JP2006292551A - Titanium oxide analyzing method and titanium oxide analyzer carrying out it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for obtaining the mixing ratio distribution image of a titanium oxide sample wherein a anatase type crystal and a rutile type crystal coexist in a non-uniform mixing ratio. <P>SOLUTION: The whole of the region to be measured of the surface of the titanium oxide sample is irradiated with monochromatic incident X-rays and the diffracted X rays from the respective regions of the region to be measured of the surface of the titanium oxide sample are discriminated and detected by a two-dimensional sensitive detector to form an intensity distribution image. The wavelength of the monochromatic incident X rays is changed to acquire the intensity distribution image of the predetermined lattice surface of the anatase type crystal and the predetermined lattice surface of the rutile type crystal and the mixing ratio distribution image converted by the division of them is formed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention irradiates the measurement surface of a titanium oxide sample in which anatase type crystals and rutile type crystals coexist, irradiates X-rays, captures X-rays diffracted from each position of the sample, and images the crystals constituting the sample and their ratios. The present invention relates to a method for analyzing titanium oxide and a titanium oxide analyzer for performing the method, characterized in that the crystal and mixing ratio constituting the sample are identified.

  Titanium oxide is used as a white pigment in paints and the like, and is used in many applications such as electronic materials, catalyst materials, ultraviolet absorbers, and photocatalysts. Three crystal forms of titanium dioxide are known: anatase, rutile, and brookite. The anatase type is stable at low temperatures and is mainly used as a photocatalyst. The rutile type is stable at high temperatures and is mainly used for paints and pigments. It is difficult to obtain only pure anatase-type crystals and only rutile-type crystals due to restrictions on the production technology of titanium oxide, and they are usually used in a state where both are mixed and produced. In some cases, there is a report that mixing both of them may give better results (for example, Patent Document 1). In any case, when using titanium oxide, it is necessary to grasp the mixed state of the anatase type crystal and the rutile type crystal as accurately as possible.

  In the analysis of a sample in which anatase type crystals and rutile type crystals are mixed, in order to determine the mixing ratio, a method using the intensity ratio of diffracted X-rays measured using an X-ray diffractometer is often used. It is used. In this method, by irradiating a specimen with copper characteristic X-rays (Cu-Kα rays), the strongest diffracted X-rays are obtained in an anatase crystal (101) plane (lattice spacing d = 0.352 nm, Bragg Paying attention to the (110) plane (lattice spacing d = 0.3247 nm, Bragg angle θ = 13.73 °) at which the strongest diffraction X-ray of the rutile crystal can be obtained. From the ratio of the diffracted X-ray intensity, the weight ratio was calculated using a calibration curve prepared in advance using a standard sample with a known mixing ratio (Non-patent Document 1, Patent Document 2).

However, the result obtained by this conventional X-ray identification method is only average information of the entire region irradiated with X-rays, and does not reflect the true value in each part constituting the region. Therefore, there is a problem when trying to understand the relationship between the mixing ratio of the crystals constituting the sample and various characteristics.
In order to further advance research and development using the characteristics of titanium oxide in the future, first of all, know the mixing ratio of the crystals composing the sample accurately, that is, the average value of the mixing ratio of the composing crystals in a wide area. However, it is important and required to accurately know the values at various points in a wide area.

JP 2004-255332 A R. A. Spurr and H.M. Myers, “Quantitative Analysis of Anatase-Rutile Mixtures with an X-Ray Diffractometer”, Analytical Chemistry, vol. 29, no. 5, pp. 760-762, 1957. JP 2004-143453 A

  The present invention is intended to meet such needs. That is, the first object is to provide a method for analyzing titanium oxide that can accurately and locally determine the mixing ratio of crystals constituting a titanium oxide sample, both locally and accurately, in a short time. To do. Moreover, it is set as the 2nd subject to provide the titanium oxide analyzer for implementing the titanium oxide analysis method.

The first challenge is
In a titanium oxide analysis method for obtaining a local mixing ratio distribution image of a mixed titanium oxide sample containing anatase type crystals and rutile type crystals non-uniformly,
Irradiate the entire region to be measured on the surface of the titanium oxide sample with a monochromatic incident X-ray having a wavelength longer than the wavelength of the titanium K absorption edge,
By limiting the angle divergence of the diffracted X-rays diffracted by the titanium oxide sample and emitted from the measurement region by the angle divergence limiting means, a predetermined scattering angle (incident X-ray optical axis) emitted from each part in the measurement region And the X-ray diffracted X-rays, the diffraction angle of the X-ray optical axis is differentiated by each detection element of the two-dimensional position sensitive detector arranged in a one-to-one correspondence corresponding to those parts. Detect
Forming and recording a two-dimensional diffracted X-ray intensity distribution image with the intensity of diffracted X-rays detected by each detecting element as each pixel value;
While the optical axis of the incident X-ray, the titanium oxide sample, the angle divergence limiting means, and the two-dimensional position sensitive detector are fixed, the wavelength of the monochromatic incident X-ray is within the wavelength range longer than the wavelength of the K absorption edge of titanium. Diffracted X-ray intensity distribution image of diffracted X-rays derived from one predetermined lattice plane of anatase-type crystal and diffracted X-ray intensity distribution of diffracted X-rays derived from one predetermined lattice plane of rutile-type crystal Get an image,
Two-dimensional mixture ratio distribution by taking the ratio of the pixel values of the corresponding pixels of those images and setting the ratio value as each pixel value, or by further converting each pixel value to a predetermined value This is solved by a titanium oxide analysis method characterized in that an image is formed and recorded.

In addition, the first problem is
In the titanium oxide analysis method for obtaining a distribution image of the local mixing ratio of a titanium oxide sample in which anatase-type crystals and rutile-type crystals coexist in a heterogeneous manner,
The entire region to be measured on the surface of the titanium oxide sample is illuminated with incident X-rays made of monochromatic X-rays having a wavelength longer than the wavelength of the K absorption edge of titanium, and is diffracted by the titanium oxide sample and emitted from the region to be measured. By restricting the angle divergence with the angle divergence limiting means, the diffracted X-rays emitted from the respective parts in the measured region can be detected by each of the two-dimensional position sensitive detectors arranged one-on-one facing these parts. Detect and distinguish with the detection element,
Forming and recording a two-dimensional diffracted X-ray intensity distribution image with the intensity of diffracted X-rays detected by each detecting element as each pixel value;
Two-dimensional position sensitive type without changing the correspondence between each part in the measurement area and each detection element of the two-dimensional position sensitive detector while fixing the optical axis of the incident X-ray and the titanium oxide sample The detector is rotated around a rotation axis extending perpendicularly to the optical axis of the incident X-ray through the center of the region to be measured within the same plane as the sample surface, and the scattering angle of the diffracted X-ray to be detected ( By changing the angle formed by the incident X-ray optical axis and the diffracted X-ray optical axis, the diffraction angle), the diffraction X-ray intensity distribution image of the diffracted X-ray derived from a predetermined lattice plane of the anatase type crystal and the rutile type A diffracted X-ray intensity distribution image of diffracted X-rays originating from a predetermined single lattice plane of the crystal, taking a ratio of pixel values of corresponding pixels of those images, and calculating the ratio value as each pixel value Or a two-dimensional mixture ratio distribution image in which each pixel value is a value after predetermined conversion. Characterized by recording also solved by titanium oxide analytical methods.
Two-dimensional position sensitive detectors are often used in making rapid measurements of X-ray diffraction. In this case, the image obtained by the two-dimensional position sensitive detector is an X-ray diffraction pattern itself, which gives information on the average of the entire sample illuminated by X-rays. On the other hand, in the titanium oxide analysis method of the present invention, in the image obtained by the two-dimensional position sensitive detector, the point on the image corresponds to the point on the sample. This will be described with reference to FIG. As shown in FIG. 1 and a schematic diagram (a) of the sample, various crystal phases are distributed in different places in the observation field. In the titanium oxide analysis method of the present invention, two-dimensional position sensitive detection is performed. The X-ray image obtained by the instrument corresponds to the position on the sample as shown in (b) and (c). That is, (b) is an image of a portion where the lattice spacing is a specific value d ₁ , and (c) is an image of a portion where the lattice value is a specific value d _2. Thus, the amount of each can be known.

