apparatus 10 according to an embodiment of the present invention.
  • the nanoparticle observation apparatus 10 includes a stage 12, a white LED 14 as a light source, condensing lenses 16 and 18, a multimode fiber 20, a polarizing filter 22, an eyepiece lens 24, a projection lens 26, and a digital device.
  • a color digital camera 28, a computer 30 as a digital processing device, and an AFM 40 as a scanning probe microscope are provided.
  • the stage 12 is movable in three dimensions, and the sample S is placed on the upper surface thereof.
  • the sample S includes a substrate P and nanoparticles N dispersed on the substrate.
  • the stage 12 also serves as a sample mounting table that is a constituent member of the AFM 40.
  • the white LED 14 is installed so that white light is irradiated to the nanoparticles from an oblique direction with respect to the upper surface of the stage 12, that is, the upper surface of the substrate P.
  • the light source may not be the white LED 14 as long as light including the three primary colors, that is, blue, green, and red can be irradiated. Examples of light sources including the three primary colors include halogen lamps and fluorescent lamps.
  • the white LED 14 is installed so that the incident angle of the white light irradiated to the nanoparticles can be changed. For this reason, it can respond to observation of the nanoparticle N provided with various materials, sizes, shapes, dispersities, and the like.
  • the condenser lens 16 converges the white light emitted from the white LED 14.
  • the multimode fiber 20 disperses and transmits the white light incident from the condenser lens 16 into many modes.
  • the condenser lens 18 converges the white light incident from the multimode fiber 20.
  • the polarization filter 22 can appropriately change the polarization of white light emitted from the white LED 14. For this reason, it can respond to observation of nanoparticles provided with various materials, sizes, shapes, dispersities, and the like.
  • the white light that has passed through the polarizing filter 22 is irradiated onto the sample S from an oblique direction with respect to the upper surface of the substrate P.
  • the white light irradiated on the sample S is scattered by the nanoparticles N.
  • scattered light having a predetermined scattering angle for example, a scattering angle of 110 ° is collected by the objective lens 24.
  • the scattered light that has passed through the objective lens 24 further passes through the projection lens 26 and forms an image on the focal plane of the color digital camera 28.
  • the color digital camera 28 is provided so as to face the upper surface of the stage 12, that is, so as to capture a scattered light image from the sample S on the stage 12. It is preferable to install an optical microscope between the stage 12 and the color digital camera 28 and use the objective lens and projection lens of the optical microscope, respectively.
  • the color digital camera 28 is attached to the real image focal position of the optical microscope, and the color digital camera 28 is focused on the upper surface of the substrate P.
  • the spatial resolution of the optical microscope may be 1 ⁇ m or more.
  • the color digital camera 28 records, as digital data, the wavelength and intensity of the scattered light in a predetermined region of the sample S out of the scattered light from the white light nanoparticles N emitted from the white LED 14.
  • the predetermined area of the sample S is, for example, within a range of several hundred ⁇ m square of the sample S corresponding to the entire visual field of the color digital camera 28.
  • the predetermined region may be the entire sample S. Note that an image by light scattering from the nanoparticles N is obtained by the color digital camera 28. However, due to the diffraction limit, the individual nanoparticles N cannot be decomposed and observed.
  • the spectrum of the scattered light corresponds to the Rayleigh scattering or Mie scattering theory. That is, theoretically, for nanoparticles having a particle size of about 100 nm or less, the light scattering spectrum can be explained by the Rayleigh scattering theory. In this case, the shorter the wavelength component of the light scattering spectrum, the higher the intensity. On the other hand, in the case of nanoparticles having a larger particle size, the light scattering spectrum has a complicated shape according to the Mie scattering theory. However, in general, the intensity of the long wavelength component of the light scattering spectrum is greater than the Rayleigh scattering condition.
  • a sample in which isolated nanoparticles are dispersed has a higher blue light ratio than a sample having many large nanoparticles due to aggregation. Therefore, it is possible to evaluate the level of the isolated particles by comparing the light scattering spectra. On the other hand, since the intensity of scattered light increases as the number of nanoparticles increases, the particle density can be estimated to some extent from the intensity of scattered light.
  • the ratio of the total scattered light intensity which is the sum of the intensities of the three primary colors from the output of the color digital camera 28, the blue light intensity, which is the intensity of the blue light, and the ratio of the blue light intensity to the total scattered light intensity, that is, “blue The blue light ratio that is “light intensity / total scattered light intensity” is calculated, and the portion of the sample S that is optimal for precisely observing the nanoparticles N is obtained using the blue light intensity and the blue light ratio as indices.
  • Conditions suitable for precise observation required by TEM, SEM, AFM, and the like are states in which isolated particles are dispersed as densely as possible.
  • a portion of the sample S having a high blue light ratio or a portion of the sample S having a high total scattered light intensity may be selected. It should be noted that a digital device other than the color digital camera 28 may be used as long as the wavelength and intensity of scattered light within a predetermined region of the sample S can be recorded as digital data.
  • the computer 30 performs image processing based on the digital data recorded by the color digital camera 28, that is, the image signal of the color digital camera 28, and sets the blue light intensity, the total scattered light intensity, and the blue light ratio in each pixel. calculate. Then, an average value of the total scattered light intensity and the blue light ratio is calculated for each predetermined portion in the predetermined region of the sample S (for example, about 10 ⁇ m square corresponding to the entire visual field of the AFM 40).
  • the blue light ratio and the total scattered light intensity can be found for each about 10 ⁇ m square portion over the entire visual field of the color digital camera 28. Thereafter, the portion of the sample S with a high blue light ratio or the portion of the sample S with a high blue light ratio and a high total scattered light intensity is precisely observed with the AFM 40.
  • a scanning probe microscope other than the AFM 40 such as a scanning tunnel microscope may be used instead of the AFM 40, or an electron microscope may be used.
  • the AFM 40 includes a stage 12, a stage control device 42, an AFM head 44, an AFM cantilever 46, and a probe 48.
  • the stage 12 also serves as a sample mounting table when the color digital camera 28 captures scattered light. That is, the sample stage used when evaluating the dispersion state of the nanoparticles N of the sample S and the sample stage used when precisely observing the nanoparticles N with the AFM 40 are shared as the stage 12. Therefore, the sample S can be managed on the same coordinate axis for the scattered light photographing using the color digital camera 28 and the precise observation by the AFM 40.
  • the stage control device 42 moves the stage 12 in three dimensions. That is, the computer 30 calculates the position of the optimum observation portion of the sample S, and the stage controller 42 moves the optimum observation portion directly below the AFM cantilever 46 based on the coordinates of the position of the optimum observation portion. The position of the stage 12 is controlled. In this way, if the sample S for scattered light imaging using the color digital camera 28 is placed on the stage 12 of the AFM 40, the optimum portion for the precise measurement of the sample S is selected, and then this sample is directly under the AFM cantilever 46. You can move parts quickly.
  • an AFM image of the nanoparticles of the sample S is acquired using the AFM head 44 and the AFM cantilever 46. Based on this image, the shape and particle size of the nanoparticle N can be evaluated.
  • time and labor for selecting the optimum observation portion of the sample S can be greatly saved. Therefore, precise observation of the nanomaterial can be performed efficiently, and the development of the nanomaterial is accelerated.
  • the nanoparticle evaluation method according to the embodiment of the present invention includes an irradiation process, a measurement process, a calculation process, an evaluation process, and an observation process.
  • the nanoparticle evaluation method of the present embodiment may be performed using the nanoparticle observation apparatus 10 or may be performed using another apparatus.
  • the irradiation step light containing the three primary colors is irradiated to the nanoparticles of the sample containing the dispersed nanoparticles.
  • the wavelength and intensity of light scattered by the nanoparticles are measured.
  • the measurement step preferably includes a process of recording the wavelength and intensity of scattered light recognized by the image sensor as digital data.
  • the total scattered light intensity, the blue light intensity, and the blue light ratio are calculated within a predetermined region of the sample from the wavelength and intensity of the scattered light measured in the measurement process.
  • the dispersion state of the nanoparticles is evaluated for each predetermined portion in the region using the blue light ratio as an index.
  • the dispersion state of the nanoparticles may be evaluated for each predetermined portion in the region, using the total scattered light intensity as an index.
