JP4852439B2 - Raman spectroscopic measurement device and Raman spectroscopic measurement method using the same - Google Patents

Raman spectroscopic measurement device and Raman spectroscopic measurement method using the same Download PDF

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JP4852439B2
JP4852439B2 JP2007022937A JP2007022937A JP4852439B2 JP 4852439 B2 JP4852439 B2 JP 4852439B2 JP 2007022937 A JP2007022937 A JP 2007022937A JP 2007022937 A JP2007022937 A JP 2007022937A JP 4852439 B2 JP4852439 B2 JP 4852439B2
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光弘 友田
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株式会社リコー
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  The present invention relates to a Raman spectroscopic measurement apparatus and a Raman spectroscopic measurement method using the same, and in particular, receives a Rayleigh reflected light from a light-transmitting film sample and generates Raman when the sample is irradiated with light. The present invention relates to a Raman spectroscopic measuring apparatus and a measuring method for detecting scattered light by a confocal optical system.

In recent years, as the speed, size, and colorization of image forming apparatuses are rapidly progressing, the trend of electrophotographic photosensitive member development is toward the addition of high functionality to devices. From the viewpoint of high sensitivity and high durability, There is a need for structural analysis of electrophotographic photoreceptor films at micron size.
Conventional methods for analyzing the depth direction of general materials have conventionally been X-ray microanalysis (EPMA), x-ray photoelectron spectroscopy (XPS), 2 Secondary ion mass spectroscopy (SIMS), Rutherford backscattering (RBS), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, etc. have been used. When analyzing from the surface of a 5 to 40 μm-thick film in an electrophotographic photosensitive member in the depth direction, there are limited methods that can be applied in situations where sample preparation is not required, confocal laser fluorescence, confocal laser Raman spectroscopy. However, due to the wide range of applications for materials, confocal laser Raman spectroscopy, which is a type of scanning probe microscope technology, is particularly important. Act and apparatus have been used.

By the way, in observation with an optical microscope, observation is performed by condensing light, which is obtained by irradiating a sample with light uniformly, with a lens. When performing analysis in the depth direction using a light-transmitting film sample with a thickness using a Raman spectroscopic measurement system combined with an ordinary optical microscope optical system, Raman scattering from non-focused Raman scattering light on the focal plane As a result, light is overlapped, and as a result, the extracted information has a blur that includes information in the vicinity of the focal position and non-focused information at the same time, and this has caused a reduction in the spatial resolution of the Raman spectrometer.
In order to solve such a problem, a confocal laser Raman spectroscopic measurement apparatus using a confocal microscope optical system has been developed and attracts attention as an effective measurement technique for depth measurement.
In a confocal microscopic optical system, when Rayleigh reflected light from a focal point or Raman scattered light (irradiating an object with monochromatic light such as a laser, scattered light having a wavelength different from that of the incident light is observed. Here, it is equal to the incident light. Scattered light of a wavelength is called Rayleigh scattered light (elastically scattered light), while scattered light having a wavelength different from that of incident light (inelastically scattered light) is called Raman scattered light.) Since only light from the sample focal point is detected by transmitting through a lens and a pinhole arranged so as to be conjugate, spatial resolution in the depth direction can be obtained. In this state, the depth profile is obtained by moving the sample position in the depth direction of the film.
The Raman scattered light observed with respect to the incident light is specific to the substance, and the substance can be specified by examining the spectrum of the scattered light. The confocal optical system can measure the profile in the depth direction of the film in units of microns. In recent years, a film structure analysis has been performed using these two functions.
However, in a general dry objective lens, there is a problem that the beam diameter expands due to the influence of the aberration due to the refractive index difference in the film, and the excitation light energy (spatial resolution) decreases in the film with respect to the surface. It was.

A general microscopic Raman apparatus that does not use a confocal optical system has a spatial resolution of several tens of micrometers and can perform nondestructive / noncontact measurement in the atmosphere.
On the other hand, the confocal laser Raman spectroscopy has a high spatial resolution (Min: 0.5 to 1 μm), and is characterized in that it can analyze the chemical structure, crystallinity, orientation, and the like of a minute part.

However, in the case of measurement using this confocal laser Raman spectroscopic measurement device, Rayleigh light having a very strong intensity (10 7 to 10 8 times) compared to Raman scattered light passes through the same optical path to the spectroscope or detector. In order to enter, the scattered light is disturbed to saturate the detector, and in the worst case, the expensive detector is destroyed. For this reason, an optical arrangement in which Rayleigh light, which becomes interference light, is removed by a blocking optical system and only Raman scattering light that is insignificantly weak is put in the spectrometer has been adopted so that each apparatus manufacturer competes.
Specifically, a confocal laser Raman spectroscopic measurement apparatus including a separation optical element that removes Rayleigh scattered light that becomes interference light and a laser light blocking optical element has been proposed.

In the configuration of the conventional Raman spectroscopic measurement apparatus, for example, as shown in FIG. 1, a laser beam emitted from a laser light source 20 is condensed by a condenser lens 21, and a first pin is focused on the focal point of the condenser lens. The hole 22 is positioned, and the diffused light beam transmitted through the pinhole is guided to the second condenser lens 24 via the separation optical element 23 serving as a dichroic mirror, and the light beam is sampled by the second condenser lens. 1 is arranged so as to collect light.
Thereafter, the light beam collected on the sample 1 is reflected from the sample 1 including Raman scattered light, returns to the dichroic mirror 23 through the second condensing lens 24 while being converged. The light that has returned to the dichroic mirror 23 is guided only to the Raman scattering light to the detection unit 26 side due to the characteristics of the dichroic mirror.
Further, the reflected light is once condensed before passing through the dichroic mirror 23 and being guided to the detection unit 26, and the second pinhole 25 is installed at the condensing position.
The first pinhole and the second pinhole are in conjugate positions with respect to the dichroic mirror (positions with the dichroic mirror as the axis of symmetry).

In the following Non-Patent Document 1, these methods are proposed.
At this time, since Rayleigh light is removed by the dichroic mirror, the concept of detecting and using Rayleigh light having interface information in the light-transmitting film sample to be used as a sample is a conventional technique. There was no.
The technical idea of a normal apparatus is that it effectively removes Rayleigh light, which is a disturbing light in Raman measurement, by providing a separation optical element and an excitation light blocking optical system (notch filter or edge filter) described later. It can be said that it was to measure only accurate Raman scattered light.

In other words, the idea of actively obtaining Rayleigh light information, which is reflected light from an “air-film” interface or “film-substrate (or lower layer)” interface, which is an interface of a light-transmitting film sample, is Never before.
With a confocal laser optical microscope that has a topography function for surface shape measurement and surface observation without acquiring Raman scattered light, it is possible to detect only laser reflected light (Rayleigh light) and extract interface information from its intensity profile. However, as described above, in the case of Raman spectroscopic measurement, since Rayleigh reflected light is removed and weak Raman scattered light is received, it is not necessary to obtain reflected light information from the interface.