  As incident X-rays composed of monochromatic X-rays having a wavelength longer than the wavelength of the K absorption edge of titanium, monochromatic X-rays generated by generating titanium characteristic X-rays using a titanium X-ray tube may be used. When titanium Kα rays are used, it is preferable to remove the Kβ rays generated at the same time using a filter. For example, copper Kα ray (8.04 keV) generally used in ordinary powder X-ray diffractometers has higher energy than titanium K absorption edge (4.97 keV). Fluorescent X-ray comes out. The purpose of the present invention is to distinguish between rutile and anatase, which are different crystal phases of titanium oxide, but this fluorescent X-ray is emitted from both rutile and anatase and becomes a background, preventing the discrimination between the two. . On the other hand, when the titanium Kα ray (4.5 keV), which is lower in energy than the K absorption edge of titanium, is used, such fluorescent X-rays are not emitted, and therefore both can be identified only by diffracted X-rays.

The second problem is
In a titanium oxide analyzer that obtains a distribution image of the local mixing ratio of a titanium oxide sample in which anatase-type crystals and rutile-type crystals coexist in a heterogeneous manner,
An X-ray generator that generates monochromatic incident X-rays having a wavelength longer than the wavelength of the K absorption edge of titanium in an optical axis invariable and wavelength-variable manner is fixedly held;
The titanium oxide sample is fixedly held so that the incident X-rays emitted from the X-ray generation unit illuminate the entire region to be measured on the surface of the titanium oxide sample;
A two-dimensional position sensitive detector consisting of a plurality of detection elements arranged in two dimensions for detecting diffracted X-rays diffracted by the titanium oxide sample and emitted from the measurement region;
In order to distinguish and detect diffracted X-rays having a predetermined scattering angle emitted from each part in the measurement region by each detection element of the two-dimensional position sensitive detector facing the parts one-to-one, Angle divergence limiting means for limiting the angle divergence of the diffracted X-rays emitted from the measurement region is provided between the titanium oxide sample and the two-dimensional position sensitive detector,
An image forming recording unit for forming and recording a two-dimensional diffracted X-ray intensity distribution image with the intensity of the diffracted X-ray detected by each detecting element as each pixel value;
While the optical axis of the incident X-ray, the titanium oxide sample, the angle divergence limiting means, and the two-dimensional position sensitive detector are fixed, the diffraction X-ray derived from a predetermined lattice plane of the rutile crystal In order to acquire a diffracted X-ray intensity distribution image and a diffracted X-ray intensity distribution image of diffracted X-rays derived from a predetermined one lattice plane of the anatase type crystal, the X-ray generation unit is at least a lattice of those lattice planes. The ability to generate monochromatic incident X-rays of two different wavelengths corresponding to the spacing;
The image forming recording unit uses each pixel value as a ratio of pixel values of corresponding pixels between the diffracted X-ray intensity distribution image acquired for the rutile crystal and the diffracted X-ray intensity distribution image acquired for the anatase crystal. Alternatively, it is possible to form and record a two-dimensional mixture ratio distribution image with each pixel value as a value after a predetermined conversion,
This is solved by a titanium oxide analyzer characterized by the following.

  At this time, this corresponds to the case where the peak wavelength of the diffracted X-ray intensity derived from the lattice plane of interest does not exactly match the wavelength theoretically determined from the Bragg equation, and the diffracted X-ray intensity distribution image at the peak wavelength. It is preferable that the wavelength of the incident X-ray can be continuously changed within a desired range with the two types of wavelengths as the centers. Also, in order to keep the two-dimensional position sensitive detector and the titanium oxide sample as close as possible so as not to reduce the detection efficiency, which lattice plane of the anatase type crystal and the rutile type crystal should be focused on? However, in the case where the incident angle of the incident X-ray exceeds 0 degree and is within the range of 3 degrees or less, one exit within the range of 75 to 105 degrees with respect to the sample surface. It is advantageous if a two-dimensional position sensitive detector is fixedly held at a position for detecting a diffracted X-ray having an angle.

In addition, the second problem is
In a titanium oxide analyzer that obtains a local mixing ratio distribution image of a titanium oxide sample in which anatase-type crystals and rutile-type crystals coexist in a heterogeneous manner,
An X-ray generator that generates incident X-rays composed of monochromatic X-rays having a wavelength longer than the wavelength of the K absorption edge of titanium is fixedly held;
The titanium oxide sample is fixedly held so that the incident X-rays emitted from the X-ray generation unit illuminate the entire region to be measured on the surface of the titanium oxide sample;
A two-dimensional position sensitive detector composed of a plurality of two-dimensionally arranged detection elements for detecting diffracted X-rays diffracted by the titanium oxide sample and emitted from the measurement region is the same plane as the sample surface Is disposed so as to be rotatable around a rotation axis extending through the center of the region to be measured and extending perpendicularly to the optical axis of the incident X-ray,
In order to distinguish and detect diffracted X-rays of one scattering angle emitted from each part in the measurement target region with each detection element of the two-dimensional position sensitive detector facing the parts one-to-one, An angle divergence limiting means for limiting the angle divergence of the diffracted X-rays emitted from the measurement region is provided integrally with the two-dimensional position sensitive detector between the titanium oxide sample and the two-dimensional position sensitive detector. Being done,
An image forming recording unit is provided for forming and recording a two-dimensional diffraction X-ray intensity distribution image having each pixel value as the intensity of the diffraction X-ray detected by each detection element;
The diffraction X-ray intensity distribution image of the diffracted X-ray derived from the predetermined one lattice plane of the rutile type crystal and the predetermined one lattice plane of the anatase type crystal with the X-ray generation portion and the titanium oxide sample fixed. In order to obtain a diffracted X-ray intensity distribution image of the derived diffracted X-ray, the two-dimensional position sensitive detector changes a correspondence relationship between each part in the measurement target region and each detection element. Without being able to be held at an angular position for detecting diffracted X-rays of two scattering angles respectively corresponding to the lattice spacing of at least their lattice planes,
The image forming recording unit uses each pixel value as a ratio of pixel values of corresponding pixels of the diffracted X-ray intensity distribution image acquired for the rutile crystal and the diffracted X-ray intensity distribution image acquired for the anatase crystal. Alternatively, it is possible to form and record a two-dimensional mixture ratio distribution image in which each pixel value is a value obtained by performing a predetermined conversion,
This is also solved by a titanium oxide analyzer characterized by the following.

