JPH06148057A - Method and instrument for measuring fine particle - Google Patents

Abstract

PURPOSE:To provide a fine particle measuring technique by which the distribu tion of particle sizes in an arbitrary sample to be measured can be automatically measured with high accuracy. CONSTITUTION:A sample 6a and sample diluting liquid 2a are supplied to a mixing tank 9 above a gravimeter 10 from a sample tank 6 and sample diluting liquid tank 2. A sample tube 15 connected with a first fine particle meter 11 and a pressurized gas introducing tube 8 are connected to the tank 9 and the sample diluting liquid 2a and a sample-diluted liquid prepared by diluting the sample 6a with the liquid 2a are supplied to the meter 11 by using a pressurized gas. A refractive index meter 12 for liquid and flowmeter 13 are connected to the sample tube 15 on the downstream side of the meter 11 and respectively measure the refractive index and flow rate of each kind of liquid immediately after passing through the meter 11. The measured results of the meter 11 are corrected by using the refractive index measured by the meter 12.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for measuring fine particles,
In particular, the present invention relates to a technology effectively applied to the measuring / analyzing instrument manufacturing industry, the chemical plant manufacturing industry, the semiconductor manufacturing industry, the semiconductor material / chemical manufacturing industry, and the like.

[0002]

2. Description of the Related Art For example, in a semiconductor device manufacturing process, as semiconductor circuits become more highly integrated and miniaturized, ultrafine foreign substances contained in various chemicals used in the process of processing semiconductor wafers also result in a product yield. Therefore, it is essential to develop a highly accurate measurement technique for the fine foreign matter in an arbitrary sample solvent.

[0003]

However, in the existing apparatus for measuring fine particles in liquid, a calibration standard solution in which standard particles such as polystyrene latex having a known particle size are monodispersed in pure water or the like is used. The calibration curve (relation A) between the obtained particle size and the scattered light pulse voltage value is used as it is. The optical refractive index values of the solvent and solute are different from those of the calibration standard solution. Since it is applied to distribution measurement, it cannot be said that the reliability of the measurement results of the particle size and the number of foreign particles in the actual measurement sample is necessarily high. In particular, in applications such as the recent semiconductor process in which the inclusion of extremely fine foreign matter poses a problem, there is a concern that the measurement accuracy will be insufficient with the above-described conventional measurement technique.

Further, in the existing device, when the number of measured fine particles exceeds the upper limit value of the device count at a high concentration, an error message is simply displayed and the particle number distribution by particle size cannot be known.

Therefore, an object of the present invention is to provide a fine particle measuring technique capable of highly accurately and automatically measuring the particle number distribution by particle size in an arbitrary actual measurement sample.

Another object of the present invention is to provide a fine particle measuring technique capable of highly accurately and automatically measuring the particle number distribution by particle size in a measurement actual sample having an arbitrary concentration.

The above and other objects and novel features of the present invention will be apparent from the description of this specification and the accompanying drawings.

[0008]

Among the inventions disclosed in the present application, a brief description will be given to the outline of typical ones.
It is as follows.

That is, according to the present invention, the pulse voltage value of Mie scattered light generated when a calibration standard solution in which standard particles of known particle size are monodispersed in a standard solvent is irradiated with light having a constant wavelength and the standard particle size. Check the first correlation with the diameter (relationship A),
According to the first correlation, the particle size and the number of particles in the actual sample are measured from the pulse voltage value and the pulse number of the scattered light, respectively, in the solution part excluding the particles in the actual sample. The optical refractive index of a certain sample solvent is measured when measuring the fine particles of the actual sample,
The first correlation (relation A) of the second correlation (relation B) between the particle size of fine particles and the scattered light pulse voltage value caused by the difference in refractive index between the standard solvent and the sample solvent when measuring the actual sample.
By correcting the deviation from the above by an automatic calculation process, the particle number distribution for each particle size corrected for the solvent refractive index is obtained.