For example, in Patent Document 1 below, only one excitation light blocking optical element is used.
The notch filter used in the following Patent Document 1 has a transmittance of almost zero in the band near the excitation laser beam wavelength, and therefore almost no Rayleigh light transmitted through the notch filter is observed. It is impossible to extract interface information (see Patent Document 1).
Also, in Patent Document 2 below, an apparatus configuration in which only a notch filter that blocks Rayleigh light is disposed on the optical path in the front stage of the spectroscope so that the Rayleigh light is removed in advance before the Raman scattered light is dispersed. Has been proposed (see Patent Document 2).

In addition, a method has been proposed in which a notch filter for removing Rayleigh scattered light is disposed on the front surface of an optical lens that collects Raman scattered light (see, for example, Patent Document 3 below).
Even in Patent Document 2, since Rayleigh light is effectively removed by the notch filter, the Rayleigh light is not detected by the detector through the spectroscope.
Further, in Patent Document 3 below, it is proposed that a notch filter for selectively blocking two types of laser light is provided at the front and rear, but as in the above document, Rayleigh light is effectively removed by the notch filter. Therefore, there is no disclosure of the idea of detecting and using Rayleigh light that becomes interface reflection information.

As a method of extracting interface information with existing equipment, in order to give interface information to the film, either the film surface or the substrate (or lower layer) interface is visually focused, and this focus is used as the base point. Another method is to scan the focal position of the confocal optical system toward another interface. In this technique, the focal position is lowered depending on the difference in refractive index in the film, unlike in the atmosphere. Since it extends, it is difficult to determine two pieces of accurate interface information from information in the depth direction of the movement amount acquired by moving the Z stage. In particular, when the film thickness is as thin as 5 μm or less, it is almost impossible to obtain accurate interface information by the above-described method due to the influence of aberration.
In this way, when it is desired to obtain the surface information of the electrophotographic photosensitive member film, even if the depth profile of the Raman spectrum can be measured by the confocal laser Raman spectrometer, there is no information on the interface of the film. It was impossible to specify whether the information was Raman scattered light from the interface, and the original purpose could not be achieved.

  In addition, a measuring apparatus having a function of switching a measurement mode between a Rayleigh light reflection / reception mode and a Raman spectroscopic mode at the time of confocal Raman measurement is known. In this case, in the Rayleigh reflection / reception mode, search for the peak of the reflection intensity, focus on one interface, check the position where the spectrum is measured, and follow the desired keyband of the Raman spectrum to measure the profile. I went.

  In addition, the “Nanofinder 30 optical unit” of Non-Patent Document 2 below can detect Raman scattered light by detecting the reflected light reflected by the edge filter with a detector of another system via a half mirror or a beam splitter. At the same time, an apparatus that can measure Rayleigh light and can compare film interface reflection information with a Raman spectrum profile is also known. However, basically, two detection systems are required, and the configuration of the measuring apparatus becomes large, leading to a problem of an increase in cost.

JP-A-6-3203 JP-A-8-327550 JP 2004-341204 A Ikehara, Nishi, "Utilization of confocal laser scanning microscope", Functional Materials, Vol.22, No.10, p20-25 (2002) http://www.tokyoinst.co.jp/products/nano/nano01.html

  Conventionally known technology removes Rayleigh light, which is stronger than Raman scattered light and becomes interference light, so Rayleigh reflected light including film interface information cannot be acquired, and analysis of light transmissive film samples There is a problem that it is difficult to extract the interface information essential for the measurement and to reflect it in the Raman measurement result.

  The present invention has been made in consideration of the above-described circumstances. In order to provide interface information necessary for depth direction analysis of a light-transmitting film sample, weak Raman scattered light is measured by a detector. On the other hand, an object of the present invention is to provide a measuring apparatus and a measuring method capable of detecting Rayleigh light including interface reflection information by the same detection optical system. In other words, the present invention specifies the surface of the Raman scattered light by obtaining the profile of the position direction of the surface analysis by Raman scattering and adding the surface analysis information by Rayleigh scattering in conjunction with this. It is an object of the present invention to provide an enabled apparatus and method.

The Raman spectroscopic measurement apparatus and the Raman spectroscopic measurement method according to the present invention for solving the above problems are specifically provided with the configurations described in the following (1) to (20).
(1): a laser light source, a microscopic optical system having an objective lens and a separation optical element that irradiates a sample with laser light and receives scattered light from the sample, a spectroscopic unit that splits the scattered light, and the spectroscopic device A light detection means for detecting the intensity of the scattered light, and a first laser light blocking optical element fixed on the front surface of the light path of the spectroscopic means on which the scattered light is incident. A second laser beam blocking optical element, wherein the transmittance of the first laser beam blocking optical element with respect to the laser beam wavelength is in the range of 10 −4 to 10 −5 , and the second laser beam blocking optical element and the transmittance with respect to laser light wavelength of the optical element 10 -6 or less, a Raman spectrometer, characterized in that it comprises a confocal microscope optical system having a pinhole in the focal plane conjugate relationship.
(2) The Raman spectroscopic measurement apparatus according to (1), wherein the first laser light blocking optical element is a notch filter.
(3) The Raman spectroscopic measurement apparatus according to (1), wherein the first laser light blocking optical element is an edge filter.
(4) The Raman spectroscopic measurement apparatus according to (1), wherein the second laser light blocking optical element is an edge filter.
(5) The Raman spectroscopic measurement apparatus according to (1), wherein the separation optical element is a dichroic mirror.
(6): The Raman spectroscopic measurement apparatus according to (1) above, wherein the NA of the dry objective lens used in the Raman spectroscopic measurement apparatus is 0.8 or more.
(7): The Raman spectroscopic measurement apparatus according to (1), wherein the objective lens of the Raman spectroscopic measurement apparatus is a plan apochromat lens.
(8) The Raman spectroscopic measurement apparatus according to (6), wherein the objective lens is provided with a correction ring.
(9) The Raman spectroscopic measurement apparatus according to (1), wherein the objective lens of the Raman spectroscopic measurement apparatus is a combination of an oil immersion lens having an NA of 1.2 or more and emulsion oil. .
(10): The oil immersion lens of the Raman spectroscopic measurement device is characterized by using emulsion oil having a refractive index value of −0.2 to −0.1 from the refractive index of the target film to be measured. The Raman spectroscopic measurement apparatus according to (9) above.
(11) The Raman spectroscopic measurement apparatus according to (10), wherein the emulsion oil has a refractive index of 1.5 to 1.6.
(12) The Raman spectroscopic measurement apparatus according to any one of (1) to (11), wherein a laser wavelength of the Raman spectroscopic measurement apparatus is not less than 540 nm and not more than 900 nm.