  Here, in order to use the characteristic X-ray of titanium as a monochromatic X-ray having a wavelength longer than the wavelength of the K absorption edge of titanium, a titanium tube may be used for the X-ray generation unit. In that case, a solution containing iodine or an iodine compound is prepared in the X-ray extraction window and directly applied thereto, or a polymer film formed by applying the solution is applied to absorb the Kβ ray. It is desirable that the filter structure be removed so that only the Kα ray of titanium can be used as the incident X-ray.

  In addition, since the scattering angle of the diffracted X-ray from the target grating surface does not always exactly match the scattering angle theoretically obtained from the Bragg condition, the two-dimensional position sensitive detector is Without changing the one-to-one correspondence between each part and each detection element, the angle position corresponding to the two scattering angles can be continuously rotated in a desired angle range, and the angle It is more preferable to set such that it can be held at an arbitrary angular position within the range.

In the titanium oxide analysis method and the titanium oxide analysis apparatus according to the present invention, the average information obtained by considering a certain region of the titanium oxide sample as one point, the region includes a plurality of portions (each portion is regarded as one point), typical. The conventional average information is obtained for a two-dimensional mixture ratio distribution image having a mixture ratio of anatase type crystal and rutile type crystal as information of each part when divided into 1000 × 1000 parts as values of each pixel. Can be obtained in the same amount of time. The mixing ratio distribution image is a predetermined distribution determined by using a standard sample with a known mixing ratio as the distribution of the ratio of the diffracted X-ray intensity derived from the predetermined lattice plane of the anatase crystal and the predetermined lattice plane of the rutile crystal. It can also be obtained as a distribution of weight ratios converted using the conversion formula.

  Conventional methods for obtaining average information pay attention to the (101) plane from which the strongest diffracted X-ray of the anatase crystal is obtained and the (110) plane from which the strongest diffracted X-ray of the rutile crystal is obtained. Although the intensity ratio was acquired, in the present invention in which information of each part of the measurement region of the titanium oxide sample is simultaneously distinguished and collected by a two-dimensional position sensitive detector, the (200) plane of the anatase crystal is Focusing on the (111) plane, (210) plane, or (211) plane of the rutile crystal, the surface of the titanium oxide sample and the detector plane of the two-dimensional position sensitive detector (the plane formed by the detection plane of each detection element) ) Are positioned in a nearly parallel state and are opposed to each other and can be arranged close to each other, which is advantageous in terms of detection efficiency.

  In the case of acquiring a diffraction X-ray intensity distribution image for a lattice plane of interest by rotating the two-dimensional position sensitive detector and changing the scattering angle while fixing the wavelength of the incident X-ray, When titanium Kα rays are used as the rays, no fluorescent X-rays are produced from titanium, and therefore, a low-background diffracted X-ray intensity distribution image can be obtained.

  When the X-ray viewing angle (angle formed between the sample surface and the incident X-ray, the target angle) is set to a low angle of more than 0 degrees and 3 degrees or less, the incident X-rays with a thin linear section are used. In addition, it becomes possible to uniformly illuminate the entire surface of the measurement area, and it is also possible to bring the titanium oxide sample and the two-dimensional position sensitive detector closer to each other. In addition, even for a sample having a thin layer of titanium oxide on the substrate, the influence of diffracted X-rays and fluorescent X-rays from the substrate can be suppressed. In the titanium oxide analyzer according to the present invention, if the X-ray generator, the titanium oxide sample, the angle divergence limiting means, and the two-dimensional position sensitive detector satisfy the above relative positional relationship, You may arrange | position so that it may arrange | position so that the surface may become horizontal, or it may arrange | position so that it may become vertical. Needless to say, when the titanium oxide sample is a sample that is not always easy to fix, such as a powder sample, the sample may be arranged horizontally.

  Hereinafter, embodiments of the present invention will be described in detail.

  As shown in FIG. 2 or FIG. 3, the titanium oxide analysis method for obtaining a local mixing ratio distribution image of a titanium oxide sample in which anatase-type crystals and rutile-type crystals coexist in a non-homogeneous mixture is used. The entire region to be measured on the surface of the titanium oxide sample is illuminated by the line (only the diffracted X-rays emitted from this region can enter the detection surface of the two-dimensional position sensitive detector), and is diffracted by the titanium oxide sample. By restricting the angular divergence of the diffracted X-rays emitted from the measured region by the angle divergence limiting means and extracting only the component of the diffracted X-rays substantially parallel to the predetermined optical axis, Diffraction X-rays with one scattering angle that is emitted are detected by distinguishing each detection element of a two-dimensional position sensitive detector placed one-on-one facing these parts, and detected by each detection element X-ray intensity for each image Forming a two-dimensional diffraction X-ray intensity distribution image to a value to be recorded.

  In the first embodiment, the incident X-ray is a monochromatic X-ray having a wavelength longer than the wavelength of the K absorption edge of titanium, and the optical axis of the incident X-ray, the titanium oxide sample, and the two-dimensional position sensitive detector are fixed. The intensity of the diffracted X-ray derived from a predetermined lattice plane of the anatase crystal is changed to the pixel value by changing the wavelength of the monochromatic incident X-ray within a wavelength range longer than the wavelength of the titanium K absorption edge. The diffraction X-ray intensity distribution image to be obtained and the diffraction X-ray intensity distribution image having the pixel value as the intensity of the diffracted X-ray derived from a predetermined lattice plane of the rutile crystal are obtained as described above, and the correspondence between these images The ratio of the pixel values of the pixels to be taken is taken, and a two-dimensional mixture ratio distribution image is formed and recorded with the ratio value as each pixel value. At that time, a conversion formula for converting the intensity ratio of diffracted X-rays to the lattice plane of interest into a weight ratio using a sample whose mixing ratio of anatase type crystal and rutile type crystal is known is calculated in advance. A two-dimensional mixture ratio distribution image may be formed in which each pixel value is a weight ratio value converted using.

More specifically, the two-dimensional position-sensitive type has a scattering angle (diffraction angle, an angle formed by the optical axis of incident X-rays and the optical axis of diffracted X-rays) at a predetermined value 2θ ₀ (Bragg angle θ ₀ ). The detector is fixedly arranged, and Bragg conditions (2d _A sin θ ₀ = λ _A , 2d _R sin θ ₀ == the lattice spacings d _A and d _R of the lattice planes determined in advance of the anatase type crystal and the rutile type crystal, respectively. The diffraction X-ray intensity distribution images at the respective wavelengths λ _A and λ _R satisfying λ _R ) are obtained, and the rutile type obtained at the wavelength λ _R in the diffraction X-ray intensity distribution image of the anatase crystal obtained at the wavelength λ _A A diffracted X-ray intensity distribution image of the crystal is divided to create a two-dimensional mixture ratio distribution image having the diffracted X-ray intensity ratio as each pixel value or the weight ratio converted by the conversion formula as each pixel value. Since each pixel of this image has a one-to-one correspondence with each part in the measurement area, the ratio of anatase crystals is large in a certain part in the measurement area due to light and darkness or color distribution of the image. Then, it is clear at a glance that the ratio of rutile crystals is large. It is also possible to represent the mixture ratio by a number from each pixel value.