  • the sample may include a substrate and nanoparticles dispersed on the substrate, and in the irradiation step, light may be irradiated obliquely with respect to the upper surface of the substrate.
  • FIG. 2 (a) shows the scattered light spectrum (scattering angle 110 °) as a result of theoretical calculation when nine types of SiO 2 true spherical particles having a particle diameter of 50 to 1000 nm are irradiated with white light at an incident angle of 70 °. ing.
  • FIG. 2B shows the relationship between incident light, particles, scattered light, incident angle, and scattering angle. The calculation of the scattered light spectrum was performed based on the Mie scattering theory. As shown in FIG. 2A, the scattered light spectrum monotonously decreases toward the long wavelength side in the particle having a particle diameter of 50 nm which is the Rayleigh scattering region. On the other hand, for particles having a particle diameter exceeding 100 nm, the center of the scattered light spectrum is shifted to the red side, and the scattered light spectrum is complicated.
  • FIG. 3 shows the particle size dependence of the blue light ratio that characterizes the scattered light spectrum from the spherical particles. From the calculation result of FIG. 2, the ratio of the blue light component (420 to 470 nm) to the visible range total scattered light intensity (total scattered light intensity) was calculated.
  • FIG. 3A shows that the inflection point of the particle diameter can be changed by changing the incident angle.
  • FIG.3 (b) it turns out that the inflection point of a particle diameter changes by selecting the polarization
  • the observation portion of the sample is selected based on the dispersion state of the nanoparticles for each predetermined portion of the sample evaluated in the evaluation step, and at least one of the electron microscope and the scanning probe microscope is observed.
  • selecting the observation portion of the sample a portion where the blue light ratio of the sample is high or a portion where the blue light ratio of the sample is high and the total scattered light intensity is high is selected.
  • the nanoparticle evaluation method of this embodiment is particularly effective when the average particle size of the nanoparticles is 50 to 100 nm.
  • a sample containing nanoparticles was observed using a nanoparticle observation apparatus in which an optical microscope was installed between the stage and the color digital camera.
  • the optical microscope was equipped with a long working distance objective lens (magnification 9 times, numerical aperture 0.28, infinite focus correction) and a projection lens (focal length 200 mm).
  • a color digital camera (2048 ⁇ 1536 pixels, pixel pitch 3.2 ⁇ m) was installed on the real image focal plane of the optical microscope. As a result, a range of 640 ⁇ 480 ⁇ m square could be taken with a spatial resolution of about 1 ⁇ m.
  • the sample used was obtained by dispersing silica particles having an average diameter of 100 nm on a flat Si substrate by three kinds of methods.
  • Sample A was prepared by a freeze vacuum drying method with relatively little aggregation.
  • Sample B was prepared by a freeze vacuum drying method in which large aggregates were easily formed.
  • Sample C was produced by natural drying which is generally used.
  • As the light source a high-intensity white power LED (input power 3 W) was used.
  • the light emitted from the white LED was condensed on a multimode fiber (core diameter 300 ⁇ m) by a condenser lens, and the emitted light from this fiber was condensed on the sample surface by a condenser lens.
  • a polarizing filter is provided between the condenser lens on the exit light side of the multimode fiber and the sample so that the polarization of the exit light can be controlled.
  • the incident angle to the sample can be changed by changing the position of the condenser lens on the emission light side of the multimode fiber.
  • the dispersion state of the sample nanoparticles was evaluated using white light with no polarization and an incident angle of 45 to 50 °.
  • the exposure time of the color digital camera was set to such an extent that the intensity did not exceed at each pixel, and the background at the same exposure time was also measured. After shooting, it was saved in a color digital camera as a TIFF file so that pixel information was not lost.
  • FIG. 4 shows images obtained when the scattered light from Sample A, Sample B, and Sample C is photographed with a color digital camera.
  • the background was subtracted, and the true scattered light intensity of each pixel of Sample A, Sample B, and Sample C was determined for the three primary colors.
  • the wavelength of blue light was 420 to 470 nm
  • the wavelength of green light was 490 to 600 nm
  • the wavelength of red light was 540 to 680 nm.
  • averaging was performed in units of 32 ⁇ 32 pixels (10 ⁇ 10 ⁇ m), and the entire region was evaluated using the total scattered light intensity of the three primary colors and the blue light ratio as indices.
  • FIG. 5 shows optical microscope images of Sample A, Sample B, and Sample C, an analysis image in which the magnitude of the total scattered light intensity is represented by color shading, and an analysis image in which the level of the blue light ratio is represented by color shading. It is.
  • the lighter the color the greater the total scattered light intensity or the higher the blue light ratio.
  • sample A a portion having a high total scattered light intensity and a high blue light ratio was present in an island shape.
  • FIG. 6 is an SEM image of Sample A to which glycerin has been added. In the order from FIG. 6A to FIG. 6C, the magnification is changed from low to high.
  • FIG. 7 is an SEM image of Sample B. The magnification in FIG. 7 (a) is lower than the magnification in FIG. 7 (b). 5 and 6, the island-like portion of the sample A having a large total scattered light intensity and a high blue light ratio is composed of isolated particles and microaggregates, and there are no micrometer-class large aggregates. It was confirmed.
  • the total scattered light intensity increases as the number of nanoparticles increases.
  • the blue light ratio indicates good dispersibility, and the influence of the aggregate can be reduced by measuring the portion of the sample where the blue light ratio is high. From FIG. 5 to FIG. 7, it was found that the portion with many isolated particles was widely distributed in the sample A compared with the sample B.
  • the region on the left side of Sample C has a high particle density, but the blue light ratio is low, indicating that there are many aggregates.
  • the area on the right side of the sample C has a low particle density. In general, it can be expected that the lower the particle density, the less likely it is to agglomerate. However, from the image of sample C in FIG. It was found that there are few parts (high blue light ratio).
  • the total scattered light intensity and the blue light ratio vary greatly depending on the location.
  • the blue light ratio is small in the region where the total scattered light intensity is large.
  • the region where the total scattered light intensity is high is considered to be a region where a large number of nanoparticles are aggregated.
  • there are portions where the blue light ratio is low and it has been found that the particles are not necessarily aggregated if the particle density is low.
  • the portion of the sample having a low density of nanoparticles is not necessarily suitable for observation, and that it is effective to select an optimal location according to the present invention.
  • Nanoparticle observation device 12 Stage 14 White LED 16, 18 Condensing lens 20 Multimode fiber 22 Polarizing filter 24 Objective lens 26 Projection lens 28 Color digital camera 30 Computer 40 AFM 42 Stage Controller 44 AFM Head 46 AFM Cantilever 48 Probe S Sample P Substrate N Nanoparticle

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Abstract

In the present invention, a part of a sample where nanoparticles are to be quantitatively observed with precision by an electron microscope (TEM, SEM), an atomic force microscope (AFM), etc., is selected by a simple method using an optical microscope, etc. A nanoparticle observation device 10 is provided with a stage 12, a white LED 14, a color digital camera 28, a computer 30, and an AFM 40. The white LED 14 is provided so as to irradiate nanoparticles in a sample S on the stage 12 with white light from an oblique direction. The color digital camera 28 stores, as digital data, the wavelength and intensity of scattered light which results from the light from the white LED 14 being scattered by the nanoparticles. The computer 30 calculates, on the basis of the digital data stored in the color digital camera 28, a blue light intensity which is the intensity of blue light and a total scattered light intensity which is the sum of the light intensities of three primary color lights. A part of the sample S where the total scattered light intensity, and the blue light intensity/the total scattered light intensity are high is observed with precision by the AFM 40.

Description

ナノ粒子評価方法およびナノ粒子観察装置Nanoparticle evaluation method and nanoparticle observation apparatus
 本発明は、ナノ粒子の分散状態を評価する方法と、ナノ粒子の形状等を観察する装置に関する。 The present invention relates to a method for evaluating the dispersion state of nanoparticles and an apparatus for observing the shape of the nanoparticles.