(13): a laser light source, a polarizer for adjusting the polarization direction of the laser, a microscopic optical system having a separation optical element and an objective lens that irradiates a sample with laser light and receives scattered light from the sample, and the scattering In a Raman spectroscopic measurement apparatus comprising: an analyzer and a depolarizing plate for selecting a polarization characteristic of light; a spectroscopic unit that splits the scattered light; and a photodetection unit that detects the intensity of the scattered light. A first laser light blocking optical element fixed on the front surface of the optical path of the spectroscopic means on which the scattered light is incident, and a replaceable second laser light blocking optical element, and the first laser light blocking optical element The transmittance of the device with respect to the laser beam wavelength is 10 -Four -10 -Five And the transmittance of the second laser light blocking optical element to the laser light wavelength is 10 -6 A Raman spectroscopic measurement apparatus including a confocal microscope optical system including a pinhole that is conjugated with a focal plane as follows.
(14) The Raman spectroscopic measurement apparatus according to (13), wherein the polarizer of the Raman spectroscopic measurement apparatus is a total reflection polarizer.
(15) The Raman spectroscopic measurement apparatus according to (13), wherein the analyzer of the Raman spectroscopic measurement apparatus is an absorption polarizer.
(16) The Raman spectroscopic measurement apparatus according to (13), wherein the depolarizer of the Raman spectroscopic measurement apparatus is a crystal depolarization plate.

(17): Using the Raman spectroscopic measurement device according to any one of (1) to (12) above, the reflected light at the film interface is received by receiving the leaky light of the Rayleigh light in the first laser light blocking optical element. It is a Raman spectroscopic measurement method characterized by detecting the intensity and acquiring interface information of the film interface in association with a spectral data profile for each depth position by the Raman spectroscopy.
(18): Using the Raman spectroscopic measurement apparatus according to any one of (13) to (16) above, the reflected light at the film interface is received by receiving the leaky light of the Rayleigh light in the first laser light blocking optical element. This is a Raman spectroscopic measurement method characterized by detecting the intensity and acquiring interface information of the film interface in association with the polarized Raman intensity data profile for each position by the Raman spectroscopy.
(19): In the Raman spectroscopic measurement method described in (17) or (18) above, the object to be measured is an electrophotographic photoreceptor film, and the measurement range of the film thickness to be measured is selected to be 3 to 40 μm. The Raman spectroscopic measurement method.
(20): In the Raman spectroscopic measurement method described in (19) above, the extinction coefficient: κ of the film to be measured is κ = λ / 0.016π (λ: excitation light wavelength cm) or less. This is a characteristic Raman spectroscopic measurement method.

According to the present invention, a laser light source, a microscopic optical system having an objective lens and a separation optical element that irradiates a sample with laser light and receives scattered light from the sample, and a spectroscopic unit that splits the scattered light, A light detecting means for detecting the intensity of the scattered scattered light, and a first laser light blocking optical element fixed to the front of the optical path of the spectroscopic means on which the scattered light is incident, A replaceable second laser light blocking optical element, wherein the transmittance of the first laser light blocking optical element with respect to the laser light wavelength is in the range of 10 −4 to 10 −5 , and the second laser transmittance to laser light wavelength of the light blocking optical element is 10 -6 or less, the Raman spectrometer, characterized in that it comprises a confocal microscope optical system having a pinhole in the focal plane conjugate relationship, the light Transparent In the analysis of the film structure of an object with a conductive film, it is possible to detect weak leaky light leakage, and to receive both Rayleigh light and Raman scattered light with a single detection system, providing film interface information It is possible to provide a measuring apparatus and a measuring method capable of analyzing a film structure at a submicron size.

Hereinafter, a Raman spectroscopic measurement apparatus and a Raman spectroscopic measurement method according to the present invention will be described in detail with reference to the drawings.
Typical examples of the structure of the light-transmitting film of the photoconductor that is the subject in the present invention are listed below.
FIG. 2 is a diagram showing a layer structure of a photosensitive drum in which an intermediate layer 3 is formed on an aluminum drum 2 and a charge generation layer 4 and a charge transport layer 5 are sequentially formed thereon. Layer 5 forms a photosensitive layer.
In FIG. 2, the intermediate layer 3 has a function as a binder for adhering and fixing the photosensitive layer to a conductive substrate, and contains “fine pigment particles” in order to suppress adverse effects such as charging unevenness.
In FIG. 2, the charge generation layer 4 is a layer that generates “positive and negative charge pairs” by irradiation with light of a specific wavelength, and the charge transport layer 5 is a layer of positive and negative charges generated in the charge generation layer 4. Among these, it is a layer having a function of transporting charges of a predetermined polarity to the surface of the photosensitive layer.
The thicknesses of the intermediate layer 3, the charge generation layer 4, and the charge transport layer 5 are preferably 2 to 6 μm, 1 μm or less, and about 15 to 35 μm, respectively. Therefore, the preferable thickness as the photosensitive layer is about 15 to 36 μm. Become.
The layer thickness of the intermediate layer 3 is generally in the range of 2 to 6 μm as described above. However, in order to achieve a satisfactory function as a binder and a light shielding effect on the conductive substrate, The thickness of the layer 3 is preferably 3 μm or more.
Among these, there is a need to use the apparatus or method of the present embodiment for structural analysis for analyzing the component gradient in the charge transport layer 5 that becomes a light transmissive film, for example.
As Rayleigh light, it is possible to receive reflected light from the surface of the charge transport layer 5 and the surface (interface) of the intermediate layer 3.

The confocal laser Raman spectroscopic measurement apparatus irradiates a single point on the light-transmitting film sample 1 and detects only scattered light from that point. Basically, the focal point of the laser light is made coincident with the focal point of the objective lens 34, and a pinhole 35 is placed at the rear focal point of the objective lens 34 so that the Raman scattered light other than the focal point is efficiently cut.
In the case of the reflection type, excitation and detection are performed with the same objective lens.
Since the Raman scattered light from a depth other than the focal point is not focused at the pinhole position, the interference light is efficiently cut (as shown in FIG. 1, the broken line portion indicating the path of the reflected light from the non-focal point Most of the reflected light is shielded by pinholes).
Since the light beam is focused twice in the illumination system and the detection system, the detection light is a convolution integral of the excitation light intensity distribution and the Raman scattered light intensity distribution, and the spatial resolution in the optical axis (depth) direction and S Both / N ratios increase.
However, in the film, the beam diameter expands due to the effects of chromatic aberration and spherical aberration due to the difference in refractive index. Therefore, it is necessary to suppress the expansion using a plan apochromat lens, oil immersion lens, emulsion oil, or correction ring. It becomes.
Plan apochromat lenses are lenses that have been corrected for aberrations by combining special glasses with low refractive index, high dispersion, high refractive index, low dispersion, etc., and chromatic aberration is practically corrected, and the flatness of the image plane is the highest level. It is a lens.
The correction ring is a ring-shaped hardware attached to the objective lens. By rotating it, a part of the lens group moves in the direction of the optical axis, and this aberration is caused by an error in the refractive index of the film. It works to counteract. Since the oil immersion lens is designed assuming a homogeneous immersion system, there is usually no correction ring.
The difference between a lens with a correction ring and a normal lens is obvious, especially when the NA is increased, the spatial resolution decreases significantly without correction, while the correction ring maintains a high spatial resolution. The difference becomes more pronounced.
An oil immersion lens is a device in which oil having a refractive index of the order of glass is generally filled between a lens and a film to eliminate the influence of air and lens refraction. In a dry lens, the medium through which light passes from the lens to air and further to the target film changes and refraction occurs. If the emulsion oil used in combination with the oil immersion lens has a refractive index of 1.5 to 1.6 which is close to that of the lens or film, the influence of light refraction can be eliminated. This is an effective means for increasing the spatial resolution in the film when an objective lens having a large NA is used.
In the case of using a confocal microscope optical system, the NA greatly contributes to the spatial resolution at the time of measurement, so that the film structure analysis at a submicron size becomes possible by setting the NA to 1.2 or more. . Moreover, since the influence of aberration in the film can be reduced by using emulsion oil, the problem that the excitation light energy is reduced in the film relative to the film surface can be solved.
Regarding the refractive index of the emulsion oil described above, the refractive index can be obtained by a spectroscopic ellipsometer.
As a result, a clear Raman spectrum is obtained in the depth direction (thickness direction of the film sample) for each step by moving the stage in the Z direction, and a three-dimensional analysis is possible.
The confocal microscope optical system can achieve excellent spatial resolution in the depth direction by including a pinhole conjugate with the focal plane on the object.
In general, as the measurement target film becomes thicker, the aberration increases and the spatial resolution decreases accordingly.Therefore, even when an oil immersion lens or emulsion oil is used, for example, in the case of an electrophotographic photoreceptor, the range of film thickness that can be measured is 3 to 40 μm. If the film is thinner than 3 μm, the spatial resolution is insufficient and the Raman signal overlaps, making accurate measurement impossible. Above 40 μm, the spread of the beam spot diameter due to aberration increases, the spatial resolution decreases, and the intensity of the incident laser beam Will drop significantly.