Theoretically, even if the wavelengths satisfying the Bragg condition with respect to the lattice spacings d _A and d _R are λ _A and λ _R , they may actually deviate slightly from these wavelengths. When acquiring a distribution image, the wavelength is swept continuously in the vicinity of these wavelengths (for example, in the range of about 0.01 to 0.02 nm and the energy is in the range of about 100 to 200 eV), and the intensity becomes strongest. It is necessary to acquire a diffraction X-ray intensity distribution image at a wavelength. In this method, the optical axis of the incident X-ray, the sample position, the position of angle divergence limiting means, and the position of the two-dimensional position sensitive detector at the time of image acquisition for the anatase crystal and at the time of image acquisition for the rutile crystal Is unchanged and only the wavelength of the incident X-rays changes. Therefore, by selecting a grating surface used for comparison to the sample and the angular divergence limiting means and two-dimensional position sensitive detector is 2 [Theta] ₀ that does not interfere with the two-dimensional position sensitive regardless of the size and shape of the sample A diffracted X-ray intensity distribution image can be efficiently acquired by bringing the mold detector close to the sample. As a lattice plane representing each type, it is not necessary to use an anatase type (101) plane and a rutile type (110) plane which are the strongest lines in the intensity profile.

  FIG. 2 is a conceptual diagram of a titanium oxide analyzer for carrying out the titanium oxide analysis method according to the first embodiment. The X-ray generator 1 has a linear cross section that is variable in wavelength and wide in the horizontal direction by, for example, monochromating continuous X-rays from synchrotron radiation or a rotating anti-cathode X-ray source with a monochromator such as a monochromator. A monochromatic incident X-ray 2 having a wavelength longer than the wavelength of the K absorption edge of titanium is generated. The optical axis of the incident X-ray 2 is constant regardless of the wavelength. The titanium oxide sample 3 is fixed and held by the sample support 4 so that the viewing angle (angle formed between the optical axis of the incident X-ray and the sample surface) is 1 °, and is shown hatched on the sample surface. The entire measurement area A is illuminated by the incident X-ray 2. The two-dimensional position sensitive detector 5 in which a plurality of detection elements are arranged two-dimensionally has a scattering angle of 85 ° (diffraction angle 2θ = 85 °) that is diffracted by the sample and emitted from the measured region A on the sample surface. ) Is fixedly held by a detector support 6 at a position where a diffracted X-ray 8 having a) is detected.

  The two-dimensional position sensitive detector 5 can be a two-dimensional detector that gives information of a position on a plane expressed by XY coordinates, for example, a charge coupled device (= CCD) camera. Between the sample 3 and the two-dimensional position sensitive detector 5, angle divergence limiting means 7 is provided. The angle divergence limiting means 7 can be a fine tube assembly. In FIG. 2, the angle divergence limiting means 7 is provided integrally with the two-dimensional position sensitive detector 5, but is not necessarily integrated. The angle divergence limiting means 7 limits the angle divergence of the diffracted X-rays 8 emitted from the measurement area A and extracts only a component substantially parallel to a predetermined optical axis. As a result, an emission angle of 84 ° with respect to the sample surface (a viewing angle of 1 ° and a scattering angle of 85 °) from each part of the area A to be measured, which is approximately the same size as the detection element of the two-dimensional position sensitive detector 5. Therefore, each detection element facing each part detects the diffracted X-rays 8 emitted at an angle of 84 ° with respect to the sample surface. Then, a two-dimensional diffracted X-ray intensity distribution image having the diffracted X-ray intensity detected by each detecting element as each pixel value is created and recorded by an image forming recording unit (not shown).

Using this apparatus, the intensity of the diffracted X-ray from the (200) plane (d _A = 0.1892 nm) of the anatase crystal and the diffracted X-ray from the (210) plane (d _R = 0.2054 nm) of the rutile crystal When the weight ratio of both is evaluated from the ratio to the intensity of the anatase crystal, the wavelength of incident X-rays is continuously changed in the vicinity of λ _A = 0.2556 nm according to the Bragg condition. The wavelength λ _{1 at} which the intensity of the diffracted X-ray from the maximum is searched for, and a two-dimensional diffracted X-ray intensity distribution image at that wavelength is obtained. On the other hand, the wavelength of the incident X-ray is continuously changed in the vicinity of λ _R = 0.2775 nm to find the wavelength λ _{2 at} which the intensity of the diffracted X-ray from the (210) plane of the rutile crystal is maximum, and at that wavelength The two-dimensional diffraction X-ray intensity distribution image is acquired. Then, the value of each pixel of the diffracted X-ray intensity distribution image acquired for the (210) plane of the rutile crystal is used as the value of the corresponding pixel of the diffracted X-ray intensity distribution image acquired for the (200) plane of the anatase crystal. Two-dimensional weight ratio distribution in which each pixel value is a weight ratio obtained by dividing by, and applying to a conversion formula between the diffracted X-ray intensity ratio and the weight ratio prepared in advance using a sample with a known mixing ratio An operation for forming an image is performed in the image forming recording unit.

  Since each pixel of the created weight ratio distribution image has a one-to-one correspondence with each part in the region to be measured A, the anatase type of titanium oxide at each part in the region to be measured A from this weight ratio distribution image. The mixing ratio of crystals and rutile crystals can be known.

  In the apparatus shown in FIG. 2, the two-dimensional position sensitive detector 5 is fixedly arranged at a position where the scattering angle 2θ is 85 ° (detects diffracted X-rays emitted at 84 ° with respect to the sample surface). However, it may be arranged at another scattering angle position. However, if it is considered that the detection efficiency is increased by bringing the sample 3 as close as possible, a position for detecting a diffracted X-ray having an emission angle with respect to the sample surface that is one angle within a range of about 75 ° to 105 °. It is good to do. More preferably, it is desirable to arrange at an angular position as close as possible to the angular position facing the sample (detecting diffracted X-rays emitted at 90 ° with respect to the sample surface).

  Here, an example in which the viewing angle is 1 ° is shown, but the viewing angle does not have to be 1 °. However, in order to uniformly illuminate the entire measurement area A using incident X-rays having a wide and narrow linear cross section in the horizontal direction, the viewing angle cannot be increased too much. Further, when the viewing angle increases, it may be necessary to increase the distance between the two-dimensional position sensitive detector 5 and the sample 3 so as not to block the incident X-ray 2. Therefore, it is disadvantageous in terms of detection efficiency. Furthermore, if the sample 3 is a substrate in which a thin layer of titanium oxide is formed on the substrate, it is advantageous to reduce the incident angle in order to keep the background low. Therefore, as a guideline, it is preferable that the viewing angle is greater than 0 degree and less than or equal to 3 degrees with respect to the sample surface, which is so-called thin film arrangement. In addition, if a larger viewing angle is required due to the arrangement of the apparatus or the shape of the sample, the shape of the incident X-ray is slightly changed in order to uniformly illuminate the entire measurement area, and If the two-dimensional position sensitive detector is used at a distance, it is possible to obtain a desired image while sacrificing spatial resolution and detection efficiency.

Here, an example in which the (200) plane of the anatase crystal and the (210) plane of the rutile crystal are used in an apparatus in which the two-dimensional position sensitive detector is disposed at a position for detecting diffracted X-rays with a scattering angle of 85 degrees. However, the lattice plane to be used is the scattering angle position of the two-dimensional position sensitive detector and the wavelength range in which incident X-rays can be used (generally usable X-ray is 0). In many cases, the wavelength is shorter than about .31 nm (4 keV), and the K absorption edge of titanium, which is the limit on the short wavelength side, takes into account 0.2497 nm (4.97 keV), and the diffraction X-ray intensity In this arrangement, a (111) plane (d _R = 0.2188 nm, wavelength sweep in the vicinity of λ _R = 0.296 nm) may be used instead of the (210) plane of the rutile crystal. You may use The arrangement with a slightly smaller scattering angle than this arrangement is easier to use as the wavelength of incident X-rays, so long as the apparatus has a two-dimensional position sensitive detector at a position where the scattering angle 2θ = 100 °. The (200) plane (d _A = 0.1892 nm, wavelength sweeping in the vicinity of λ _A = 0.290 nm) is used as the lattice plane of the anatase crystal, and the (211) plane (d _R = 0.16874 nm is used as the lattice plane of the rutile crystal. , Λ _R = 0.259 nm (wavelength sweep) may be used.