Further, the present invention provides a method for measuring fine particles according to claim 1, which comprises a plurality of dilution solvents which are almost free of fine particles and which are soluble and transparent to the actual sample to be measured and have different optical refractive index values. The measurement actual sample is diluted by each to measure the fine particles, and when the refractive index of the fine particles in the measurement actual sample and the diluting solvent match, the scattered light pulse intensity of the fine particles is minimized. The refractive index of the fine particles is automatically measured, and when measuring the actual measurement sample, the particle size of the fine particles and the scattered light pulse voltage value generated due to the difference in the refractive index between the solute (foreign matter fine particles) and the standard particles in the actual measurement sample The deviation from the first correlation (relationship A) in the correlation (relationship C) is corrected by an automatic calculation process to obtain the solute refractive index-corrected particle number distribution by particle size.

Further, according to the present invention, in the method for measuring fine particles according to claim 1 or 2, when the refractive index of the solvent or the fine particles of the actual measurement sample is known separately, the refractive index value can be externally determined by an operator or by an arbitrary operator. The first correlation of the fourth correlation (relation D) between the particle size of fine particles and the scattered light pulse voltage value inputted from the storage medium.
By correcting the deviation from the correlation (relation A) by the automatic calculation process, the particle number distribution by particle size corrected for the solvent and solute refractive index is obtained.

Further, the present invention provides a method for measuring fine particles according to claim 1, 2 or 3, wherein the number of measured fine particles in an actual measurement sample exceeds a measurable upper limit value due to high concentration,
Automatically dilutes and remeasures the actual sample.

Further, according to the present invention, a pulse voltage value of scattered light generated when a calibration standard solution obtained by monodispersing standard particles of known particle size in a standard solvent is irradiated with light of a constant wavelength, and the particle size of the standard particles. And a liquid for measuring the particle size and the number of fine particles in the actual measurement sample from the pulse voltage value and the pulse number of the scattered light, respectively, based on this first correlation. In the medium fine particle measuring device, the optical solvent of the sample solvent, which is the solution portion excluding the fine particles in the actual measurement sample different from the calibration standard solution, is arranged on the flow path behind the first fine particle meter for measuring the first correlation. Refractive index measuring means for automatically measuring the refractive index, and measurement based on the optical refractive index of the sample solvent measured by this refractive index measuring means occurs due to the difference in refractive index between the standard solvent and the sample solvent when measuring the actual sample. Particle size and dispersion The deviation from the first correlation (relationship A) of the second correlation (relationship B) with the optical pulse voltage value is corrected by an automatic calculation process to obtain the particle number distribution by particle size corrected for the solvent refractive index. And a first calculating means for obtaining.

Further, according to the present invention, in the fine particle measuring apparatus according to the fifth aspect, a sample tank for storing and supplying the actual measurement sample, a measurement actual sample containing almost no fine particles and a soluble and transparent diluent solvent are provided. A diluting liquid tank to be stored / supplied, a measurement actual sample and a diluent solvent are mixed at a desired ratio and supplied to the first fine particle meter, and a measurement actual solution supplied from this mixing tank to the first fine particle meter. A flow rate measuring means for measuring the flow rate of the sample, a second fine particle meter provided in the diluting solvent supply path from the sample tank to the mixing tank, and a diluting solvent of several kinds having different optical refractive index values. By diluting the actual measurement sample with each and measuring the fine particles with the first fine particle meter, the scattered light pulse intensity of the fine particles is minimized when the foreign particles in the measurement actual sample and the diluting solvent have the same refractive index. , Measuring the refractive index of fine particles in the actual sample automatically The first correlation of the third correlation (relation C) between the particle diameter of the fine particles and the scattered light pulse voltage value, which is generated due to the difference in the refractive index between the solute (foreign particle fine particles) and the standard particles during the measurement of the actual sample to be measured. It is provided with a third calculation means for obtaining a solute refractive index-corrected particle number distribution by particle size by correcting a deviation from the correlation (relation A) by an automatic calculation process.