In such a Raman spectroscopic measurement apparatus, the Raman scattered light is saturated by the detector (spectrometer) by setting the transmittance of the laser light to a range of 10 −4 to 10 −5 by the first laser light blocking optical element. I will not let you. That is, as shown in FIG. 3, it becomes possible to receive Rayleigh scattered light with sufficient sensitivity, and the interface information of the film can be extracted. The replaceable second laser light blocking optical element has a laser light transmittance of 10 −6 or less, so that it is possible to completely remove Rayleigh light that becomes interference light when measuring Raman scattered light. Thus, it is possible to analyze the film structure by highly sensitive Raman spectroscopy.
The transmittance of the laser light blocking optical element can be determined by, for example, a spectral reflectance measuring device.

  The Raman spectroscopic measurement apparatus of this embodiment can measure Raman scattered light and Rayleigh light with the same detection optical system.

The laser beam used for excitation in confocal Raman spectroscopy may be selected by selecting a wavelength at which a molecule to be detected has no fluorescence and having Raman activity, and is generally dimmed using a combination of several ND filters. .
Using the laser beam intensity need only be 1 to 100 mW / cm 2 degrees at the exit port, thereafter, the intensity of a light transmissive film sample of the sample, several nW / μm 2 ~ number .mu.W / [mu] m 2 range of about Adjust so that
In general, the higher the laser light intensity, the stronger the Raman scattered light intensity that is detected and the S / N ratio is improved, but it is also necessary to consider sample destruction, fading, response to strong light, and the like. The determination of the laser light intensity condition is one of the most important items because the light-transmitting film sample has different absorption intensity and light resistance.
If the wavelength is short, the Raman scattering intensity increases in inverse proportion to the fourth power of the wavelength.
The laser wavelength is preferably 540 nm or more in consideration of light damage of the charge transport layer 5 serving as a target film and generation of fluorescence in the film which is not preferable for Raman measurement, and when considering the Raman scattering intensity as described above, the wavelength is A shorter value is preferable, and as a result of examination, it was confirmed that suitable measurement is possible when the thickness is 900 nm or less.

A sample stage is attached to the microscope portion of the Raman spectroscopic measurement apparatus, and the incident light and the detection light (Raman scattered light) are moved by the objective lens while moving the stage on which the light-transmitting film sample is placed in the Z-axis direction. The spatial resolution is created by condensing the light. A piezo element or a stepping motor moving mechanism is installed on the sample stage, and a light transmissive film sample is scanned in the Z direction (thickness direction).
The confocal laser microscope can scan the light transmissive film sample in the optical axis direction by moving the stage in the Z direction of the microscope. As described above, the spatial resolution largely depends on the NA of the objective lens. In order to achieve a high spatial resolution, a method using an oil immersion lens instead of a dry objective lens can be considered.
In general, if the dry objective lens is not NA (numerical aperture) 0.8 or more, the spatial resolution at the time of depth direction analysis: 0.5-2 μm cannot be secured, especially in the case of a thin film of 5 μm or less. Clear film structure analysis becomes impossible.
NA is an important value that determines the performance of the objective lens, and is a value related to the depth of focus (spatial resolution) and brightness. It is also called NA (Numerical Aperture) and is represented by the following equation.
NA = n · sin θ (where n is the refractive index of the medium between the film and the objective lens, and θ is the angle formed by the optical axis and the light beam entering the outermost side of the objective lens). Spatial resolution is improved.
In order to achieve both a high optical system throughput and a small focused beam spot, generally, the diameter of the laser beam applied to the lens is set equal to the incident diameter of the microscope objective lens.

FIG. 4A shows an example when it is desired to obtain film interface information.
As shown in the figure, the scattered light generated from the light-transmitting film sample 1 as a sample is removed from the laser with the edge filter 38 (see FIG. 4B) serving as the second laser light blocking element removed. A separation optical element 33 that separates light having the same wavelength as the light traveling from the light source 30 to the sample (Rayleigh light) and Raman scattered light, and a notch filter 37 that serves as a first laser light blocking optical element, is transmitted through the separation optical element. The change in the light amount of the Rayleigh light leaking from the first laser light blocking optical element is confirmed, and the position of the film interface in the optical axis direction is specified from the position where the light amount reaches a peak.

At this time, in order to obtain Rayleigh light as interface reflection from the film interface, the film and medium (for example, air when using a dry objective lens, emulsion oil when using an oil immersion lens) are used. The difference in refractive index is important. In particular, in order to secure Rayleigh reflected light on the film surface, the following formula: reflectance R = ((N−N 1 ) 2 + κ 2 ) / (N + N 1 ) 2 + κ 2 )・ (1)
N: Refractive index of the film to be measured
N 1 : refractive index of the medium
From the extinction coefficient of the film to be measured, it has been found that the reflectance at the interface: R needs to be 0.1% or more. In general, if the difference in refractive index increases, it becomes easier to ensure interface reflection. In that case, the effect of aberration due to the difference in refractive index between the lens, medium, and film induces a decrease in spatial resolution and energy density. Become. For this reason, it is preferable to use an emulsion oil having a refractive index difference of −0.2 to −0.1, which is determined from the refractive index of the target film, for measurement.

In the confocal optical system, the laser light is condensed in a narrow region by the objective lens and irradiated with the light-transmitting film sample, so that the excitation light has a high intensity that is not comparable to normal spectroscopic measurement.
For this reason, the Rayleigh light component leaking from the notch filter 37 serving as the first laser light blocking optical element has an intensity comparable to the Raman scattered light.
This light is incident on a spectroscope, which is a spectroscopic means for dispersing Raman scattered light, and a light intensity profile having the same wavelength as the laser excitation light is measured by a detector 36, which is a photodetection means, and interface information on the film is extracted.