For example, in an apparatus in which a two-dimensional position sensitive detector is arranged at a position where the scattering angle 2θ = 75 °, although it is not an optimum arrangement, the (103) plane (d _A = 0) is used as the lattice plane of the anatase crystal. 2431 nm, wavelength sweep near λ _A = 0.296 nm) or (004) plane (d _A = 0.2378 nm, wavelength sweep near λ _A = 0.290 nm) or (112) plane (d _A = 0.2332 nm) , Λ _A = 0.284 nm in the vicinity of a wavelength sweep) as a rutile crystal lattice plane (101) plane (d _R = 0.2487 nm, λ _R = 0.303 nm wavelength sweep) or (200) plane ( _{d R = 0.2297nm, λ R =} 0.280nm wavelength sweep in the vicinity) or (111) plane _{(d R = 0.2188nm, λ R} = 0.266nm wavelength sweep in the vicinity) is not impossible to use a .

  In the second embodiment, as the incident X-ray, a monochromatic X-ray having a wavelength longer than the wavelength of the K absorption edge of titanium, for example, a characteristic X-ray of titanium, particularly Kα ray, is used. With the sample fixed, the 2D position sensitive detector can be placed on the same plane as the sample surface without changing the correspondence between each part in the measurement area and each detection element of the 2D position sensitive detector. By changing the scattering angle of the diffracted X-rays detected by rotating (turning) around the rotation axis extending perpendicularly to the optical axis of the incident X-ray through the center of the region to be measured, A diffraction X-ray intensity distribution image of diffracted X-rays derived from a predetermined single lattice plane and a diffraction X-ray intensity distribution image of diffracted X-rays derived from a predetermined single lattice plane of a rutile crystal are obtained, and Take the ratio of the pixel values of the corresponding pixels in the image, and use the ratio value as each pixel value. The values of conversion and weight ratio to form a mixture ratio distribution image of the two-dimensional to each pixel value is recorded using the Rumoshikuwa previously obtained conversion formula.

For example, when titanium Kα rays are used, the wavelength of incident X-rays is determined to be λ ₀ = 0.2749 nm. Therefore, the Bragg condition (with respect to the lattice spacing d _A of the lattice plane of the anatase crystal is determined ( 2d _A sin θ _A = λ ₀ ) _A diffraction angle (scattering angle) 2θ _A satisfying a diffraction angle (scattering angle) 2θ _A is arranged to obtain a diffraction X-ray intensity distribution image, and a predetermined lattice of a rutile crystal A diffraction X-ray intensity distribution image is obtained by placing a two-dimensional position sensitive detector at a diffraction angle 2θ _R that satisfies the Bragg condition (2d _R sin θ _R = λ ₀ ) with respect to the lattice spacing d _{R of the} surface. _A two-dimensional intensity ratio distribution image is created by dividing the diffraction X-ray intensity distribution image of the rutile crystal acquired at the 2θ _R position by the diffraction X-ray intensity distribution image of the anatase crystal acquired at the 2θ _A position.

The reason why the monochromatic X-ray having a wavelength longer than the wavelength of the K absorption edge of titanium is used as the incident X-ray is that the fluorescent X-ray from the titanium is not generated, so that the background of the diffraction X-ray intensity distribution image can be kept low. It is. Theoretically, even if the Bragg angles satisfying the Bragg conditions with respect to the lattice spacings d _A and d _R are θ _A and θ _R , they may actually deviate slightly from these angles. When acquiring an intensity distribution image, the two-dimensional position sensitive detector is continuously rotated in the vicinity of each of the scattering angles 2θ _A and 2θ _B , and is angularly scanned and held at the detector angular position where the intensity is strongest. Thus, it is necessary to acquire a diffraction X-ray intensity distribution image (the angle scanning range varies depending on the condition of the sample, etc., but it is usually sufficient to scan about 2 ° across the diffraction angle).

Therefore, the two-dimensional position sensitive detector corresponds to at least 2θ _A and 2θ _R around the rotation axis extending perpendicularly to the optical axis of the incident X-ray through the center of the region to be measured in the sample plane. It is necessary to be able to rotate (swivel movement) in the angular region including the position, and in order to find the strongest intensity position by angle scanning, it is continuously rotated in the range of several degrees around each of these positions. It must be able to be held wherever possible. It is sufficient that the two-dimensional position sensitive detector can be moved in an angular region between these positions and not included in the angular scanning range for searching for the strongest intensity position. Therefore, the lattice plane representing each type of crystal needs to be a plane that generates diffracted X-rays having a scattering angle that can be detected by the two-dimensional position-sensitive detector in terms of the device configuration. Also in this embodiment, it is not always necessary to use the lattice plane that is the strongest line of each crystal type.

In FIG. 3, the conceptual diagram of the titanium oxide analyzer for implementing the titanium oxide analysis method which concerns on 2nd embodiment is shown. The X-ray generator 11 is a characteristic X-ray of titanium having a wavelength longer than the wavelength of the K absorption edge of titanium (Kα ray; wavelength 0.2749 nm, X-ray energy 4510 eV, Kβ ray: wavelength 0.2514 nm, X-ray energy) 4931 eV), which is fixedly held by the X-ray tube support section 20. The X-ray extraction window of the X-ray tube 11 includes a filter that absorbs Kβ rays. The filter is configured by directly applying a solution containing iodine or an iodine compound to the X-ray extraction window or attaching a polymer film formed by applying the solution. As a result, Kβ rays are absorbed and removed, and only titanium Kα rays are used as incident X-rays.
Therefore, in the drawing, incident X-rays 12 having a linear cross section that is wide in the substantially horizontal direction and emitted from the X-ray tube 11 are composed of titanium Kα rays. However, it is not always necessary to use a titanium tube to convert the titanium Kα ray into an incident X-ray. By using a monochromator or the like to monochromate continuous X-rays obtained from synchrotron radiation or a rotating cathode X-ray source. An incident X-ray having a wavelength longer than the wavelength of the K absorption edge of titanium may be obtained.

  The titanium oxide sample 13 has a viewing angle (angle formed by the optical axis of the incident X-ray and the sample surface) θi of 1 °, and the longitudinal direction of the incident X-ray cross section is substantially parallel to the sample surface. In addition, the entire measurement area A ′ indicated by hatching on the sample surface is fixed and held by the sample support portion 14 so as to be illuminated by the incident X-rays 12. A two-dimensional position sensitive detector 15 in which a plurality of detection elements are two-dimensionally arranged is incident X-rays by the detector support 16 through the center of the measurement area A ′ in the same plane as the sample surface. It is held so as to be rotatable (turnable) around a rotation axis 19 extending perpendicularly to the twelve optical axes. In the case of the apparatus shown in FIG. 3, the two-dimensional position sensitive detector 15 has an angle formed by the normal of the detector surface and the optical axis of the incident X-ray (the scattering angle of the detected diffracted X-ray (the diffraction angle). ) Can be moved on an arc centered on the rotation axis 19 in the range of approximately 80 ° to 97 ° and can be held at a desired angular position within the angular range.