 ナノ材料の性能向上や安全性評価に向けて、ナノ粒子の形状評価の精密化が求められている。電子顕微鏡(TEM、SEM)や原子間力顕微鏡(AFM)を用いれば、ナノメートルオーダーの個々の粒子が観察できる。このため、ナノ粒子の形状等の観察は、TEM等を用いて行われている。しかしながら、TEM等は、空間分解能が高い分、視野が狭い。不均一に分散されたナノ粒子を有する試料は、粒子が凝集して積み重なっている部分もあれば、粒子が存在しない部分もある。したがって、不均一に分散されたナノ粒子を有する試料では、TEM等でどの部分を観察すべきかが容易にわからない。従来は、観察者の勘を頼りに試料のいろいろな部分を見て、ナノ粒子が均一に分散された最適な観察部分を選定していた。 】 To improve the performance of nanomaterials and to evaluate safety, it is necessary to refine the shape evaluation of nanoparticles. If an electron microscope (TEM, SEM) or an atomic force microscope (AFM) is used, individual particles of nanometer order can be observed. For this reason, the observation of the shape and the like of the nanoparticles is performed using TEM or the like. However, TEM and the like have a narrow field of view due to high spatial resolution. A sample having non-uniformly dispersed nanoparticles includes a part where the particles are aggregated and stacked, and a part where the particles are not present. Therefore, in a sample having nanoparticles dispersed unevenly, it is not easy to know which part should be observed with a TEM or the like. In the past, depending on the intuition of the observer, various parts of the sample were viewed, and the optimal observation part in which the nanoparticles were uniformly dispersed was selected.
 一方、光学顕微鏡は視野が広いので、ナノ粒子が重なってしまっている部分など、明らかに観察に適さない部分を特定することが可能である。しかし、光の回折限界のため、直径が1μm以下の粒子の分散状態を直接観察することは困難である。光学顕微鏡を用いた一度の観察によって、試料の数百μm角の広い領域から、TEM等で観察すべき部分を短時間で選定できれば望ましい。TEM等を用いた精密測定の視野は数μm角であるため、TEM等を用いたナノ粒子の精密測定の前段階で、試料の数μm角の部分でナノ粒子の分散状態が光学顕微鏡を用いて評価できれば、効率的にナノ粒子の精密測定ができる。 On the other hand, since the optical microscope has a wide field of view, it is possible to specify a portion that is clearly unsuitable for observation, such as a portion where nanoparticles overlap. However, due to the diffraction limit of light, it is difficult to directly observe the dispersion state of particles having a diameter of 1 μm or less. It is desirable that a portion to be observed with a TEM or the like can be selected in a short time from a wide region of several hundred μm square of the sample by a single observation using an optical microscope. Since the field of precision measurement using TEM etc. is several μm square, the dispersion state of nanoparticles in the part of several μm square of the sample is measured using an optical microscope at the stage before precise measurement of nanoparticles using TEM etc. If it can be evaluated, accurate measurement of nanoparticles can be performed efficiently.
 本発明は上記事情に鑑みてなされたものであり、TEMやAFM等でナノ粒子を定量的に精密観察すべき試料の部分を、光学顕微鏡等を用いた簡便な手法によって選定することを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to select a portion of a sample for which a nanoparticle should be observed quantitatively and precisely with a TEM, an AFM, or the like by a simple technique using an optical microscope or the like. To do.
 本発明のナノ粒子評価方法は、分散しているナノ粒子を含む試料のナノ粒子に、三原色を含む光を照射する照射工程と、ナノ粒子による光の散乱光の波長と強度を測定する測定工程と、測定工程で測定された散乱光の波長と強度から、三原色の光の強度の総和である全散乱光強度と、青色の光の強度である青色光強度と、全散乱光強度に対する青色光強度の割合である青色光比率とを、試料の所定の領域内で算出する算出工程と、青色光比率を指標として、ナノ粒子の分散状態を領域内の所定の部分ごとに評価する評価工程を有している。 The nanoparticle evaluation method of the present invention includes an irradiation step of irradiating a nanoparticle of a sample containing dispersed nanoparticles with light containing three primary colors, and a measurement step of measuring the wavelength and intensity of light scattered by the nanoparticle. From the wavelength and intensity of the scattered light measured in the measuring process, the total scattered light intensity, which is the sum of the intensity of the three primary colors, the blue light intensity, which is the intensity of the blue light, and the blue light relative to the total scattered light intensity A calculation step of calculating a blue light ratio, which is a ratio of intensity, in a predetermined region of the sample, and an evaluation step of evaluating the dispersion state of the nanoparticles for each predetermined portion in the region using the blue light ratio as an index. Have.
 本発明のナノ粒子観察装置は、分散しているナノ粒子を含む試料を載置するためのステージと、試料が載置された状態で、ステージの上面に対して斜め方向から、ナノ粒子に三原色を含む光を照射するように設けられた光源と、光源から照射された光のナノ粒子による散乱光のうち、試料の所定の領域内の散乱光の波長と強度をデジタルデータとして記録するデジタル機器と、デジタル機器が記録したデジタルデータに基づいて、青色の光の強度である青色光強度と、三原色の光の強度の総和である全散乱光強度とを算出するデジタル処理装置と、ステージの上面と対向するように設けられた探針、およびステージを三次元に移動するステージ制御装置を備える走査型プローブ顕微鏡を有している。 The nanoparticle observation apparatus of the present invention includes a stage for placing a sample containing dispersed nanoparticles, and the three primary colors of the nanoparticles from an oblique direction with respect to the upper surface of the stage in a state where the sample is placed. A digital device that records the wavelength and intensity of scattered light in a predetermined region of the sample as digital data out of the light source provided to irradiate light including the light, and the light scattered by the nanoparticles of the light emitted from the light source And a digital processing device that calculates a blue light intensity that is the intensity of blue light and a total scattered light intensity that is a sum of the light intensity of the three primary colors based on digital data recorded by the digital device, and an upper surface of the stage And a scanning probe microscope including a stage control device that moves the stage in three dimensions.
 本発明の他のナノ粒子観察装置は、分散しているナノ粒子を含む試料を載置するためのステージと、試料が載置された状態で、ステージの上面に対して斜め方向から、ナノ粒子に三原色を含む光を照射するように設けられた光源と、光源から照射された光のナノ粒子による散乱光のうち、試料の所定の領域内の散乱光の波長と強度をデジタルデータとして記録するデジタル機器と、デジタル機器が記録したデジタルデータに基づいて、青色の光の強度である青色光強度と、三原色の光の強度の総和である全散乱光強度とを算出するデジタル処理装置と、ステージの上面と対向するように設けられた電子銃と、ステージを三次元に移動するステージ制御装置とを備える電子顕微鏡を有している。 Another nanoparticle observation apparatus according to the present invention includes a stage for placing a sample containing dispersed nanoparticles, and a nanoparticle from an oblique direction with respect to the upper surface of the stage in a state where the sample is placed. The light source provided to irradiate light including the three primary colors and the wavelength and intensity of the scattered light in a predetermined region of the sample among the light scattered by the nanoparticles of the light emitted from the light source are recorded as digital data A digital device, a digital processing device for calculating a blue light intensity that is an intensity of blue light and a total scattered light intensity that is a sum of the intensity of three primary colors based on digital data recorded by the digital device, and a stage An electron microscope provided with an electron gun provided so as to face the upper surface and a stage control device for moving the stage in three dimensions.
 本発明によれば、光学顕微鏡等を用いた簡便な手法によって、TEMやAFM等でナノ粒子を定量的に精密観察すべき試料の部分が選定できる。 According to the present invention, it is possible to select a portion of a sample where the nanoparticles should be observed quantitatively and precisely with a TEM, an AFM, or the like by a simple method using an optical microscope or the like.
本発明の実施形態に係るナノ粒子観察装置の模式図。The schematic diagram of the nanoparticle observation apparatus which concerns on embodiment of this invention. 各種真球粒子に白色光を照射したときの散乱光スペクトルの理論計算結果(a)と、入射光、粒子、散乱光、入射角、および散乱角の関係を説明するための図(b)。The figure (b) for demonstrating the relationship of the theoretical calculation result (a) of a scattered light spectrum when white light is irradiated to various spherical particles, and incident light, particle | grains, scattered light, an incident angle, and a scattering angle. 青色光比率の粒子径依存性を示すグラフ。The graph which shows the particle diameter dependence of a blue light ratio. 実施例の試料からの散乱光をカラーデジタルカメラで撮影したときの画像。The image when the scattered light from the sample of an Example is image | photographed with the color digital camera. 実施例の試料の光学顕微鏡像と、全散乱光強度および青色光比率の解析画像。The optical microscope image of the sample of an Example, and the analysis image of a total scattered light intensity | strength and a blue light ratio. 実施例の試料AのSEM像。The SEM image of the sample A of an Example. 実施例の試料BのSEM像。The SEM image of the sample B of an Example.