Further, according to the present invention, in the fine particle measuring apparatus according to the fifth or sixth aspect, when the refractive index of the solvent or the fine particles of the actual measurement sample is known separately, the refractive index value can be externally determined by an operator or arbitrarily. From the first storage medium to the first or second calculating means, and the deviation of the fourth correlation (relationship D) between the particle size of the particles and the scattered light pulse voltage value from the first correlation (relationship A). The particle number distribution for each particle size corrected for the refractive index of the solvent and solute is obtained by correction by the automatic calculation process.

Further, according to the present invention, in the fine particle measuring apparatus according to claim 6 or 7, the mixing tank is provided so that the concentration of the number of measured fine particles in the actual measurement sample does not exceed the measurable upper limit value of the first fine particle meter. It controls the dilution ratio by the dilution solvent in.

[0017]

According to the above-described fine particle measuring technique of the present invention, for example, various optical system parameters of the first fine particle meter such as the flow cell, the incident light source, and the reflected light detecting section, and the fine particle diameter and scattered light by the calibration standard solution. From the Mie scattered light intensity equation using the first correlation (relation A) with the pulse voltage value, the particle diameter of the fine particles and the scattered light pulse voltage value with the optical refractive index of the sample solvent and the solute as external parameters The second to fourth correlations (empirical formulas) unique to the first fine particle meter are obtained.
Then, the measured or key input refractive index values of the actual sample solvent and solute are substituted into this empirical formula to accurately measure the particle size of fine particles such as foreign matter.

For a high-concentration fine particle sample, for example, the dilution / remeasurement value does not exceed the upper limit value of the device count by using the main component solvent of the sample containing almost no fine particles such as foreign substances as the dilution solvent. To set the dilution ratio automatically.

[0019]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The method and apparatus for measuring fine particles, which is an example of the present invention, will be described in detail below with reference to the drawings.

FIG. 1 is a conceptual diagram showing an example of the structure of a particle measuring apparatus which is an embodiment of the present invention.

The mixing tank 9 mounted on the weighing scale 10 is connected to the sample tank 6 via the sample liquid collecting pipe 7 and the diluting liquid collecting pipe 3.
And the sample diluent bath 2 is connected. A pressurized gas introduction pipe 5 to which clean pressurized gas is supplied from the outside is connected to the sample tank 6, and the internal sample 6a is pressure-fed into the sample liquid collecting pipe 7 so as to supply to the mixing tank 9. To do. Similarly,
A pressurized gas introducing pipe 1 is connected to the sample diluting liquid tank 2, and the sample diluting liquid 2 a therein is supplied to the mixing tank 9 through the diluting liquid sampling pipe 3. The diluting liquid collection tube 3 has a second path
A fine particle meter 4 is provided to monitor the presence or absence of fine particles in the sample dilution liquid 2a that passes through the dilution liquid sampling tube 3 and reaches the mixing tank 9.

A sample tube 15 in which a first fine particle meter 11 is provided and a pressurized gas introduction tube 8 are connected to the mixing tank 9, and a clean supply which acts from the outside through the pressurized gas introduction tube 8 is applied. Sample 6 for the first fine particle meter 11 by the pressurized gas
The contents liquid such as a, the sample diluent 2a, and the sample 6a diluted with the sample diluent 2a is supplied.

The first fine particle meter 1 in the sample tube 15
A flow meter 13 is provided on the downstream side of 1 to measure the flow rates of various liquids immediately after passing through the first fine particle meter 11.

The first fine particle meter 11 and the second fine particle meter 4 pass, for example, an actual sample to be measured through a flow cell (not shown) having optical transparency and chemical resistance, and at that time, a laser beam is applied to the sample. It is composed of a laser light scattering type fine particle measuring mechanism that measures the pulse of scattered light emitted from foreign particles by irradiating the surface of the particle with an unillustrated light receiving element as an electric signal.

In this case, a liquid refractometer 12 is provided downstream of the first fine particle meter 11 in the sample tube 15, and the refractive index of various liquids immediately after passing through the first fine particle meter 11 is measured. It is possible to do.

Each part of the pressurized gas introduction tube 1 to the sample tube 15 is
It is controlled collectively under the control of the system control unit 14. Further, the system control unit 14 is based on various information input by the operator via the first fine particle meter 11 and the liquid refractometer 12, the flow meter 13, the weight meter 10 and a keyboard (not shown). Various control operations and calculations as described below are performed.