At any angular position within this angular range, the normal passing through the center of the detector surface points to the center of the measurement area A ′, and each detection element always expects the same part in the measurement area A ′.
Between the sample 13 and the two-dimensional position sensitive detector 15, angle divergence limiting means 17 is provided integrally with the two-dimensional position sensitive detector 15, and the diffraction X emitted from the measurement area A ′. Limits the angular divergence of the line 18 and extracts only the component approximately parallel to the normal of the detector plane. As a result, the diffracted X-rays 18 having one scattering angle emitted from each part having the same size as the detection element of the two-dimensional position sensitive detector 15 in the measurement area A ′ are opposed to each part on a one-to-one basis. Each detecting element to detect separately detects. Then, a two-dimensional diffraction X-ray intensity distribution image having the diffraction X-ray intensity detected by each detection element as each pixel is created and recorded by an image forming recording unit (not shown).

Using the apparatus shown in FIG. 3, the intensity of diffracted X-rays from the (200) plane (d _A = 0.1892 nm) of the anatase crystal and the (210) plane (d _R = 0.2054 nm) of the rutile crystal Λ ₀ = 0.2749 nm in the case of evaluating the mixing ratio of the two based on the ratio of the diffracted X-ray intensity to the two-dimensional position sensitive detector position according to the Bragg condition, the scattering angle is 2θ _A. = A scanning angle 2θ _{1 at} which the intensity of the diffracted X-ray from the (200) plane of the anatase crystal is maximized by rotating the angle near the position where it becomes = 93.18 ° is found. A two-dimensional diffraction X-ray intensity distribution image is acquired at the scattering angle position.

On the other hand, the intensity of the diffracted X-ray from the (210) plane of the rutile crystal is maximized by continuously rotating the two-dimensional position sensitive detector 15 in the vicinity of 2θ _R = 84.0 ° and performing angular scanning. locate the composed scattering angle 2 [Theta] _2, to obtain the two-dimensional diffraction X-ray intensity distribution image in the scattering angle position. Then, the value of each pixel of the diffracted X-ray intensity distribution image acquired for the (210) plane of the rutile crystal is used as the value of the corresponding pixel of the diffracted X-ray intensity distribution image acquired for the (200) plane of the anatase crystal. Two-dimensional weight ratio in which each pixel value is a weight ratio obtained by dividing it by a conversion formula between a diffraction X-ray intensity ratio and a weight ratio prepared in advance using a sample with a known mixing ratio. A distribution image is created and recorded in the image formation recording unit. Since each pixel of the created weight ratio distribution image has a one-to-one correspondence with each part in the measurement area A ′, titanium oxide at each part in the measurement area A ′ is determined from this weight ratio distribution image. The mixing ratio of the anatase type crystal and the rutile type crystal can be known.

The rotation angle range of the two-dimensional position sensitive detector 15 is approximately 80 ° to 97 ° in the apparatus shown in FIG. 3, but this angle range varies depending on the lattice plane to be noticed. For example, if the (200) plane is left as the target for the anatase type crystal, and the (101) plane of the rutile type crystal (d _R = 0.2487 nm, angle scan near 2θ _R = 67.10 °) is used, If the rotation angle range is approximately 63 ° to 97 ° and the (111) plane of rutile crystal (d _R = 0.2188 nm, angular scanning near 2θ _R = 77.8 °) is used, approximately 74 ° to 97 If the (211) plane of rutile crystal (d _R = 0.16874 nm, angle scan in the vicinity of 2θ _R = 109.09 °) is used, the angle may be approximately 89 ° to 113 °.

However, since the distance between the two-dimensional position sensitive detector 15 and the sample 13 is always fixed, the diffracted X-rays are efficiently detected by bringing them as close as possible within a range in which the incident X-rays are not blocked by any member. With this in mind, it is desirable to select the lattice plane to be noted so that the rotation angle range is as narrow as possible in the vicinity of 90 °.
Although it is an unfavorable angle in terms of the configuration of the apparatus, in principle, the (103) plane of anatase type crystal (d _A = 0.2431 nm, angle scan in the vicinity of 2θ _A = 68.86 °), (004) plane (D _A = 0.2378 nm, angle scan near 2θ _A = 70.62 °), (112) plane (d _A = 0.2332 nm, angle scan near 2θ _A = 72.23 °), etc. The intensity ratio may be examined.

  2 and 3, the samples 3 and 13 and the two-dimensional position sensitive detectors 5 and 15 are as far as possible in the range where the incident X-rays are not blocked by the angle divergence limiting means 7 and 17. It is advantageous in terms of the intensity of diffracted X-rays to be close.

  As the angle divergence limiting means 7 and 17, a capillary plate in which synthetic silica capillaries (for example, 6 microns in diameter and 1 mm in length) are assembled in a disk shape (for example, 20 mm in diameter) as shown in FIG. And the like which have been processed in the same manner.

As the two-dimensional position sensitive detectors 5 and 15, a multi-element semiconductor detector, a CCD camera having an X-ray detection capability, a CMOS image sensor, or the like can be used. Instead of directly detecting X-rays, a detector having a scintillator that emits light by X-rays and detecting the light emitted from the scintillator may be used.

  The image forming recording unit is a computer, records all data in the computer, and performs data processing and imaging processing. The function of the computer can be built in a two-dimensional position sensitive detector as a microchip, and includes it.

In order to confirm the effect of the present invention, about 8 mm (about 13 mm in diameter and 2 mm in thickness) of a sample in which powders of anatase type titanium oxide and rutile type titanium oxide as shown in FIG. X-rays (energy 4600 eV, wavelength 0.2695 nm) having a size of (horizontal) × about 0.4 mm (vertical) were incident at about 1 degree (imaging time 1 second × 100 times). The mixed distribution state of this sample is known. In the figure, R in the observation field is a region where a lot of rutile is distributed, and A is a region where a lot of anatase is distributed. X-rays were illuminated over the entire observation field of 8 mm square indicated by broken lines. 76 degrees (the rutile (210) plane, the angle at which reflection corresponding to d = 0.2054 nm is obtained) and 84 degrees (the anatase (200) plane, the angle at which reflection corresponding to d = 0.1892 nm is obtained) (B) and (c) are obtained by obtaining the X-ray images at two scattering angles and then extracting the distribution state of rutile titanium oxide and anatase titanium oxide by arithmetic processing. This result corresponds very well to the mixed state of the prepared sample, and it can be shown as a clear image that rutile and anatase have different distributions. The images of (b) and (c) show the distributions when the mixing ratio of rutile to anatase is 1: 0 and 0: 1, respectively. In addition, it is possible to indicate which part has a certain mixing ratio, for example, a mixing ratio such as 1: 1 or 2: 1, which part is large and which part is small, and (b) and (c)
An image showing what the mixing ratio at each of the points on the sample is can be obtained by simple division between the images.

The above X-ray image information is consistent with the actual distribution status, and can accurately identify the distribution status and quantity ratio of crystals in an actual sample developed two-dimensionally, both globally and locally. confirmed. On the other hand, when the sample shown in FIG. 5A is measured by a conventional powder X-ray diffractometer, the X-ray illuminates the R region and the A region at the same time. Since it is the average value of the intensity of the diffracted X-rays, it is completely unknown how the mixture is distributed and only the average mixture ratio of the entire region including the R region and the A region can be obtained. Therefore, using a small X-ray beam that can illuminate only a part of the sample, the measurement must be repeated while changing the position of the illuminated sample. It becomes too enormous and identification in a short time like the method according to the present invention is impossible.
The present invention analyzes the crystal mixing ratio information at each position of the sample in a short time by irradiating the entire surface with the X-ray for a short time while the X-ray irradiating part and the sample are fixed without moving. It can be provided and provides an excellent identification means.