 以下、本発明のナノ粒子観察装置およびナノ粒子評価方法について、実施形態と実施例に基づいて詳細に説明する。図面は、ナノ粒子観察装置、ナノ粒子観察装置の構成部材、およびナノ粒子観察装置の周辺部材を模式的に表したものであり、これらの実物の寸法および寸法比は、図面上の寸法および寸法比と必ずしも一致していない。重複説明は適宜省略する。なお、2つの数値の間に「~」を記載して数値範囲を表す場合には、この2つの数値も数値範囲に含まれるものとする。 Hereinafter, the nanoparticle observation apparatus and the nanoparticle evaluation method of the present invention will be described in detail based on embodiments and examples. The drawings schematically show the nanoparticle observation device, the constituent members of the nanoparticle observation device, and the peripheral members of the nanoparticle observation device. The dimensions and size ratios of these objects are the dimensions and dimensions on the drawings. It is not necessarily consistent with the ratio. A duplicate description will be omitted as appropriate. In the case where a numerical range is indicated by describing “˜” between two numerical values, the two numerical values are also included in the numerical range.
(ナノ粒子観察装置)
 図1は、本発明の実施形態に係るナノ粒子観察装置10を模式的に示している。ナノ粒子観察装置10は、ステージ12と、光源である白色LED14と、集光レンズ16,18と、マルチモードファイバー20と、偏光フィルター22と、接眼レンズ24と、投影レンズ26と、デジタル機器であるカラーデジタルカメラ28と、デジタル処理装置であるコンピュータ30と、走査型プローブ顕微鏡であるAFM40とを備えている。
(Nanoparticle observation equipment)
FIG. 1 schematically shows a nanoparticle observation apparatus 10 according to an embodiment of the present invention. The nanoparticle observation apparatus 10 includes a stage 12, a white LED 14 as a light source, condensing lenses 16 and 18, a multimode fiber 20, a polarizing filter 22, an eyepiece lens 24, a projection lens 26, and a digital device. A color digital camera 28, a computer 30 as a digital processing device, and an AFM 40 as a scanning probe microscope are provided.
 ステージ12は、三次元に移動可能で、その上面に試料Sを載置する。試料Sは、基板Pと、基板上で分散しているナノ粒子Nを備えている。ステージ12は、AFM40の構成部材である試料載置台を兼ねている。白色LED14は、ステージ12の上面、すなわち基板Pの上面に対して斜め方向から、ナノ粒子に白色光が照射されるように設置されている。なお、光源は、三原色、すなわち青色、緑色、および赤色を含む光が照射できれば、白色LED14でなくもよい。三原色を含む光源として、ハロゲンランプや蛍光灯などが例示できる。また、白色LED14は、ナノ粒子に照射する白色光の入射角が変更できるように設置されている。このため、様々な材質、大きさ、形状、および分散度等を備えるナノ粒子Nの観察に対応できる。 The stage 12 is movable in three dimensions, and the sample S is placed on the upper surface thereof. The sample S includes a substrate P and nanoparticles N dispersed on the substrate. The stage 12 also serves as a sample mounting table that is a constituent member of the AFM 40. The white LED 14 is installed so that white light is irradiated to the nanoparticles from an oblique direction with respect to the upper surface of the stage 12, that is, the upper surface of the substrate P. The light source may not be the white LED 14 as long as light including the three primary colors, that is, blue, green, and red can be irradiated. Examples of light sources including the three primary colors include halogen lamps and fluorescent lamps. Moreover, the white LED 14 is installed so that the incident angle of the white light irradiated to the nanoparticles can be changed. For this reason, it can respond to observation of the nanoparticle N provided with various materials, sizes, shapes, dispersities, and the like.
 集光レンズ16は、白色LED14から射出された白色光を収束する。マルチモードファイバー20は、集光レンズ16から入射した白色光を多くのモードに分散して伝送する。集光レンズ18は、マルチモードファイバー20から入射した白色光を収束する。本実施形態では、偏光フィルター22は、白色LED14が射出した白色光の偏光を適宜変えることができる。このため、様々な材質、大きさ、形状、および分散度等を備えるナノ粒子の観察に対応できる。偏光フィルター22を通過した白色光は、基板Pの上面に対して斜め方向から試料Sに照射される。 The condenser lens 16 converges the white light emitted from the white LED 14. The multimode fiber 20 disperses and transmits the white light incident from the condenser lens 16 into many modes. The condenser lens 18 converges the white light incident from the multimode fiber 20. In the present embodiment, the polarization filter 22 can appropriately change the polarization of white light emitted from the white LED 14. For this reason, it can respond to observation of nanoparticles provided with various materials, sizes, shapes, dispersities, and the like. The white light that has passed through the polarizing filter 22 is irradiated onto the sample S from an oblique direction with respect to the upper surface of the substrate P.
 試料Sに照射された白色光は、ナノ粒子Nによって散乱される。このうち、所定の散乱角、例えば散乱角110°の散乱光が対物レンズ24によって集光される。対物レンズ24を通過した散乱光は、さらに投影レンズ26を通過して、カラーデジタルカメラ28の焦点面に結像される。本実施形態では、カラーデジタルカメラ28は、ステージ12の上面と対向するように、すなわちステージ12上の試料Sからの散乱光像を撮影できるように設けられている。ステージ12とカラーデジタルカメラ28の間に光学顕微鏡を設置して、この光学顕微鏡の対物レンズと投影レンズをそれぞれ利用するのが好ましい。この場合、光学顕微鏡の実像焦点位置にカラーデジタルカメラ28を取り付け、カラーデジタルカメラ28のフォーカスを基板Pの上面に合わせる。光学顕微鏡の空間分解能は、1μm以上であってもよい。 The white light irradiated on the sample S is scattered by the nanoparticles N. Among these, scattered light having a predetermined scattering angle, for example, a scattering angle of 110 ° is collected by the objective lens 24. The scattered light that has passed through the objective lens 24 further passes through the projection lens 26 and forms an image on the focal plane of the color digital camera 28. In the present embodiment, the color digital camera 28 is provided so as to face the upper surface of the stage 12, that is, so as to capture a scattered light image from the sample S on the stage 12. It is preferable to install an optical microscope between the stage 12 and the color digital camera 28 and use the objective lens and projection lens of the optical microscope, respectively. In this case, the color digital camera 28 is attached to the real image focal position of the optical microscope, and the color digital camera 28 is focused on the upper surface of the substrate P. The spatial resolution of the optical microscope may be 1 μm or more.
 カラーデジタルカメラ28は、白色LED14から照射された白色光のナノ粒子Nによる散乱光のうち、試料Sの所定の領域内の散乱光の波長と強度をデジタルデータとして記録する。ここで、試料Sの所定の領域内とは、例えば、カラーデジタルカメラ28の全視野に対応する試料Sの数百μm角の範囲内である。試料Sの大きさによっては、所定の領域内が試料S全体の場合もある。なお、カラーデジタルカメラ28でナノ粒子Nからの光散乱による像が得られる。しかし、回折限界のため、個々のナノ粒子Nを分解して観察することはできない。 The color digital camera 28 records, as digital data, the wavelength and intensity of the scattered light in a predetermined region of the sample S out of the scattered light from the white light nanoparticles N emitted from the white LED 14. Here, the predetermined area of the sample S is, for example, within a range of several hundred μm square of the sample S corresponding to the entire visual field of the color digital camera 28. Depending on the size of the sample S, the predetermined region may be the entire sample S. Note that an image by light scattering from the nanoparticles N is obtained by the color digital camera 28. However, due to the diffraction limit, the individual nanoparticles N cannot be decomposed and observed.