The operation of the fine particle measuring method and apparatus of this embodiment will be described below.

(1) In case where the standard solution for calibrating in-liquid fine particle meter and the actual sample solvent (solution portion excluding foreign particle) are different in optical refractive index First, the liquid installed behind the first fine particle meter 11 The refractometer 12 measures the optical refractive index value of the sample solvent. On the other hand, a first flow cell, an incident light source, a reflected light detection unit, etc. not shown
From the Mie scattered light intensity formula using the optical system parameters of the fine particle meter 11 and the first correlation (relation A) between the particle size of fine particles by the calibration standard solution and the scattered light pulse voltage value, the sample solvent and the solute are An empirical formula (relation B) (relation C) (relation D) between the particle diameter of the fine particles and the scattered light pulse voltage value unique to the first fine particle meter 11 having the optical refractive index as an external parameter is obtained in advance, The system control unit 14 has a function of automatically calculating the particle size of the fine particles whose refractive index is corrected from the scattered light pulse voltage value. Then, the refractive index value of the sample solvent measured by the liquid refractometer 12 is transmitted to the system control unit 14, and the solvent refractive index corrected (relation B) particle size distribution by particle size is obtained.

(2) When the standard particles and the actual sample solute (foreign matter fine particles) have different optical refractive indices First, the sample 6a is placed in the sample tank 6 and a clean inert gas such as nitrogen containing no foreign matter particles. Is introduced into the sample tank 6 through the pressurized gas introduction pipe 5 to pressurize the sample liquid surface, and the sample 6a is pressure-fed to the mixing tank 9. Weighing scale 10 located below the mixing tank 9
The weight of the sample flowing into the tank was measured, and the sample liquid sampling pipe 7 that had been immersed under the sample liquid surface of the sample tank 6 just before reaching the specified amount was pulled up to the liquid surface, and the sample liquid remaining in the pipe Is expelled into the mixing tank 9 with the inert gas flowing out from the pressurized gas introduction pipe 5.

Further, several kinds of comparative solvents which are substantially free of fine foreign particles and are soluble and transparent to the actual sample 6a and have different optical refractive index values are prepared. Put one of them in the sample diluent bath 2. Similarly, a clean inert gas such as nitrogen containing no foreign matter particles is introduced into the sample diluting liquid tank 2 through the pressurized gas introduction pipe 1 to pressurize the liquid surface of the solvent, and the comparative solvent is sent under pressure to the second particle meter 4. Then, the particle number distribution for each particle size is measured, and after confirming that the solvent does not contain foreign particles, the solvent is poured into the mixing tank 9. Similarly, the weight of the comparative solvent that has flowed into the tank is measured by a weight scale 10 located below the mixing tank 9, and the diluting liquid sampling tube that is immersed under the sample liquid level in the sample diluting liquid tank 2 immediately before reaching the specified amount. 3 is pulled above the liquid surface, and the solvent liquid remaining in the pipe is expelled into the mixing tank 9 by the inert gas flowing out from the pressurized gas introduction pipe 1.

In this way, the actual sample to be measured is mixed and diluted with the comparative solvent at an appropriate ratio, and then a clean inert gas such as nitrogen containing no foreign matter particles is mixed by the pressurized gas introduction pipe 8 into the mixing tank 9.
It is introduced into the inside and pressurizes the mixed sample liquid surface, and the first fine particle meter 11
The mixed sample is fed under pressure to measure the particle number distribution by particle size, and the liquid refractive index 12 measures the optical refractive index value of the mixed sample.

Further, since a series of operations are similarly performed using different kinds of comparison solvents, each time the measurement using one kind of comparison solvent is completed, the sample dilution solution tank 2, the dilution solution collection tube 3, the second The fine particle meter 4, the mixing tank 9, the first fine particle meter 11, the liquid refractometer 12, and the flow meter 13 are washed with an appropriate solvent, and then,
The particle number distribution by particle size in the mixed sample is measured for each of the changed comparative solvents, and the optical refractive index value of the mixed sample is measured by the liquid refractometer 12.