  Titanium oxide is a substance that has been used for many applications such as electronic materials, catalyst materials, ultraviolet absorbers, photocatalysts, etc. for a long time, but its importance has been recognized and reviewed again in recent research. For example, a self-cleaning function that absorbs ultraviolet rays and decomposes adhering dirt by coating glass or a wall surface by using a function of decomposing harmful substances and naturally washing with rainwater is one example. Such an example is only an example and does not stop. In any case, as the use of titanium oxide progresses, it is required to accurately grasp, manage, or control the distribution state of the titanium oxide crystals to be constructed and thoroughly control the quality. It is clear that the present invention is a technology suitable for such a field, and it is expected that it will be widely adopted and spread in the technical field using titanium oxide in the future.

It is a conceptual diagram which shows what kind of X-ray image is acquired in this invention. (a) is a schematic diagram of a sample. Various crystal phases are distributed in different places in the observation field. (b) and (c) schematically show the acquired X-ray images. That is, (b) is an image of a portion where the lattice spacing is a specific value d ₁ , and (c) is an image of a portion where the lattice value is a specific value d ₂ . Furthermore, the amount can be known from the brightness of the image. It is a conceptual diagram of the titanium oxide analyzer for enforcing the titanium oxide analysis method which concerns on 1st embodiment of this invention. It is a conceptual diagram of the titanium oxide analyzer for enforcing the titanium oxide analysis method which concerns on 2nd embodiment of this invention. It is the external view which cut and shown partially the capillary plate which is an angle divergence limiting means used in the Example. This is an example applied to a titanium oxide sample (a) having a different distribution of rutile and anatase. (b) and (c) are obtained by extracting the distribution of rutile and anatase from experimentally obtained X-ray images.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 X-ray generation part 2 Incident X-ray 3 Titanium oxide sample 4 Sample support part 5 Two-dimensional position sensitive type detector 6 Detector support part 7 Angular divergence limiting means 8 Diffracted X-ray 9 Detector support part 11 X-ray generation part ( X-ray tube, titanium tube)
12 incident X-ray 13 titanium oxide sample 14 sample support 15 two-dimensional position sensitive detector 16 detector support 17 angle divergence limiting means 18 diffracted X-ray 19 rotation axis 20 X-ray tube support A measurement area A ′ Measurement area

Claims (20)