 光を散乱させるナノ粒子の粒径に応じて、散乱光のスペクトルはレーリー散乱やミー散乱理論に対応する。すなわち、理論的には、粒径100nm程度以下のナノ粒子では、光散乱スペクトルがレーリー散乱理論で説明できる。この場合、光散乱スペクトルの短波長成分ほど強度が大きくなる。一方、それよりも粒径が大きいナノ粒子では、光散乱スペクトルがミー散乱理論に従って複雑な形状となる。しかし、一般に、レーリー散乱条件より光散乱スペクトルの長波長成分の強度が大きくなる。したがって、孤立したナノ粒子が分散した試料では、凝集による大きなナノ粒子が多い試料と比較して青色光比率が高くなる。このため、光散乱スペクトルの比較により、孤立粒子の比率の高低について評価が可能である。一方、散乱光の強度はナノ粒子数が多いほど強くなるので、散乱光の強度から粒子密度がある程度推定できる。 Depending on the particle size of the nanoparticles that scatter the light, the spectrum of the scattered light corresponds to the Rayleigh scattering or Mie scattering theory. That is, theoretically, for nanoparticles having a particle size of about 100 nm or less, the light scattering spectrum can be explained by the Rayleigh scattering theory. In this case, the shorter the wavelength component of the light scattering spectrum, the higher the intensity. On the other hand, in the case of nanoparticles having a larger particle size, the light scattering spectrum has a complicated shape according to the Mie scattering theory. However, in general, the intensity of the long wavelength component of the light scattering spectrum is greater than the Rayleigh scattering condition. Therefore, a sample in which isolated nanoparticles are dispersed has a higher blue light ratio than a sample having many large nanoparticles due to aggregation. Therefore, it is possible to evaluate the level of the isolated particles by comparing the light scattering spectra. On the other hand, since the intensity of scattered light increases as the number of nanoparticles increases, the particle density can be estimated to some extent from the intensity of scattered light.
 そこで、カラーデジタルカメラ28の出力から三原色の光の強度の総和である全散乱光強度と、青色の光の強度である青色光強度と、全散乱光強度に対する青色光強度の比、すなわち「青色光強度/全散乱光強度」である青色光比率を算出して、青色光強度と青色光比率を指標として、ナノ粒子Nを精密観察するのに最適な試料Sの部分を求める。TEM、SEM、およびAFM等で求められる精密観察に適した条件は、なるべく孤立した粒子が高密度に分散している状態である。したがって、青色光比率が高い試料Sの部分や、全散乱光強度が大きい試料Sの部分を選択すればよい。なお、試料Sの所定の領域内の散乱光の波長と強度をデジタルデータとして記録できれば、カラーデジタルカメラ28以外のデジタル機器を使用してもよい。 Therefore, the ratio of the total scattered light intensity, which is the sum of the intensities of the three primary colors from the output of the color digital camera 28, the blue light intensity, which is the intensity of the blue light, and the ratio of the blue light intensity to the total scattered light intensity, that is, “blue The blue light ratio that is “light intensity / total scattered light intensity” is calculated, and the portion of the sample S that is optimal for precisely observing the nanoparticles N is obtained using the blue light intensity and the blue light ratio as indices. Conditions suitable for precise observation required by TEM, SEM, AFM, and the like are states in which isolated particles are dispersed as densely as possible. Therefore, a portion of the sample S having a high blue light ratio or a portion of the sample S having a high total scattered light intensity may be selected. It should be noted that a digital device other than the color digital camera 28 may be used as long as the wavelength and intensity of scattered light within a predetermined region of the sample S can be recorded as digital data.
 コンピュータ30は、カラーデジタルカメラ28が記録したデジタルデータに基づいて、すなわちカラーデジタルカメラ28の画像信号を取り込んで画像処理し、青色光強度と、全散乱光強度と、青色光比率を各画素で算出する。そして、試料Sの所定の領域内の所定の部分(例えば、AFM40の全視野に対応する約十μm角)ごとに、全散乱光強度と青色光比率の平均値を算出する。 The computer 30 performs image processing based on the digital data recorded by the color digital camera 28, that is, the image signal of the color digital camera 28, and sets the blue light intensity, the total scattered light intensity, and the blue light ratio in each pixel. calculate. Then, an average value of the total scattered light intensity and the blue light ratio is calculated for each predetermined portion in the predetermined region of the sample S (for example, about 10 μm square corresponding to the entire visual field of the AFM 40).
 こうして、カラーデジタルカメラ28の全視野にわたって、約十μm角の部分ごとに、青色光比率と全散乱光強度がわかる。その後、青色光比率が高い試料Sの部分、または青色光比率が高く全散乱光強度が大きい試料Sの部分を、AFM40で精密観察する。本実施形態ではAFM40を用いたが、AFM40に代えて、走査型トンネル顕微鏡等のAFM40以外の走査型プローブ顕微鏡を用いてもよいし、電子顕微鏡を用いてもよい。 Thus, the blue light ratio and the total scattered light intensity can be found for each about 10 μm square portion over the entire visual field of the color digital camera 28. Thereafter, the portion of the sample S with a high blue light ratio or the portion of the sample S with a high blue light ratio and a high total scattered light intensity is precisely observed with the AFM 40. Although the AFM 40 is used in the present embodiment, a scanning probe microscope other than the AFM 40 such as a scanning tunnel microscope may be used instead of the AFM 40, or an electron microscope may be used.
 AFM40は、ステージ12と、ステージ制御装置42と、AFMヘッド44と、AFMカンチレバー46と、探針48とを備えている。ステージ12は、カラーデジタルカメラ28で散乱光を撮影するときの試料載置台を兼ねている。すなわち、試料Sのナノ粒子Nの分散状態を評価するときに使用する試料載置台と、AFM40でナノ粒子Nを精密観察するときに使用する試料載置台が、ステージ12として共用されている。したがって、カラーデジタルカメラ28を用いた散乱光撮影とAFM40による精密観察が同じ座標軸上で、試料Sを管理することができる。 The AFM 40 includes a stage 12, a stage control device 42, an AFM head 44, an AFM cantilever 46, and a probe 48. The stage 12 also serves as a sample mounting table when the color digital camera 28 captures scattered light. That is, the sample stage used when evaluating the dispersion state of the nanoparticles N of the sample S and the sample stage used when precisely observing the nanoparticles N with the AFM 40 are shared as the stage 12. Therefore, the sample S can be managed on the same coordinate axis for the scattered light photographing using the color digital camera 28 and the precise observation by the AFM 40.
 ステージ制御装置42は、ステージ12を三次元に移動する。すなわち、コンピュータ30によって、試料Sの最適観察部分の位置が計算され、この最適観察部分の位置の座標に基づいて、最適観察部分がAFMカンチレバー46の直下に移動するように、ステージ制御装置42でステージ12の位置が制御される。このように、カラーデジタルカメラ28を用いた散乱光撮影のための試料SをAFM40のステージ12上に置けば、試料Sの精密測定に最適な部分を選定した後、AFMカンチレバー46の直下にこの部分をすぐに移動できる。 The stage control device 42 moves the stage 12 in three dimensions. That is, the computer 30 calculates the position of the optimum observation portion of the sample S, and the stage controller 42 moves the optimum observation portion directly below the AFM cantilever 46 based on the coordinates of the position of the optimum observation portion. The position of the stage 12 is controlled. In this way, if the sample S for scattered light imaging using the color digital camera 28 is placed on the stage 12 of the AFM 40, the optimum portion for the precise measurement of the sample S is selected, and then this sample is directly under the AFM cantilever 46. You can move parts quickly.
 その後、AFMヘッド44とAFMカンチレバー46を用いて、試料Sのナノ粒子のAFM画像が取得される。この画像に基づいて、ナノ粒子Nの形状や粒径等が評価できる。このように、ナノ粒子観察装置10によれば、試料Sの最適観察部分の選択のための時間と労力を大幅に省くことができる。このため、ナノ材料の精密観察を効率よく行うことができ、ナノ材料の開発が加速される。 Thereafter, an AFM image of the nanoparticles of the sample S is acquired using the AFM head 44 and the AFM cantilever 46. Based on this image, the shape and particle size of the nanoparticle N can be evaluated. Thus, according to the nanoparticle observation apparatus 10, time and labor for selecting the optimum observation portion of the sample S can be greatly saved. Therefore, precise observation of the nanomaterial can be performed efficiently, and the development of the nanomaterial is accelerated.