In FIG. 4A, a laser beam emitted from a laser light source 30 is condensed by a condensing lens 31, a first pinhole 32 is positioned on a focal point by the condensing lens 31, and this pinhole is transmitted. The diffused luminous flux is guided to the second condenser lens 34 via the separation optical element 33 that becomes a dichroic mirror, and the luminous flux is condensed on the light-transmitting film sample 1 by the second condenser lens 34. It was configured to make it.
Thereafter, the light beam collected on the light transmissive film sample 1 is reflected from the light transmissive film sample 1 as light containing Raman scattered light, and is focused through the second light collecting lens 34. Return to the dichroic mirror 33. In the light returning to the dichroic mirror 33, only the Raman scattered light travels toward the detection unit 36 having the spectroscopic means and the light detection means due to the characteristics of the dichroic mirror.
Further, the reflected light is once condensed before being guided to the detection unit 36 through the dichroic mirror 33, and after passing through the notch filter 37 serving as the first laser light blocking optical element, the reflected light is disposed at the condensing position. 2 is guided through the second pinhole 35 to the detection unit 36.
FIG. 3 is a diagram showing the result of acquiring the interface information of the film as the object from the leaked light of Rayleigh light using such an apparatus of the present invention.
Thereafter, when measuring the Raman spectrum in the Z direction, the second laser light blocking optical that selectively transmits only light in the wavelength band that matches the Raman scattered light to be detected before the spectroscope serving as the spectroscopic means. The element 38 is rearranged. For example, as shown in FIG. 4B, a notch filter 37 serving as a first laser light blocking optical element for blocking Rayleigh light and an edge filter 38 serving as a second laser light blocking optical element are provided. When the Raman scattered light is separated and detected, the Rayleigh light is completely removed from the optical path.
In the configuration shown in FIG. 4B, the stage is scanned in the Z direction under the same conditions as when the light leaked from the preceding stage of Rayleigh light is received, and data in the Z direction of the Raman spectrum is acquired.
The notch filter 37, which is a first laser light blocking optical element used for removing Rayleigh light, is a filter using a dielectric multilayer film. FIG. 5 shows the optical characteristics of this filter. As illustrated in FIG. 5, this filter does not transmit only a specific wavelength. By laminating a dielectric multilayer film and optimizing the film thickness, it is possible to remove light in a band of about 20 nm around the design wavelength.
As the notch filter 37, a holographic notch filter formed by recording an interference pattern formed by two mutually coherent laser beams can be used.

However, as shown in FIG. 5B, these notch filters 37 cannot cut Rayleigh light by 100%. However, by using the notch filter, it is possible to prevent very strong Rayleigh scattered light in the vicinity of the wavelength of the excitation laser beam that saturates the detector from entering the detector.
Also, an edge filter described later can be used as the first laser light blocking optical element 37.

The light separated by the dichroic mirror 33 that is the separation optical element described above also includes a lot of Rayleigh light.
In the Raman spectroscopic microscope, the excitation light component (Rayleigh light) irradiated to the light-transmitting film sample and the Raman scattered light generated from the light-transmitting film sample are separated using a dichroic mirror that can split the wavelength. Is done.
Ideally, the dichroic mirror used for separating the reflected light (Rayleigh light) and Raman scattered light of the pump laser light has a transmittance characteristic that changes binaryly at a specific wavelength. However, even if the actual transmittance characteristic changes relatively steeply, the transmittance does not become 0 or 1.
For this reason, the light separated by the dichroic mirror includes not only Raman scattered light but also Rayleigh light.
Therefore, the optical element 37 of the first laser light blocking optical element is required not only to transmit the light to be detected but also to have a function of blocking undesired (excitation) light.

The almost complete removal of Rayleigh light by the second laser light blocking optical element can be performed relatively easily if the measurement bands of the excitation laser light and the Raman scattered light are relatively far apart. This can be done by using an element in which an absorbent containing a diffusing agent is diffused on a glass substrate, or by providing an edge filter formed by coating an interference film on the glass substrate.
The characteristics of the edge filter are, for example, as shown in FIG. 6, and in the example of this figure in which the laser beam is 488 nm, the wavelength shorter than 490 nm can be completely removed. For example, in the case of using a dielectric multilayer film, if the optimum design is performed, the light of the shorter wavelength side is removed almost 100% at intervals of about 30 nm before and after the wavelength separation design position, and conversely the Raman Light on the long wavelength side including scattered light can be transmitted. According to the present embodiment, the leaky Rayleigh light transmitted through the dichroic mirror 33, the notch filter or the edge filter 37 is separated from the Raman scattered light by inserting the edge filter 38 into the optical path after the notch filter or the edge filter 37. And can be removed.

  A spectroscope serving as a spectroscopic means splits Raman scattered light by a diffraction grating. When there is a point (area) conjugate with the focal plane on the optical path immediately before entering the spectroscope, two perpendicular slits (cross slits) are placed in the XY plane of that portion, so that a set of slits is formed. It is possible to play the role of a confocal pinhole (second pinhole 35) in the confocal optical system, thereby generating a spatial resolution in the Z-axis direction. The cross slit also contributes to the wavelength resolution when acquiring the Raman spectrum.

  As described above, the confocal laser Raman spectroscopic microscope has a confocal microscope optical system and includes a pinhole conjugate with the focal plane in front of the spectroscope. In a confocal microscope, Raman scattered light from other than the focal point is blocked by a pinhole, so unnecessary light from inside the film other than the focal point and Raman scattered light from inside the light-transmitting film sample are almost completely removed. Is possible.

As shown in FIG. 4A, the laser beam that has passed through the first pinhole 32 is guided to the light-transmitting film sample 1 and guided to the optical path of the objective lens 34 by the dichroic mirror 33 that is a separation optical element. It is burned. Thereafter, the Raman scattered light from the light-transmitting film sample 1 is guided through the dichroic mirror 33 to the detection unit 36 including the spectroscopic means. A second pinhole 35 is also placed in front of the detection unit 36, and each of the two pinholes is at a confocal position having a focal point.
The light transmitted through the second pinhole 35 is incident on a spectroscope configured in the detector and dispersed, and then a multi-channel detector (for example, CCD: Charge Coupled Device) or a single-channel detector (for example, APD). : Detected by Avalanche Photodiode).

As described above, the dichroic mirror 33 used as the separation optical element is a mirror that separates light of two or more wavelength ranges by the dielectric multilayer film, and transmits the wavelength range of the laser light from the laser light source to transmit light. In contrast to the case where the reflected light of the Raman scattered light from the film sample is transmitted, conversely, the laser light source that becomes the Raman scattered light is transmitted through a longer wavelength region and reflects the wavelength light of the laser light source. It also has characteristics.
FIG. 7 is an example of a characteristic diagram of a dichroic mirror having a characteristic of reflecting a wavelength region of a laser light source when light having a wavelength of 488 nm is used as excitation laser light.