In the titanium oxide analysis method for obtaining a distribution image of the local mixing ratio of a titanium oxide sample in which anatase-type crystals and rutile-type crystals coexist in a heterogeneous manner,
Illuminate the entire region to be measured on the surface of the titanium oxide sample with a monochromatic incident X-ray having a wavelength longer than the wavelength of the titanium K absorption edge,
By limiting the angle divergence of the diffracted X-rays diffracted by the titanium oxide sample and emitted from the measurement region by the angle divergence limiting means, the diffracted X-rays having a predetermined scattering angle emitted from each part in the measurement region can be obtained. The two-dimensional position sensitive detectors placed one-on-one opposite to those parts are detected separately by each detection element,
Forming and recording a two-dimensional diffracted X-ray intensity distribution image with the intensity of diffracted X-rays detected by each detecting element as each pixel value;
While the optical axis of the incident X-ray, the titanium oxide sample, the angle divergence limiting means, and the two-dimensional position sensitive detector are fixed, the wavelength of the monochromatic incident X-ray is within the wavelength range longer than the wavelength of the K absorption edge of titanium. Diffracted X-ray intensity distribution image of diffracted X-rays derived from one predetermined lattice plane of anatase-type crystal and diffracted X-ray intensity distribution of diffracted X-rays derived from one predetermined lattice plane of rutile-type crystal Get an image,
Two-dimensional mixture ratio distribution by taking the ratio of the pixel values of the corresponding pixels of those images and setting the ratio value as each pixel value, or by further converting each pixel value to a predetermined value A method for analyzing titanium oxide, comprising forming and recording an image. In the titanium oxide analysis method for obtaining a distribution image of the local mixing ratio of a titanium oxide sample in which anatase-type crystals and rutile-type crystals coexist in a heterogeneous manner,
The entire region to be measured on the surface of the titanium oxide sample is illuminated with incident X-rays made of monochromatic X-rays having a wavelength longer than the wavelength of the K absorption edge of titanium, and is diffracted by the titanium oxide sample and emitted from the region to be measured. By restricting the angle divergence with the angle divergence limiting means, the diffracted X-rays emitted from the respective parts in the measured region can be detected by each of the two-dimensional position sensitive detectors arranged one-on-one facing these parts. Detect and distinguish with the detection element,
Forming and recording a two-dimensional diffracted X-ray intensity distribution image with the intensity of diffracted X-rays detected by each detecting element as each pixel value;
Two-dimensional position sensitive type without changing the correspondence between each part in the measurement area and each detection element of the two-dimensional position sensitive detector while fixing the optical axis of the incident X-ray and the titanium oxide sample Changing the scattering angle of diffracted X-rays detected by rotating the detector around a rotation axis extending perpendicularly to the optical axis of incident X-rays through the center of the region to be measured in the same plane as the sample surface The diffraction X-ray intensity distribution image of the diffracted X-ray derived from the predetermined one lattice plane of the anatase crystal and the diffracted X-ray intensity distribution image of the diffracted X-ray derived from the predetermined one lattice plane of the rutile crystal are Acquired,
Take a ratio of the pixel values of the corresponding pixels in those images, and use the ratio value as each pixel value, or a two-dimensional mixture ratio distribution image with each pixel value as a predetermined converted value. A method for analyzing titanium oxide, comprising forming and recording.   The method for analyzing titanium oxide according to claim 2, wherein the incident X-ray is a characteristic X-ray of titanium generated from a titanium X-ray tube.   The titanium oxide analysis method according to claim 3, wherein a filter that absorbs titanium Kβ rays is attached to the titanium X-ray tube.   The filter that absorbs Kβ rays is configured by directly applying a solution containing iodine or an iodine compound to an X-ray extraction window or by attaching a polymer film formed by applying the solution. The method for analyzing titanium oxide according to claim 4. The crystal lattice plane when acquiring a diffraction X-ray intensity distribution image on the predetermined one lattice plane is any one of (111) plane, (210) plane, and (211) plane in the rutile crystal. The diffraction X-ray intensity distribution image of the diffracted X-rays derived from each lattice plane is obtained in an anatase type crystal, which is (200) plane. The method for analyzing titanium oxide according to Item. In a titanium oxide analyzer that obtains a local mixing ratio distribution image of a titanium oxide sample in which anatase-type crystals and rutile-type crystals coexist in a heterogeneous manner,
An X-ray generator that generates monochromatic incident X-rays having a wavelength longer than the wavelength of the K absorption edge of titanium in an optical axis invariable and wavelength-variable manner is fixedly held;
The titanium oxide sample is fixedly held so that the incident X-rays emitted from the X-ray generation unit illuminate the entire region to be measured on the surface of the titanium oxide sample;
A two-dimensional position sensitive detector consisting of a plurality of detection elements arranged in two dimensions for detecting diffracted X-rays diffracted by the titanium oxide sample and emitted from the measurement region;
In order to distinguish and detect diffracted X-rays having a predetermined scattering angle emitted from each part in the measurement region by each detection element of the two-dimensional position sensitive detector facing the parts one-to-one, Angle divergence limiting means for limiting the angle divergence of the diffracted X-rays emitted from the measurement region is provided between the titanium oxide sample and the two-dimensional position sensitive detector,
An image forming recording unit for forming and recording a two-dimensional diffracted X-ray intensity distribution image with the intensity of the diffracted X-ray detected by each detecting element as each pixel value;
While the optical axis of the incident X-ray, the titanium oxide sample, the angle divergence limiting means, and the two-dimensional position sensitive detector are fixed, the diffraction X-ray derived from a predetermined lattice plane of the rutile crystal In order to acquire a diffracted X-ray intensity distribution image and a diffracted X-ray intensity distribution image of diffracted X-rays derived from a predetermined one lattice plane of the anatase type crystal, the X-ray generation unit is at least a lattice of those lattice planes. The ability to generate monochromatic incident X-rays of two different wavelengths corresponding to the spacing;
The image forming recording unit uses each pixel value as a ratio of pixel values of corresponding pixels of the diffraction X-ray intensity distribution image acquired for the rutile crystal and the diffraction X-ray intensity distribution image acquired for the anatase crystal. Alternatively, the titanium oxide analyzer can form and record a two-dimensional mixture ratio distribution image in which each pixel value is a value obtained by performing a predetermined conversion.   The titanium oxide analyzer according to claim 7, wherein the wavelength of the incident X-ray can be continuously changed in a desired range with the two types of wavelengths as the centers.   The titanium oxide sample is fixed and held so that the viewing angle is between 0 ° and 3 °, and the incident X-ray has a wide linear cross section in a direction parallel to the sample surface. The two-dimensional position sensitive detector is fixedly held at a position for detecting diffracted X-rays having one exit angle within a range of 75 to 105 degrees with respect to the sample surface. Item 9. The titanium oxide analyzer according to Item 7 or Item 8.   The crystal lattice plane when acquiring a diffraction X-ray intensity distribution image on the predetermined one lattice plane is any one of (111) plane, (210) plane, and (211) plane in the rutile crystal. The diffraction X-ray intensity distribution image of the diffracted X-rays derived from each lattice plane is obtained in an anatase-type crystal (200) plane. The titanium oxide analyzer described in the item. In a titanium oxide analyzer that obtains a local mixing ratio distribution image of a titanium oxide sample in which anatase-type crystals and rutile-type crystals coexist in a heterogeneous manner,
An X-ray generator that generates incident X-rays having a monochromatic X-ray having a wavelength longer than the wavelength of the K absorption edge of titanium is fixed and held, and the incident X-rays emitted from the X-ray generator are converted into the titanium oxide. The titanium oxide sample is fixed and held so as to illuminate the entire measurement area on the surface of the sample,
A two-dimensional position sensitive detector composed of a plurality of two-dimensionally arranged detection elements for detecting diffracted X-rays diffracted by the titanium oxide sample and emitted from the measurement region is the same plane as the sample surface Is disposed so as to be rotatable around a rotation axis extending through the center of the region to be measured and extending perpendicularly to the optical axis of the incident X-ray,
In order to distinguish and detect diffracted X-rays of one scattering angle emitted from each part in the measurement target region with each detection element of the two-dimensional position sensitive detector facing the parts one-to-one, An angle divergence limiting means for limiting the angle divergence of the diffracted X-rays emitted from the measurement region is provided integrally with the two-dimensional position sensitive detector between the titanium oxide sample and the two-dimensional position sensitive detector. Being done,
An image forming recording unit for forming and recording a two-dimensional diffracted X-ray intensity distribution image with the intensity of the diffracted X-ray detected by each detecting element as each pixel value;
The diffraction X-ray intensity distribution image of the diffracted X-ray derived from the predetermined one lattice plane of the rutile type crystal and the predetermined one lattice plane of the anatase type crystal with the X-ray generation portion and the titanium oxide sample fixed. In order to obtain a diffracted X-ray intensity distribution image of the derived diffracted X-ray, the two-dimensional position sensitive detector changes a correspondence relationship between each part in the measurement target region and each detection element. Without being able to be held at an angular position for detecting diffracted X-rays of two scattering angles respectively corresponding to the lattice spacing of at least their lattice planes,
The image forming recording unit sets each pixel value as a ratio of pixel values of corresponding pixels of the diffracted X-ray intensity distribution image acquired for the rutile crystal and the diffracted X-ray intensity distribution image acquired for the anatase crystal, or Furthermore, a titanium oxide analyzer characterized in that it can form and record a two-dimensional mixture ratio distribution image in which each pixel value is a value after a predetermined conversion.   The titanium oxide analyzer according to claim 11, wherein the X-ray generation unit includes an X-ray tube that generates characteristic X-rays of titanium.   13. The X-ray generator according to claim 11 or 12, wherein the X-ray generation unit includes a filter that absorbs titanium Kβ rays, and titanium Kα rays are emitted as the incident X-rays. Titanium oxide analyzer.   The filter that absorbs Kβ rays is configured by an X-ray extraction window directly coated with a solution containing iodine or an iodine compound, or an X-ray extraction window to which a polymer film coated with the solution is attached. The titanium oxide analyzer according to claim 13, wherein the titanium oxide analyzer is a thing.   The two scattering angles are 77.80 ° and 93.18 °, and the crystal lattice plane when the diffraction X-ray intensity distribution image on the predetermined one lattice plane is acquired is (111) in the rutile crystal. The diffraction X-ray intensity distribution image of the diffracted X-ray derived from each lattice plane is obtained in the ()) plane and the (200) plane in the anatase type crystal. Titanium oxide analyzer.   The two scattering angles are 84.00 ° and 93.18 °, and the crystal lattice plane when acquiring the diffraction X-ray intensity distribution image on the predetermined one lattice plane is (210 The diffracted X-ray intensity distribution image of the diffracted X-rays derived from each lattice plane is acquired in the anatase type crystal according to claim 13 or claim 14. The described titanium oxide analyzer.   The two scattering angles are 109.09 ° and 93.18 °, and the crystal lattice plane when obtaining the diffraction X-ray intensity distribution image on the predetermined one lattice plane is (211 in the rutile crystal. The diffracted X-ray intensity distribution image of the diffracted X-rays derived from each lattice plane is acquired in the anatase type crystal according to claim 13 or claim 14. The described titanium oxide analyzer.   The crystal lattice plane when acquiring a diffraction X-ray intensity distribution image on the predetermined one lattice plane is any one of (111) plane, (210) plane, and (211) plane in the rutile crystal. The diffracted X-ray intensity distribution image of the diffracted X-rays derived from each lattice plane is obtained in the anatase type crystal, which is a (200) plane. Titanium oxide analyzer.   The two-dimensional position sensitive detector can continuously operate in a desired angle range around the two scattering angles without changing the correspondence between each part in the measurement region and each detection element. The titanium oxide analyzer according to any one of claims 11 to 18, characterized in that the titanium oxide analyzer can be rotated at any angle and can be held at an arbitrary angular position within the angular range.   The titanium oxide sample is fixed and held so that the viewing angle is between 0 ° and 3 °, and the incident X-ray has a wide linear cross section in a direction parallel to the sample surface. The titanium oxide analyzer according to any one of claims 11 to 19, wherein the titanium oxide analyzer is characterized in that