(ナノ粒子評価方法)
 本発明の実施形態に係るナノ粒子評価方法は、照射工程と、測定工程と、算出工程と、評価工程と、観察工程とを備えている。本実施形態のナノ粒子評価方法は、ナノ粒子観察装置10を使って行ってもよいし、他の装置を使って行ってもよい。照射工程では、分散しているナノ粒子を含む試料のナノ粒子に、三原色を含む光を照射する。測定工程では、ナノ粒子による光の散乱光の波長と強度を測定する。測定工程では、撮像素子で認識された散乱光の波長と強度をデジタルデータとして記録する過程を含むことが好ましい。
(Nanoparticle evaluation method)
The nanoparticle evaluation method according to the embodiment of the present invention includes an irradiation process, a measurement process, a calculation process, an evaluation process, and an observation process. The nanoparticle evaluation method of the present embodiment may be performed using the nanoparticle observation apparatus 10 or may be performed using another apparatus. In the irradiation step, light containing the three primary colors is irradiated to the nanoparticles of the sample containing the dispersed nanoparticles. In the measurement process, the wavelength and intensity of light scattered by the nanoparticles are measured. The measurement step preferably includes a process of recording the wavelength and intensity of scattered light recognized by the image sensor as digital data.
 算出工程では、測定工程で測定された散乱光の波長と強度から、全散乱光強度と、青色光強度と、青色光比率を、試料の所定の領域内で算出する。評価工程では、青色光比率を指標として、ナノ粒子の分散状態を領域内の所定の部分ごとに評価する。評価工程では、さらに全散乱光強度を指標として、ナノ粒子の分散状態を領域内の所定の部分ごとに評価してもよい。試料が、基板と、基板上で分散しているナノ粒子とを含み、照射工程では、基板上面に対して斜め方向に光を照射してもよい。 In the calculation step, the total scattered light intensity, the blue light intensity, and the blue light ratio are calculated within a predetermined region of the sample from the wavelength and intensity of the scattered light measured in the measurement process. In the evaluation step, the dispersion state of the nanoparticles is evaluated for each predetermined portion in the region using the blue light ratio as an index. In the evaluation step, the dispersion state of the nanoparticles may be evaluated for each predetermined portion in the region, using the total scattered light intensity as an index. The sample may include a substrate and nanoparticles dispersed on the substrate, and in the irradiation step, light may be irradiated obliquely with respect to the upper surface of the substrate.
 図2(a)は、粒子径50~1000nmの9種類のSiO真球粒子に、入射角70°で白色光を照射したときの散乱光スペクトル(散乱角110°)を理論計算結果で示している。図2(b)は、入射光、粒子、散乱光、入射角、および散乱角の関係を示している。この散乱光スペクトルの計算は、ミー散乱理論に基づいて行った。図2(a)に示すように、レーリー散乱領域である粒子径50nmの粒子では、散乱光スペクトルが長波長側に向けて単調に減少している。一方、粒子径100nmを超える粒子では、散乱光スペクトルの重心が赤色側に偏移するとともに、散乱光スペクトルが複雑化している。 FIG. 2 (a) shows the scattered light spectrum (scattering angle 110 °) as a result of theoretical calculation when nine types of SiO 2 true spherical particles having a particle diameter of 50 to 1000 nm are irradiated with white light at an incident angle of 70 °. ing. FIG. 2B shows the relationship between incident light, particles, scattered light, incident angle, and scattering angle. The calculation of the scattered light spectrum was performed based on the Mie scattering theory. As shown in FIG. 2A, the scattered light spectrum monotonously decreases toward the long wavelength side in the particle having a particle diameter of 50 nm which is the Rayleigh scattering region. On the other hand, for particles having a particle diameter exceeding 100 nm, the center of the scattered light spectrum is shifted to the red side, and the scattered light spectrum is complicated.
 図3は、真球微粒子からの散乱光スペクトルを特徴づける青色光比率の粒子径依存性を示している。図2の計算結果から、青色光成分(420~470nm)の可視域全散乱光強度(全散乱光強度)に対する比率を計算した。図3(a)によれば、入射角を変えることで、粒子径の変曲点を変えることができることがわかる。図3(b)では、入射光の偏光を選択することで、粒子径の変曲点が変化することがわかる。図3(a)および図3(b)により、入射角と偏光の選択によって、評価に必要なナノ粒子の粒径のしきい値(評価基準粒径)を変化させることが可能であることがわかる。 FIG. 3 shows the particle size dependence of the blue light ratio that characterizes the scattered light spectrum from the spherical particles. From the calculation result of FIG. 2, the ratio of the blue light component (420 to 470 nm) to the visible range total scattered light intensity (total scattered light intensity) was calculated. FIG. 3A shows that the inflection point of the particle diameter can be changed by changing the incident angle. In FIG.3 (b), it turns out that the inflection point of a particle diameter changes by selecting the polarization | polarized-light of incident light. 3 (a) and 3 (b), it is possible to change the threshold value (evaluation reference particle size) of the particle size of the nanoparticles necessary for the evaluation by selecting the incident angle and the polarized light. Recognize.
 観察工程では、評価工程で評価した試料の所定の部分ごとのナノ粒子の分散状態に基づいて、試料の観察部分を選定し、電子顕微鏡および走査型プローブ顕微鏡の少なくとも一方で観察部分を観察する。試料の観察部分の選定では、試料の青色光比率が高い部分、または試料の青色光比率が高く全散乱光強度が大きい部分を選定する。本実施形態のナノ粒子評価方法は、ナノ粒子の平均粒径が50~100nmであるときに特に有効である。 In the observation step, the observation portion of the sample is selected based on the dispersion state of the nanoparticles for each predetermined portion of the sample evaluated in the evaluation step, and at least one of the electron microscope and the scanning probe microscope is observed. In selecting the observation portion of the sample, a portion where the blue light ratio of the sample is high or a portion where the blue light ratio of the sample is high and the total scattered light intensity is high is selected. The nanoparticle evaluation method of this embodiment is particularly effective when the average particle size of the nanoparticles is 50 to 100 nm.
 ステージとカラーデジタルカメラの間に光学顕微鏡を設置したナノ粒子観察装置を用いて、ナノ粒子を含む試料を観察した。光学顕微鏡は、長作動距離対物レンズ(倍率9倍、開口数0.28、無限焦点補正)と、投影レンズ(焦点距離200mm)を備えていた。光学顕微鏡の実像焦点面にカラーデジタルカメラ(2048×1536画素、画素ピッチ3.2μm)を設置した。これにより640×480μm角の範囲が、空間分解能約1μmで撮影可能であった。 A sample containing nanoparticles was observed using a nanoparticle observation apparatus in which an optical microscope was installed between the stage and the color digital camera. The optical microscope was equipped with a long working distance objective lens (magnification 9 times, numerical aperture 0.28, infinite focus correction) and a projection lens (focal length 200 mm). A color digital camera (2048 × 1536 pixels, pixel pitch 3.2 μm) was installed on the real image focal plane of the optical microscope. As a result, a range of 640 × 480 μm square could be taken with a spatial resolution of about 1 μm.
 試料は、平坦なSi基板上に平均直径100nmのシリカ粒子を3種類の手法で分散したものを用いた。試料Aは、凝集が比較的少ない凍結真空乾燥法により作製した。試料Bは、大きな凝集体ができやすい凍結真空乾燥法により作製した。試料Cは、通常一般に用いられている自然乾燥により作製した。光源は、高輝度白色パワーLED(投入電力3W)を用いた。白色LEDから射出された光は、集光レンズでマルチモードファイバー(コア径300μm)に集光され、このファイバーからの射出光を集光レンズで試料面上に集光した。 The sample used was obtained by dispersing silica particles having an average diameter of 100 nm on a flat Si substrate by three kinds of methods. Sample A was prepared by a freeze vacuum drying method with relatively little aggregation. Sample B was prepared by a freeze vacuum drying method in which large aggregates were easily formed. Sample C was produced by natural drying which is generally used. As the light source, a high-intensity white power LED (input power 3 W) was used. The light emitted from the white LED was condensed on a multimode fiber (core diameter 300 μm) by a condenser lens, and the emitted light from this fiber was condensed on the sample surface by a condenser lens.