When the refractive index of the foreign matter particles in the actual sample and the refractive index of the mixed sample solvent (the mixed solution portion of the sample solution excluding the foreign matter particles and the comparative solvent) match, the scattered light pulse intensity of the foreign matter particles is Since it becomes the minimum, the particle number distribution by particle size of the mixed sample measured using several types of comparative solvents has the lowest particle size / low particle number distribution. The optical refractive index of the fine particles is approximated, and the particle number distribution for each particle size corrected by the solute refractive index (relation C) by the system controller 14 is obtained as in the case of the solvent refractive index correction (relation B).

(3) When the refractive index of the solvent or foreign particles of the actual sample is known First, the sample 6a is placed in the mixing tank 9. A clean inert gas such as nitrogen containing no foreign matter particles is introduced into the mixing tank 9 through the pressurized gas introduction pipe 8 to pressurize the sample liquid surface, and the sample 6a is pressure-fed to the first particle meter 11 to obtain a particle size. After measuring the different particle number distribution, the sample amount is measured by the flow meter 13 and the liquid is drained. After that, the refractive index values of the solvent and the foreign particles of the actual sample are input to the system control unit 14 from a keyboard (not shown) or the like, and the solvent and solute refractive index-corrected particle number distribution by particle size (relationship D).
Ask for. It should be noted that the refractive index values of the solvent and the foreign particles of the actual sample may be stored in a predetermined storage medium in advance and read by the system control unit 14 as necessary.

(4) When the number of measured fine particles in an actual sample is completely unknown prior to the measurement, or when there is a possibility that the upper limit of measurable by the apparatus may be exceeded at a high concentration. A clean inert gas such as nitrogen that does not contain nitrogen is introduced into the sample tank 6 through the pressurized gas introduction pipe 5 to pressurize the sample liquid surface and pressure-feed it to the mixing tank 9. Further, a clean inert gas such as nitrogen containing no foreign matter particles is introduced into the mixing tank 9 through the pressurized gas introduction pipe 8 to pressurize the sample liquid surface, and the sample is pressure-fed to the first particle meter 11 to measure the particle size. After measuring the different particle number distribution, the sample amount is measured by the flow meter 13 and the liquid is drained.

If the number of fine particles to be measured exceeds the upper limit of device measurement at a high concentration, the flow rate of the sample amount a (ml / min) that has passed through the first fine particle meter 11 immediately before the upper limit is exceeded. And the automatic dilution remeasurement is performed at a minimum magnification determined by the ratio (b / a) between the measured value and the specified sample amount b (ml / min) specific to the first fine particle meter 11.

The procedure is to put the sample 6a in the sample tank 6 and
A clean inert gas such as nitrogen containing no foreign particles is introduced into the sample tank 6 through the pressurized gas introducing pipe 5 to pressurize the sample liquid surface, and the sample 6a is pressure-fed to the mixing tank 9. The weight of the sample that has flowed into the tank is measured with a weight scale 10 located below the mixing tank 9, and the sample liquid sampling pipe 7 that has been immersed under the sample liquid surface of the sample tank 6 immediately before reaching the specified amount is placed on the liquid surface. And the sample liquid remaining in the tube is expelled into the mixing tank 9 with the inert gas flowing out from the pressurized gas introduction tube 5. Further, the main component solvent of this sample is used as a dilution solvent (sample dilution liquid 2a) and the sample dilution liquid tank 2 is used.
Similarly, a clean inert gas such as nitrogen containing no foreign matter particles is introduced into the sample dilution liquid tank 2 through the pressurized gas introduction pipe 1 to pressurize the liquid surface of the solvent, and then compared with the second fine particle meter 4. The solvent is pressure-fed and the particle number distribution by particle size is measured to confirm that the diluting solvent does not contain foreign fine particles, and then the solvent is poured into the mixing tank 9. Similarly, the weight of the comparative solvent that has flowed into the tank is measured by a weight scale 10 located below the mixing tank 9, and the diluting liquid sampling tube that is immersed under the sample liquid level in the sample diluting liquid tank 2 immediately before reaching the specified amount. Three
Is pulled up to the liquid surface, and the solvent liquid remaining in the pipe is expelled into the mixing tank 9 by the inert gas flowing out from the pressurized gas introduction pipe 1.