In FIG. 4, the light is condensed by the objective lens 34 and irradiated to one point of the light-transmitting film sample 1, and the Raman scattered light is taken into the optical path by the same objective lens 34. In the embodiment, an oil immersion lens is used as the objective lens, and emulsion oil having a refractive index of 1.52 is further used. The refractive index of the emulsion oil can be measured by applying the ultrathin film on the Si-wafer with a spin coater and then measuring the refractive index of the emulsion oil with a spectroscopic ellipsometer.
In this state, the stage on which the light-transmitting film sample 1 is placed is moved in the Z-axis direction by a piezo drive or a stepping motor moving mechanism as necessary.
When receiving Rayleigh light leakage light, the laser has a transmittance of 10 −4 to 10 −5 serving as the first laser light blocking optical element before entering the detection unit 36 as shown in FIG. Only a notch filter or an edge filter 37 may be used. When a Raman spectrum is acquired, a transmittance of 10 −6 that becomes a second laser light blocking optical element is obtained as shown in FIG. 4B. Further, an edge filter 38 having the above is disposed to completely cut Rayleigh light.

Also, when measuring the polarization Raman intensity data profile for each position in the Z direction in association with the film interface information, gas lasers etc. are polarized for the time being, but the direction of the axis is spatially fixed with more stringent polarization. In order to extract only the components along, for example, as shown in FIGS. 11A and 11B, a polarizer 39 is set. Among the polarizers, when a Glan-Thompson prism, which is a total reflection type polarizer, is used, it has very high polarization characteristics, and high-purity linearly polarized light can be obtained as compared with a polarizing filter.
Thereafter, the laser beam is condensed by the objective lens 34 and irradiated to the sample 1 with a diameter of about 0.1 mm. When examining the polarization component of the Raman scattered light, the analyzer 40 is installed after the separation optical element 33. When a polaroid plate that is an absorption polarizer is used among the analyzers, the incident power is limited, but it is suitable for weak Raman scattered light, and is advantageous in that it is small, light, inexpensive, and easy to install in a space. Have.
In the latter spectroscopic means, the reflectance differs depending on whether it is parallel or perpendicular to the direction of the groove of the diffraction grating, so the light transmission characteristics of the spectroscope differ, and the polarization characteristics of scattered light remain polarized. In addition, since the transmission characteristics of the spectroscope are superimposed on the Raman intensity, it is important to break the polarization through the depolarization plate 41 once the polarization component is selected and unnecessary polarization components are cut. Become. As the depolarizing plate 41, it is preferable to use a quartz crystal depolarizing plate.
Other measurement procedures are the same steps as the Z-direction Raman spectrum measurement method described above.

For example, at the time of Raman spectrum measurement, as shown in FIG. 4B, the excitation light emitted from the laser light source is reflected by the dichroic mirror 33, and the reflected laser light is transmitted through the objective lens 34 so as to transmit light. Of the Rayleigh scattered light and Raman scattered light emitted from the irradiated position of the light transmissive film sample 1 and irradiated with the focal position of the film sample 1, only weak Raman scattered light having a wavelength different from that of the laser light is notched. The filter or the edge filter 37 and the edge filter 38 are configured to pass through.
As described above, for the separation of the excitation light and the Raman scattered light, it is ideal that the notch filter 37 has a transmittance characteristic that does not transmit only a specific wavelength, in this case, the excitation light. As described above, the actual light blocking ratio is not 100%, but slightly leaks light of Rayleigh light.
The interface reflection information of the light transmissive sample film is acquired from this leaky Rayleigh light.

  In the notch filter 37, the reflected light beam from the light-transmitting film sample has a high transmittance of 90% or more of light in a band other than a narrow wavelength band of about 20 nm (Raman scattered light) centering on the oscillation wavelength of the excitation laser light source. And transmitted to the detection unit 36. If the edge filter 38 is further transmitted here, the wavelength selectivity of the Raman scattered light can be further enhanced.

FIG. 5B shows an example of a notch filter.
Thus, the notch filter transmits some excitation light having an excitation light wavelength (in this case, 488 nm wavelength) (in other words, the transmittance is not zero). For this reason, the excitation light (Rayleigh light) reflected by the light transmissive film sample passes through the notch filter 37, which is an excitation light blocking optical element, together with the Raman scattered light generated from the light transmissive film sample. Even so, it is transparent.

As described above, in the Raman spectrum measurement according to the present invention, this leakage light becomes noise. Therefore, when receiving the Raman scattered light, the Raman scattering of the detection target is detected before the detection unit 36 that detects the Raman scattered light. In order to detect only the light, the replaceable edge filter 38 having a replaceable transmittance of 10 −6 or less that selectively transmits light in a wavelength band suitable for the Raman scattered light to be detected is rearranged. .

  In general, the upper limit of the film thickness value for quantitative measurement determined by optical properties is naturally determined for submicron-sized film structure analysis to which film interface information is given. Since the penetration depth into the film is the reciprocal of the absorption coefficient of the film, for example, when the object to be measured is an electrophotographic photosensitive film, when the maximum value of the film thickness required for the film structure analysis is 40 μm, From λ / 4πκ, it can be seen that measurement is possible if the film has an extinction coefficient κ of κ = λ / 0.016π (λ: excitation light wavelength cm) or less.

FIG. 8 is a diagram showing an example of the result of the charge transport layer 25 μm film obtained by the measurement method of the present invention. The Raman excitation laser wavelength was 633 nm, and the extinction coefficient κ of the charge transport layer at this time was measured separately using a spectroscopic ellipsometer (JAWoollam WVASE32) with a film formed on Si-Wafer. Κ = λ / 0 It was κ = 0 value that was .016π or less. The refractive index of the charge transport layer was 1.68 at 633 nm.
When the transmittance of the notch filter 37 having the configuration shown in FIG. 4A is set to 10 −4 , a “Rayleigh light leakage light profile (interfacial reflection intensity distribution diagram)” that becomes Rayleigh light leakage light is obtained, and FIG. An edge filter having a transmittance of 10 −6 is arranged in the configuration shown in FIG. 6 to acquire a Raman spectrum in the depth direction in a state where Rayleigh light is removed, and follow the peak of a characteristic Raman band of an arbitrary molecule. Thus, the “molecular weight profile in the film” profile is obtained.
Here, the transmittance of the notch filter and the edge filter is measured with a spectral transmittance measuring device (Matsushita Techno Trading F20 device) for the laser light blocking optical element. Further, a 60 × oil immersion lens is used for the objective lens 34 in FIG. 4, and emulsion oil having a refractive index of 1.52 is used between the lens and the sample. The difference between the charge transport layer and the refractive index of 1.68 is -0.16, and the total NA is 1.42. The refractive index of emulsion oil is measured by coating emulsion oil on Si-Wafer with a spin coater and measuring the complex refractive index (refractive index, extinction coefficient) of emulsion oil with a spectroscopic ellipsometer (JAWoollam WVASE32).
In this way, it is possible to obtain a profile of the film structure to which the film interface information in the light transmissive film sample 1 is given.