 マルチモードファイバーの射出光側の集光レンズと試料の間に偏光フィルターを設けて、射出光の偏光を制御できるようにした。また、マルチモードファイバーの射出光側の集光レンズの位置を変えて、試料への入射角が変えられるようにした。本実施例では、無偏光で入射角45~50°の白色光を用いて、試料のナノ粒子の分散状態を評価した。カラーデジタルカメラの露光時間は、各画素での強度オーバーが起きない程度に設定し、同じ露光時間でのバックグラウンドも測定した。撮影後、画素情報の損失が起きないように、TIFF形式のファイルとしてカラーデジタルカメラに保存した。試料A、試料B、および試料Cからの散乱光をカラーデジタルカメラで撮影したときの画像を図4に示す。 ∙ A polarizing filter is provided between the condenser lens on the exit light side of the multimode fiber and the sample so that the polarization of the exit light can be controlled. In addition, the incident angle to the sample can be changed by changing the position of the condenser lens on the emission light side of the multimode fiber. In this example, the dispersion state of the sample nanoparticles was evaluated using white light with no polarization and an incident angle of 45 to 50 °. The exposure time of the color digital camera was set to such an extent that the intensity did not exceed at each pixel, and the background at the same exposure time was also measured. After shooting, it was saved in a color digital camera as a TIFF file so that pixel information was not lost. FIG. 4 shows images obtained when the scattered light from Sample A, Sample B, and Sample C is photographed with a color digital camera.
 カラーデジタルカメラに保存したTIFFファイルをコンピュータで読み込んだ後、バックグラウンドを差し引いて、試料A、試料B、および試料Cの各画素の真の散乱光強度を三原色について求めた。なお、青色光の波長は420~470nm、緑色光の波長は490~600nm、赤色光の波長は540~680nmとした。そして、32×32画素(10×10μm)の単位で平均化して、三原色の全散乱光強度および青色光比率を指標として、全領域の評価を行った。 After reading the TIFF file stored in the color digital camera with a computer, the background was subtracted, and the true scattered light intensity of each pixel of Sample A, Sample B, and Sample C was determined for the three primary colors. The wavelength of blue light was 420 to 470 nm, the wavelength of green light was 490 to 600 nm, and the wavelength of red light was 540 to 680 nm. Then, averaging was performed in units of 32 × 32 pixels (10 × 10 μm), and the entire region was evaluated using the total scattered light intensity of the three primary colors and the blue light ratio as indices.
 図5は、試料A、試料B、および試料Cの光学顕微鏡の画像、全散乱光強度の大小を色の濃淡で表わした解析画像、および青色光比率の高低を色の濃淡で表わした解析画像である。図5では、色が薄いほど、全散乱光強度が大きい、または青色光比率が高い。試料Aでは、全散乱光強度が大きく、青色光比率が高い部分が島状に存在していた。図6は、グリセリンを添加した試料AのSEM画像である。図6(a)から図6(c)の順に、低倍率から高倍率になっている。図7は試料BのSEM画像である。図7(a)の倍率は、図7(b)の倍率より低い。図5および図6より、試料Aの全散乱光強度が大きく、青色光比率が高い島状の部分は、孤立粒子と微小凝集体で構成されており、マイクロメータークラスの大凝集体は存在しないことが確認された。 FIG. 5 shows optical microscope images of Sample A, Sample B, and Sample C, an analysis image in which the magnitude of the total scattered light intensity is represented by color shading, and an analysis image in which the level of the blue light ratio is represented by color shading. It is. In FIG. 5, the lighter the color, the greater the total scattered light intensity or the higher the blue light ratio. In sample A, a portion having a high total scattered light intensity and a high blue light ratio was present in an island shape. FIG. 6 is an SEM image of Sample A to which glycerin has been added. In the order from FIG. 6A to FIG. 6C, the magnification is changed from low to high. FIG. 7 is an SEM image of Sample B. The magnification in FIG. 7 (a) is lower than the magnification in FIG. 7 (b). 5 and 6, the island-like portion of the sample A having a large total scattered light intensity and a high blue light ratio is composed of isolated particles and microaggregates, and there are no micrometer-class large aggregates. It was confirmed.
 全散乱光強度は、ナノ粒子数が多いほど大きくなる。1回の精密観察でなるべく多くのナノ粒子を計測するためには、試料の全散乱光強度が大きな部分を測定することが有利である。一方、青色光比率は分散性の良さを示しており、試料の青色光比率が高い部分を測定することで、凝集体の影響を軽減できる。図5から図7より、試料Bと比較して試料Aは、孤立粒子の多い部分が広く分布することがわかった。 The total scattered light intensity increases as the number of nanoparticles increases. In order to measure as many nanoparticles as possible by one precise observation, it is advantageous to measure a portion where the total scattered light intensity of the sample is large. On the other hand, the blue light ratio indicates good dispersibility, and the influence of the aggregate can be reduced by measuring the portion of the sample where the blue light ratio is high. From FIG. 5 to FIG. 7, it was found that the portion with many isolated particles was widely distributed in the sample A compared with the sample B.
 図5に示すように、試料Cの左側の領域は、粒子密度が高いものの、青色光比率が低いことから、凝集体が多いことがわかる。一方、試料Cの右側の領域は粒子密度が低い。粒子密度が低いほど凝集しにくいと一般的には予想できるが、図5の試料Cの画像より、必ずしも粒子密度が低ければ粒子が凝集しにくいわけではなく、粒子密度がある程度高く、かつ凝集が少ない(青色光比率が高い)部分があることがわかった。 As shown in FIG. 5, the region on the left side of Sample C has a high particle density, but the blue light ratio is low, indicating that there are many aggregates. On the other hand, the area on the right side of the sample C has a low particle density. In general, it can be expected that the lower the particle density, the less likely it is to agglomerate. However, from the image of sample C in FIG. It was found that there are few parts (high blue light ratio).
 図5に示すように、試料Bでは、全散乱光強度および青色光比率がほぼ均一であるが、青色光比率が0.6を超えている領域がなかった。図7より、試料Bの光学顕微鏡画像で観測される点状の領域は、大凝集体であることが確認された。この結果は、青色光比率と全散乱光強度から予想されるものであり、本発明の青色光比率、または青色光比率および全散乱光強度を指標として、ナノ粒子の分散状態を試料の所定の領域内の所定の部分ごとに評価する方法が有効であることを示している。 As shown in FIG. 5, in Sample B, the total scattered light intensity and the blue light ratio were almost uniform, but there was no region where the blue light ratio exceeded 0.6. From FIG. 7, it was confirmed that the point-like region observed in the optical microscope image of Sample B is a large aggregate. This result is expected from the blue light ratio and the total scattered light intensity. Using the blue light ratio of the present invention or the blue light ratio and the total scattered light intensity as an index, the dispersion state of the nanoparticles is determined as a predetermined value of the sample. This shows that the evaluation method for each predetermined part in the region is effective.
 一方、図5に示すように、試料Cでは、全散乱光強度および青色光比率が場所により大きく異なる。全体的に見ると、全散乱光強度が大きい領域では青色光比率が小さい。全散乱光強度大きい領域は、多数のナノ粒子が凝集している領域であるからだと考えられる。また、全散乱光強度が小さい領域であっても、青色光比率が低い部分もあり、必ずしも粒子密度が低ければ粒子が凝集しにくいわけではないことが判明した。ナノ粒子が不均一に分散された試料では、一般的になるべく凝集体が少ない部分を観察するために、粒子濃度が低い部分を観察部分として選定する傾向があった。しかし、本実施例の結果から、必ずしも試料のナノ粒子の密度が低い部分が観察に適しているわけではなく、本発明により最適な場所を選択することが有効であることがわかった。 On the other hand, as shown in FIG. 5, in the sample C, the total scattered light intensity and the blue light ratio vary greatly depending on the location. As a whole, the blue light ratio is small in the region where the total scattered light intensity is large. The region where the total scattered light intensity is high is considered to be a region where a large number of nanoparticles are aggregated. Further, even in a region where the total scattered light intensity is small, there are portions where the blue light ratio is low, and it has been found that the particles are not necessarily aggregated if the particle density is low. In a sample in which nanoparticles are dispersed non-uniformly, there is a tendency to select a portion having a low particle concentration as an observation portion in order to observe a portion having as few aggregates as possible. However, from the results of this example, it was found that the portion of the sample having a low density of nanoparticles is not necessarily suitable for observation, and that it is effective to select an optimal location according to the present invention.