In this way, the actual sample to be measured is mixed with the diluting solvent at an appropriate ratio, and then a clean inert gas such as nitrogen containing no foreign matter particles is introduced into the mixing tank 9 through the pressurized gas introducing pipe 8. Then, the liquid surface of the mixed sample is pressurized, and the mixed sample is sent under pressure to the first fine particle meter 11 to measure the particle number distribution by particle size. Furthermore,
The optical refractive index value of the mixed sample is measured by the liquid refractometer 12 and transmitted to the system control unit 14 to obtain the solvent refractive index-corrected (relationship B) particle number distribution by particle size. When the refractive index of the foreign particle is known, the refractive index value of the foreign particle is further input to the system control unit 14 to obtain the particle number distribution (relation D) by the solvent and solute refractive index correction.

Although the invention made by the present inventor has been specifically described based on the embodiments, the invention is not limited to the above embodiments, and various modifications can be made without departing from the scope of the invention. Needless to say.

[0040]

The effects obtained by the typical ones of the inventions disclosed in the present application will be briefly described as follows.
It is as follows.

That is, the actual sample to be measured is passed through a flow cell that is optically transparent and has chemical resistance, and at that time, the sample is irradiated with laser light and a pulse of scattered light emitted from the foreign particles is received by the light receiving element. In the laser light scattering type liquid particle measuring device that measures as an electric signal, the particle size of foreign particles is corrected considering the optical refractive index of the actual sample solution and foreign particles, so the particle size measurement accuracy is better than before. Can be improved.

Further, since the high-concentration fine particle sample can be automatically diluted and re-measured, the particle number distribution according to the particle size in the measurement actual sample having an arbitrary concentration can be measured with high accuracy and automatically.

[Brief description of drawings]

FIG. 1 is a conceptual diagram showing an example of the configuration of a particle measuring apparatus that is an embodiment of the present invention.

[Explanation of symbols]

 1 Pressurized Gas Introducing Tube 2 Sample Diluting Liquid Tank 2a Sample Diluting Liquid 3 Diluting Liquid Collecting Tube 4 Second Fine Particle Meter 5 Pressurized Gas Introducing Tube 6 Sample Tank 6a Sample 7 Sample Liquid Collecting Tube 8 Pressurized Gas Introducing Tube 9 Mixing Tank 10 Weight Meter 11 First Fine Particle Meter 12 Liquid Refractive Index Meter 13 Flowmeter 14 System Controller 15 Sample Tube

Claims (8)