FIG. 12 is a diagram showing an example of the result of the charge transport layer 17 μm film having the extinction coefficient κ = λ / 0.016π or less obtained by the measurement method of the present invention. When the transmittance of the notch filter 37 having the configuration shown in FIG. 11A is set to 10 −4 , a “Rayleigh light leakage light profile (interfacial reflection intensity distribution diagram)” which becomes the leakage light of Rayleigh light is obtained, and FIG. An edge filter 38 having a transmittance of 10 −6 is arranged in the configuration shown in FIG. 6 to obtain a polarization Raman spectrum in the depth direction in a state where Rayleigh light is removed, and a peak of a characteristic Raman band of an arbitrary molecule The polarization Raman intensity profile is acquired.
Here, the transmittance values of the notch filter and the edge filter were measured for the laser light blocking optical element with a spectral transmittance measuring device (Matsushita Techno Trading F20 device). An objective lens with a correction ring was used as the objective lens 34 in FIG.
In this way, it is possible to obtain a polarized Raman intensity data profile for each position in the Z direction to which film interface information in the light transmissive film sample 1 is given.

As a comparative example, FIG. 9 shows the interface reflection light “Rayleigh light leakage light profile (interface reflection intensity distribution diagram)” obtained when the transmittance of the notch filter 37 having the configuration shown in FIG. 4A is 10 −8 . Show.
As shown in FIG. 9, when the attenuation factor of Rayleigh light in the notch filter 37 is large, even if light transmitted through the notch filter is received in the wavelength region near the excitation light, it is clear from the light transmissive film sample. Interface reflection light could not be acquired.
Further, when the transmittance of the notch filter 37 is 10 −3 , as shown in FIG. 10, the Rayleigh light (excitation light wavelength region in the figure) is sufficiently attenuated by the dichroic mirror and the notch filter when receiving the Raman scattered light. Otherwise, Rayleigh light is superimposed on the Raman spectrum, and as a result, the S / N ratio of the Raman spectrum is significantly reduced.
In the configuration shown in FIG. 4B, Rayleigh light is also superimposed on the Raman spectrum when the transmittance of the edge filter 38 is about 10 −3 .
Further, an oil immersion lens is used for the objective lens 34 in FIG. 4A, and emulsion oil having a refractive index of 1.479 that has a refractive index difference of −0.201 with respect to a film to be measured having a refractive index of 1.68 is used as the lens. -When used between samples, refraction due to the difference in refractive index occurs between the lens and the emulsion oil, and also between the films, so that the beam spot of the laser beam expands due to the influence of aberrations, resulting in sufficient spatial resolution. Could not be obtained. Also, when a refractive liquid having a refractive index of 2.0 is used, a difference in refractive index is generated, so that the spatial resolution is lowered, and the film thickness is 20 μm as compared with the case of using 1.5 to 1.6 emulsion oil. As a result, the beam spot diameter expanded and the intensity of the excitation laser apparently decreased, so that accurate measurement could not be performed.
In the case where the refractive index of the emulsion oil is 1.63, which is close to the refractive index of the film, as shown in FIG. 13, the reflectance on the film surface represented by the formula (1) becomes small, so Rayleigh light on the film surface. The reflected light could not be acquired, and the desired film structure analysis could not be performed.

It is a schematic block diagram of the optical system which detects only the Raman scattered light of the conventional Raman spectrometer. FIG. 3 is a diagram showing a layer configuration example of a multilayer electrophotographic photosensitive member as an example having a transparent film structure. It is explanatory drawing which shows the result of having acquired the interface information of the film | membrane of a test object from the leak light of Rayleigh light by the measuring apparatus of this embodiment. It is a structural example of the measuring apparatus of this embodiment, and is a figure which shows the structural example of the optical system which interrupts | blocks Rayleigh light and separates Raman scattered light, (a) is the structural example which enabled it to input interface information ( (B) is a configuration example in which interface information can be excluded. It is a schematic diagram which shows the optical characteristic of the laser beam cutoff optical element used for the removal of Rayleigh light of this embodiment. It is a schematic diagram which shows the characteristic of the edge filter used for the optical system of this embodiment. It is a transmittance | permeability characteristic explanatory drawing of the dichroic mirror which has the characteristic which reflects the wavelength range of the laser light source of this embodiment. It is explanatory drawing which shows an example of the measurement result of the interface reflection intensity distribution obtained by this embodiment, and the molecular weight profile in a film | membrane. In this embodiment, it is explanatory drawing which shows the interface reflection intensity distribution figure in case the attenuation factor of Rayleigh light is large. It is explanatory drawing which shows the example which made the attenuation factor of Rayleigh light small in this embodiment, and reduced S / N of the Raman spectrum remarkably. It is a structural example which attached the polarizer 39 of the measuring apparatus of this invention embodiment, and is a figure which shows the structural example of the optical system which interrupts | blocks Rayleigh light and separates Raman scattered light, (a) can input interface information In this configuration example (the edge filter 38 is not provided), (b) is a configuration example in which interface information can be excluded. It is the polarization Raman intensity profile and Rayleigh light leakage light profile of the charge transport layer obtained by the measurement method of the present invention. It is the polarization Raman intensity profile and Rayleigh light leakage light profile of the charge transport layer obtained by the measurement method of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Sample 2 Aluminum drum 3 Intermediate | middle layer 4 Charge generation layer 5 Charge transport layer 20 Laser light source 21 Condensing lens 22 1st pinhole 23 Separation optical element 24 2nd condensing lens 25 2nd pinhole 26 Detection part 30 Laser light source 31 Condensing lens 32 First pinhole 33 Separation optical element 34 Second condensing lens 35 Second pinhole 36 Detector 37 Notch filter 38 Edge filter 39 Polarizer 40 Analyzer 41 Depolarization plate

Claims (20)