10 ナノ粒子観察装置
12 ステージ
14 白色LED
16,18 集光レンズ
20 マルチモードファイバー
22 偏光フィルター
24 対物レンズ
26 投影レンズ
28 カラーデジタルカメラ
30 コンピュータ
40 AFM
42 ステージ制御装置
44 AFMヘッド
46 AFMカンチレバー
48 探針
S  試料
P  基板
N  ナノ粒子
10 Nanoparticle observation device 12 Stage 14 White LED
16, 18 Condensing lens 20 Multimode fiber 22 Polarizing filter 24 Objective lens 26 Projection lens 28 Color digital camera 30 Computer 40 AFM
42 Stage Controller 44 AFM Head 46 AFM Cantilever 48 Probe S Sample P Substrate N Nanoparticle

Claims (12)

  1.  分散しているナノ粒子を含む試料の前記ナノ粒子に、三原色を含む光を照射する照射工程と、
     前記ナノ粒子による前記光の散乱光の波長と強度を測定する測定工程と、
     前記測定工程で測定された散乱光の波長と強度から、三原色の光の強度の総和である全散乱光強度と、青色の光の強度である青色光強度と、前記全散乱光強度に対する前記青色光強度の割合である青色光比率とを、前記試料の所定の領域内で算出する算出工程と、
     前記青色光比率を指標として、前記ナノ粒子の分散状態を前記領域内の所定の部分ごとに評価する評価工程と、
     を有するナノ粒子評価方法。
    An irradiation step of irradiating the nanoparticles of the sample containing dispersed nanoparticles with light containing three primary colors;
    A measurement step of measuring the wavelength and intensity of the scattered light of the light by the nanoparticles;
    From the wavelength and intensity of the scattered light measured in the measurement step, the total scattered light intensity that is the sum of the intensity of the three primary colors, the blue light intensity that is the intensity of the blue light, and the blue light relative to the total scattered light intensity A calculation step of calculating a blue light ratio, which is a ratio of light intensity, within a predetermined region of the sample;
    Using the blue light ratio as an index, an evaluation step for evaluating the dispersion state of the nanoparticles for each predetermined portion in the region;
    Nanoparticle evaluation method having
  2.  請求項1において、
     前記評価工程では、さらに前記全散乱光強度を指標として、前記ナノ粒子の分散状態を前記領域内の所定の部分ごとに評価するナノ粒子評価方法。
    In claim 1,
    In the evaluation step, a nanoparticle evaluation method for evaluating the dispersion state of the nanoparticles for each predetermined portion in the region, using the total scattered light intensity as an index.
  3.  請求項1または2において、
     前記試料が、基板と、前記基板上で分散しているナノ粒子とを含み、
     前記照射工程では、基板上面に対して斜め方向に前記光を照射するナノ粒子評価方法。
    In claim 1 or 2,
    The sample includes a substrate and nanoparticles dispersed on the substrate;
    In the irradiation step, the nanoparticle evaluation method of irradiating the light in an oblique direction with respect to the upper surface of the substrate.
  4.  請求項1から3のいずれかにおいて、
     前記評価工程で評価した前記試料の所定の部分ごとの前記ナノ粒子の分散状態に基づいて、前記試料の観察部分を選定し、電子顕微鏡および走査型プローブ顕微鏡の少なくとも一方で前記観察部分を観察する観察工程をさらに有するナノ粒子評価方法。
    In any one of Claim 1 to 3,
    The observation part of the sample is selected based on the dispersion state of the nanoparticles for each predetermined part of the sample evaluated in the evaluation step, and the observation part is observed with at least one of an electron microscope and a scanning probe microscope The nanoparticle evaluation method which further has an observation process.
  5.  請求項1から4のいずれかにおいて、
     前記ナノ粒子の平均粒径が50~100nmであるナノ粒子評価方法。
    In any one of Claim 1-4,
    A method for evaluating nanoparticles, wherein the nanoparticles have an average particle size of 50 to 100 nm.
  6.  請求項1から5のいずれかにおいて、
     前記測定工程では、撮像素子で認識された前記散乱光の波長と強度をデジタルデータとして記録する過程を含むナノ粒子評価方法。
    In any one of Claim 1 to 5,
    In the measurement step, the nanoparticle evaluation method includes a step of recording the wavelength and intensity of the scattered light recognized by the image sensor as digital data.
  7.  分散しているナノ粒子を含む試料を載置するためのステージと、
     前記試料が載置された状態で、前記ステージの上面に対して斜め方向から、前記ナノ粒子に三原色を含む光を照射するように設けられた光源と、
     前記光源から照射された前記光の前記ナノ粒子による散乱光のうち、前記試料の所定の領域内の散乱光の波長と強度をデジタルデータとして記録するデジタル機器と、
     前記デジタル機器が記録したデジタルデータに基づいて、青色の光の強度である青色光強度と、三原色の光の強度の総和である全散乱光強度とを算出するデジタル処理装置と、
     前記ステージの上面と対向するように設けられた探針と、前記ステージを三次元に移動するステージ制御装置とを備える走査型プローブ顕微鏡と、
     を有するナノ粒子観察装置。
    A stage for placing a sample containing dispersed nanoparticles;
    In a state where the sample is placed, a light source provided to irradiate light including three primary colors to the nanoparticles from an oblique direction with respect to the upper surface of the stage;
    Of the light scattered from the nanoparticles of the light emitted from the light source, a digital device that records the wavelength and intensity of the scattered light in a predetermined region of the sample as digital data;
    Based on digital data recorded by the digital device, a digital processing device that calculates a blue light intensity that is an intensity of blue light and a total scattered light intensity that is a sum of the intensity of three primary colors;
    A scanning probe microscope comprising a probe provided to face the upper surface of the stage, and a stage control device for moving the stage in three dimensions;
    Nanoparticle observation apparatus having
  8.  分散しているナノ粒子を含む試料を載置するためのステージと、
     前記試料が載置された状態で、前記ステージの上面に対して斜め方向から、前記ナノ粒子に三原色を含む光を照射するように設けられた光源と、
     前記光源から照射された前記光の前記ナノ粒子による散乱光のうち、前記試料の所定の領域内の散乱光の波長と強度をデジタルデータとして記録するデジタル機器と、
     前記デジタル機器が記録したデジタルデータに基づいて、青色の光の強度である青色光強度と、三原色の光の強度の総和である全散乱光強度とを算出するデジタル処理装置と、
     前記ステージの上面と対向するように設けられた電子銃と、前記ステージを三次元に移動するステージ制御装置とを備える電子顕微鏡と、
     を有するナノ粒子観察装置。
    A stage for placing a sample containing dispersed nanoparticles;
    In a state where the sample is placed, a light source provided to irradiate light including three primary colors to the nanoparticles from an oblique direction with respect to the upper surface of the stage;
    Of the light scattered from the nanoparticles of the light emitted from the light source, a digital device that records the wavelength and intensity of the scattered light in a predetermined region of the sample as digital data;
    Based on digital data recorded by the digital device, a digital processing device that calculates a blue light intensity that is an intensity of blue light and a total scattered light intensity that is a sum of the intensity of three primary colors;
    An electron microscope comprising an electron gun provided to face the upper surface of the stage, and a stage control device for moving the stage in three dimensions;
    Nanoparticle observation apparatus having
  9.  請求項7または8において、
     前記デジタル機器がカラーデジタルカメラであるナノ粒子観察装置。
    In claim 7 or 8,
    A nanoparticle observation apparatus in which the digital device is a color digital camera.
  10.  請求項7から9のいずれかにおいて、
     前記ステージと前記デジタル機器の間に、光学顕微鏡をさらに有するナノ粒子観察装置。
    In any of claims 7 to 9,
    A nanoparticle observation apparatus further comprising an optical microscope between the stage and the digital device.
  11.  請求項7から10のいずれかにおいて、
     前記ステージと前記光源の間に、前記光源が射出した光の偏光を変えられる偏光フィルターをさらに有するナノ粒子観察装置。
    In any of claims 7 to 10,
    The nanoparticle observation apparatus which further has a polarizing filter which can change the polarization | polarized-light of the light which the said light source inject | emitted between the said stage and the said light source.
  12.  請求項7から11のいずれかにおいて、
     前記光源が、前記ナノ粒子に照射する前記光の入射角を変更できるナノ粒子観察装置。
    In any of claims 7 to 11,
    The nanoparticle observation apparatus which can change the incident angle of the said light with which the said light source irradiates the said nanoparticle.
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