[Claims] 1. A pulse voltage value of Mie scattered light generated when a calibration standard solution in which standard particles of known particle size are monodispersed in a standard solvent is irradiated with light having a constant wavelength, and the particle size of the standard particles. This is a fine particle measuring method in which the particle size and the number of particles in the actual measurement sample are measured from the pulse voltage value and the pulse number of the scattered light, respectively, based on the first correlation (relation A). The optical refractive index of the sample solvent, which is the solution portion excluding the fine particles in the measurement actual sample, is measured during the measurement of the fine particles of the measurement actual sample, and the standard solvent and the sample solvent are measured during the measurement of the measurement actual sample. By correcting the deviation of the second correlation (relation B) from the first correlation (relation A) between the particle size of fine particles and the scattered light pulse voltage value caused by the difference in the refractive index of Solvent Refractive Index Corrected Particle Size A method for measuring fine particles, characterized by obtaining a particle number distribution. 2. The measurement actual sample is diluted with each of several kinds of diluent solvents which are substantially free of the fine particles and which are soluble and transparent to the measurement actual sample and have different optical refractive index values, to measure the fine particles. The scattered light pulse intensity of the microparticles is minimized when the refractive index of the microparticles in the measurement actual sample and the dilution solvent match, so that the refractive index of the microparticles in the measurement actual sample is automatically determined. The third correlation (relation C) between the particle size of fine particles and the scattered light pulse voltage value which is caused by the difference in the refractive index between the solute (fine particles) and the standard particles in the actual measurement sample during measurement 3. The particle count distribution according to particle size corrected for solute refractive index is obtained by correcting the deviation from the first correlation (relationship A) of) by an automatic calculation process. Method. 3. When the solvent of the actual measurement sample and the refractive index of the fine particles are known separately, the operator can obtain the refractive index value from the outside.
Alternatively, the first correlation of the fourth correlation (relation D) between the particle diameter of the fine particles and the scattered light pulse voltage value is input from any storage medium.
3. The method for measuring fine particles according to claim 1 or 2, wherein the deviation from the correlation (relation A) is corrected by an automatic calculation process to obtain a particle number distribution by particle size for which the solvent and solute refractive indices are corrected. . 4. The measuring actual sample is automatically diluted and re-measured when the number of measured fine particles in the actual measuring sample exceeds a measurable upper limit value due to a high concentration. The fine particle measuring method according to claim 1, 2, or 3. 5. A pulse voltage value of Mie scattered light generated when a calibration standard solution in which standard particles of known particle size are monodispersed in a standard solvent is irradiated with light having a constant wavelength, and the particle size of the standard particles. The measurement of the particle size and the particle number of the particles in the actual measurement sample based on the first correlation (relation A) from the pulse voltage value of the scattered light and the pulse number A sample solvent, which is a device and is a solution portion excluding the fine particles in the actual measurement sample different from the calibration standard solution, the sample solvent being arranged on the flow path after the first fine particle meter for measuring the first correlation. Refractive index measuring means for automatically measuring the optical refractive index of, and the standard solvent and the sample solvent at the time of measuring the measurement actual sample based on the optical refractive index of the sample solvent measured by this refractive index measuring means Difference in refractive index The deviation of the second correlation (relationship B) between the particle size of fine particles and the scattered light pulse voltage value from the first correlation (relationship A) is corrected by an automatic calculation process to correct the solvent refractive index. And a first calculation means for obtaining a particle number distribution for each particle diameter. 6. A sample tank for storing / supplying the measurement actual sample, a diluent tank for storing / supplying the measurement actual sample containing almost no fine particles and soluble and transparent, and the measurement actual sample. A mixing tank for mixing the sample and the diluent solvent at a desired ratio and supplying the mixture to the first fine particle meter, and a flow rate for measuring the flow rate of the actual measurement sample supplied from the mixing tank to the first fine particle meter. The measuring means, the second fine particle meter provided in the diluting solvent supply path from the sample tank to the mixing tank, and the diluting solvent of each of several kinds having different optical refractive index values are used. The measurement light sample is diluted and fine particles are measured by the first fine particle meter, and the scattered light pulse intensity of the fine particles is minimized when the fine particles in the measurement actual sample and the diluent solvent have the same refractive index. The refractive index of the fine particles in the actual sample The second correlation between the second calculation means for dynamic measurement and the particle size of fine particles and the scattered light pulse voltage value caused by the difference in refractive index between the solute (fine particles) and the standard particles at the time of measuring the actual measurement sample ( And a third calculation means for obtaining the solute refractive index-corrected particle number distribution by particle size by correcting the deviation of the relationship C) from the first correlation (relation A) by automatic calculation processing. The particle measuring device according to claim 5, which is characterized in that. 7. If the refractive index of the solvent or foreign particles of the actual measurement sample is known separately, the refractive index value is externally determined by an operator or from an arbitrary storage medium to the first or second computing means. By inputting and correcting the deviation of the fourth correlation (relationship D) between the particle size of the fine particles and the scattered light pulse voltage value from the first correlation (relationship A) by automatic calculation processing, the solvent and solute refraction The particle number measuring device according to claim 5 or 6, wherein a rate-corrected particle number distribution for each particle size is obtained. 8. The dilution ratio of the dilution solvent in the mixing tank is controlled so that the concentration of the number of measured fine particles in the actual measurement sample does not exceed the measurable upper limit of the first fine particle meter. The fine particle measuring device according to claim 6 or 7.