  1. A laser light source, a microscopic optical system having an objective lens and a separation optical element that irradiates the sample with laser light and receives scattered light from the sample, and a spectroscopic unit that splits the scattered light;
    In a Raman spectroscopic measurement device having a light detection means for detecting the intensity of the scattered light that has been dispersed,
    A first laser light blocking optical element fixed to the front of the optical path of the spectroscopic means on which the scattered light is incident, and a replaceable second laser light blocking optical element,
    The transmittance of the first laser light blocking optical element with respect to the laser light wavelength is in the range of 10 −4 to 10 −5 , and the transmittance of the second laser light blocking optical element with respect to the laser light wavelength is 10 −6. or less,
    A Raman spectroscopic measurement apparatus comprising a confocal microscope optical system including a pinhole having a conjugate relationship with a focal plane .
  2.   The Raman spectroscopic measurement apparatus according to claim 1, wherein the first laser light blocking optical element is a notch filter.
  3.   The Raman spectroscopic measurement apparatus according to claim 1, wherein the first laser light blocking optical element is an edge filter.
  4.   The Raman spectroscopic measurement apparatus according to claim 1, wherein the second laser light blocking optical element is an edge filter.
  5.   The Raman spectroscopic measurement apparatus according to claim 1, wherein the separation optical element is a dichroic mirror.
  6.   The Raman spectroscopic measurement apparatus according to claim 1, wherein the NA of the dry objective lens used in the Raman spectroscopic measurement apparatus is 0.8 or more.
  7.   The Raman spectroscopic measurement apparatus according to claim 1, wherein the objective lens of the Raman spectroscopic measurement apparatus is a plan apochromat lens.
  8. The Raman spectroscopic measurement apparatus according to claim 6 , wherein the objective lens has a correction ring.
  9.   The Raman spectroscopic measurement apparatus according to claim 1, wherein the objective lens of the Raman spectroscopic measurement apparatus is a combination of an oil immersion lens having an NA of 1.2 or more and emulsion oil.
  10. Wherein the oil immersion lens of the Raman spectrometer, claim, characterized by using an emulsion oil having a refractive index value of -0.2 to 0.1 from the refractive index of the object film to be the object to be measured 9 The Raman spectroscopic measurement apparatus described in 1.
  11. The Raman spectroscopic measurement apparatus according to claim 10 , wherein the emulsion oil has a refractive index of 1.5 to 1.6.
  12. Laser wavelength of the Raman spectrometer is a Raman spectrometer according to any one of claims 1 to 11, characterized in that at 540nm or 900nm or less.
  13. A microscopic optical system having a laser light source, a polarizer that adjusts the polarization direction of the laser, a separation optical element that irradiates the sample with laser light and receives scattered light from the sample, and an objective lens;
    An analyzer and a depolarizing plate for selecting the polarization characteristics of the scattered light;
    A spectroscopic means for splitting the scattered light;
    In a Raman spectroscopic measurement device having a light detection means for detecting the intensity of the scattered light that has been dispersed,
    A first laser light blocking optical element fixed to the front of the optical path of the spectroscopic means on which the scattered light is incident, and a replaceable second laser light blocking optical element,
    The transmittance of the first laser beam blocking optical element with respect to the laser beam wavelength is in the range of 10 −4 to 10 −5 , and the transmittance of the second laser beam blocking optical element with respect to the laser beam wavelength is 10 −6 or less . Yes,
    A Raman spectroscopic measurement apparatus comprising a confocal microscope optical system including a pinhole having a conjugate relationship with a focal plane .
  14. The Raman spectrometer according to claim 13 , wherein the polarizer of the Raman spectrometer is a total reflection polarizer.
  15. The Raman spectrometer according to claim 13 , wherein the analyzer of the Raman spectrometer is an absorptive polarizer.
  16. The Raman spectroscopic measurement apparatus according to claim 13 , wherein the depolarizer of the Raman spectroscopic measurement apparatus is a crystal depolarization plate.
  17. By Raman spectroscopic measurement apparatus according to any one of claims 1 to 12, by receiving the leakage light of the Rayleigh light to detect the reflected light intensity at the film surface in the first laser light blocking optical element, the Raman A Raman spectroscopic measurement method characterized in that interface information of a film interface is acquired in association with a spectroscopic data profile for each depth position by spectroscopy.
  18. The Raman spectroscopic measurement device according to any one of claims 13 to 16 is used to receive the leaky light of the Rayleigh light in the first laser light blocking optical element, to detect the reflected light intensity at the film interface, and to detect the Raman A Raman spectroscopic measurement method that acquires interface information of a film interface in association with a polarized Raman intensity data profile for each position by spectroscopy.
  19. The Raman spectroscopic measurement method according to claim 17 or 18 , wherein the object to be measured is an electrophotographic photosensitive member film , and the measurement range of the film thickness to be measured is selected to be 3 to 40 µm.
  20. The Raman spectroscopic measurement method according to claim 19 , wherein the extinction coefficient: κ of the film to be measured is κ = λ / 0.016π (λ: excitation light wavelength cm) or less. Measurement method.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107389657A (en) * 2017-08-15 2017-11-24 江西农业大学 Antiform oleic acid detection method of content and device in a kind of edible oil

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010036421A (en) * 2008-08-04 2010-02-18 Sumitomo Rubber Ind Ltd Printing method and printing press
KR101491854B1 (en) 2008-08-20 2015-02-09 엘지전자 주식회사 Apparatus and method for noninvasively measuring blood sugar level
JP2010117226A (en) * 2008-11-12 2010-05-27 Ricoh Co Ltd Raman spectrometric measuring instrument and method for measurement
JP5440932B2 (en) * 2009-11-30 2014-03-12 株式会社リコー Evaluation method of photosensitive layer
JP2011158327A (en) * 2010-01-29 2011-08-18 Beckman Coulter Inc Analyzer, and analyzing method
JP2012173112A (en) * 2011-02-21 2012-09-10 Ricoh Co Ltd Raman spectroscopic apparatus and raman spectroscopic method
KR101446210B1 (en) 2013-02-15 2014-10-01 서울대학교산학협력단 Fast and quantitative raman analysis method and apparatus thereof for large-area multiple bio-targets
JP6248403B2 (en) * 2013-03-28 2017-12-20 セイコーエプソン株式会社 Detection device and electronic device
JP6150167B2 (en) * 2013-08-20 2017-06-21 株式会社リコー Fine particle dispersibility evaluation apparatus and fine particle dispersibility evaluation method
WO2015141873A1 (en) * 2014-03-18 2015-09-24 서울대학교산학협력단 Raman analysis method and device for high-speed quantitative analysis of wide-area sample

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04198845A (en) * 1990-11-29 1992-07-20 Jasco Corp Method and apparatus for measuring crystal orientation and method for determining optical characteristic constant of polarizing raman apparatus
JP3316012B2 (en) * 1992-04-22 2002-08-19 株式会社日立製作所 Temperature measuring device using a micro-Raman spectrophotometer
JPH0688785A (en) * 1992-09-07 1994-03-29 Daikin Ind Ltd Luminescence-type immunoassay device
JPH08247858A (en) * 1995-03-07 1996-09-27 Toshiba Corp Optical temperature distribution sensor and temperature distribution measuring method
JPH08327550A (en) * 1995-06-02 1996-12-13 Tokai Carbon Co Ltd Raman spectrometer
JP2004245694A (en) * 2003-02-13 2004-09-02 Koji Inoue Scanning probe microscope image and laser excitation emission distribution image measuring apparatus
JP4616567B2 (en) * 2004-03-11 2011-01-19 株式会社堀場製作所 Measuring method, analyzing method, measuring device, analyzing device, ellipsometer and computer program
EP1817572A2 (en) * 2004-11-16 2007-08-15 Helicos Biosciences Corporation An optical train and method for tirf single molecule detection and analysis
JP4498081B2 (en) * 2004-09-21 2010-07-07 エスアイアイ・ナノテクノロジー株式会社 Scattering near-field microscope and measuring method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107389657A (en) * 2017-08-15 2017-11-24 江西农业大学 Antiform oleic acid detection method of content and device in a kind of edible oil
CN107389657B (en) * 2017-08-15 2019-12-17 江西农业大学 Method and device for detecting content of trans-oleic acid in edible oil

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