JP2007271553A - Physical property evaluation method of sample, and physical property evaluating device of semiconductor material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method which enables simple and quick evaluation of the physical properties of semiconductor material consisting of metal oxide particles or metal sulfide particles, in particular, constitutional component consisting of amount of crystal defects, degree of crystallization and crystalline form type and/or amorphous type, using a nondestructive means and additionally, to provide a physical property evaluating device used for the implementation of these methods. <P>SOLUTION: The physical property evaluating method of samples, irradiated with an exciting light, measuring the amounts of luminescences at a specific wavelengths generated from irradiation with the exciting light is characterized by measuring the amount of luminescence at the specific wavelength of the reference sample where physical property used as evaluation object is known; preliminarily deriving correspondence between physical properties of the reference sample and the amount of luminescence measured; measuring the amount of luminescence at the specific wavelength of a test sample, where physical property used as evaluation object is unknown; and finally evaluating the physical property of the test sample concerned through the comparison of the amount of luminescence from the test sample measured with the correspondence to the reference sample. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for evaluating physical properties of a sample and a physical property measuring apparatus used for the method, and more specifically, the amount of crystal defects, the degree of crystallinity, or the crystallinity of a semiconductor material composed of metal oxide particles or metal sulfide particles. The present invention relates to a method for simply evaluating physical properties such as constituent components (crystalline type and / or non-crystalline type) and a physical property evaluation apparatus for semiconductor materials used in the method.

As a semiconductor electrode of a dye-sensitized (wet) solar cell, a sintered body of metal oxide nanoparticles such as titanium oxide (TiO ₂ ), zinc oxide (ZnO), or magnesium oxide (MgO) is generally used. Has been used. It is known that the performance of a solar cell is easily influenced by the electrode material used and greatly depends on the amount of crystal defects such as nanoparticles and the degree of crystallization. This is thought to be because electrons injected from the dye into crystal defects and amorphous (amorphous) portions are trapped and react with substances in the electrolytic solution to reduce the current (for example, Non-Patent Document 1). reference.).

On the other hand, semiconductor materials made of metal oxide or metal sulfide particles such as TiO ₂ and ZnO are generally used as photocatalytic materials, and it is known that the photocatalytic performance is greatly influenced by the amount of crystal defects and the degree of crystallinity. Yes. This is considered to be because photoexcited electrons are trapped in crystal defects and amorphous (amorphous) portions, and a recombination reaction with holes occurs (for example, see Non-Patent Document 2).

As a means currently used as a method for evaluating the physical properties of a semiconductor material composed of metal oxide particles such as TiO ₂ and ZnO, for example, regarding the amount of crystal defects, the amount of electrons accumulated in a sample by a photochemical reaction is detected. Thus, a method for measuring the amount of crystal defects is known (for example, see Non-Patent Document 3 or 4). There is no other known technique for measuring the amount of crystal defects for powders. However, this measurement method is complicated and requires a long time, and is a destructive measurement. In addition, as a method for evaluating the physical properties of photocatalytic materials, crystal type measurement by X-ray diffraction method and specific surface area measurement by adsorption method are known, but the former is expensive and requires high-level maintenance management. The latter is a method that requires pretreatment and cannot be said to be non-destructive.

As described above, in semiconductor materials composed of metal oxides such as TiO ₂ and ZnO and sulfide particles, the physical properties such as the amount of crystal defects and the degree of crystallinity have a great influence on the performance, but the physical property evaluation is simple and easy. In fact, there is no technology that can be evaluated in a short time and non-destructively.
Kambe, S .; Murakoshi, K .; Kitamura, T .; Yanagida, S .; Kominami, H .; Kera, Y .; Solar Energy Mater.Solar Cells, 61, 427-441 (2000). Ohtani, B .; Kominami, H .; Bowman, RM; Colombo Jr., P .; Noguchi, H .; Uosaki, K .; Chem. Lett., 579-580 (1998). Ikeda, S .; Sugiyama, N .; Pal, B .; Ohtani, B .; Noguchi, H .; Uosaki, K .; Marci, G .; Palmisano, L., "Photocatalytic Activity of Transition-Metal-Loaded Titanium (IV) Oxide Powders Suspended in Aqueous Solutions: Correlation with Electron-Hole Recombination Kinetics, Phys. Chem. Chem. Phys., 3, 267-273 (2001). Ikeda, S .; Sugiyama, N .; Murakami, SS-y .; Kominami, H .; Kera, Y .; Noguchi, H .; Uosaki, K .; Phys. Chem. Chem. Phys., 5, 778- 783 (2003).

  The present invention has been developed in view of the above-described background art. From the physical properties of a semiconductor material composed of metal oxide particles or metal sulfide particles, particularly from the amount of crystal defects, crystallinity, crystal type and / or amorphous type. It is an object of the present invention to provide a method capable of simply and rapidly evaluating the constituent components by non-destructive means, and to provide an evaluation apparatus for these physical properties used for carrying out the method.

  As a result of intensive studies to solve the above problems, the present inventors evaluated the physical properties such as the amount of crystal defects and the degree of crystallinity by detecting the emission spectrum generated when the semiconductor material is irradiated with light. Found to get. That is, in the detected emission spectrum, it is found that there is a correlation between the amount of luminescence at a specific wavelength and the amount of crystal defects, the degree of crystallinity, and the constituents composed of crystalline and / or amorphous types. In addition to completing a physical property evaluation method for destructive semiconductor materials, a physical property evaluation apparatus used in the implementation of this method has also been completed.

  That is, according to the present invention, a sample physical property evaluation method for irradiating a sample with excitation light and measuring a light emission amount at a specific wavelength generated by the irradiation of the excitation light, the reference sample having a known physical property to be evaluated The light emission amount at a specific wavelength is measured, and the correspondence between the physical properties of the reference sample and the measured light emission amount is obtained in advance, and the light emission amount at a specific wavelength of the sample to be measured whose physical properties to be evaluated are unknown And measuring the physical properties of the sample to be measured by comparing the measured amount of luminescence of the sample to be measured with the correspondence obtained for the reference sample. Is provided. Here, the physical properties to be evaluated include at least one of the amount of crystal defects, the degree of crystallinity, or a constituent component composed of a crystalline form and / or an amorphous form and the content thereof.

In the physical property evaluation method of the present invention, the sample to be measured includes a semiconductor material made of metal oxide or sulfide particles. Examples of the semiconductor material include titanium oxide (TiO ₂ ), zinc oxide (ZnO), cadmium sulfide (CdS), and the like. Among them, the semiconductor material is suitably used for evaluating physical properties of a semiconductor material made of titanium oxide (TiO ₂ ).

  In the case where the physical property to be evaluated is the amount of crystal defects or the degree of crystallinity, the specific wavelength may be light having a central wavelength of 1270 ± 20 nm or 620 ± 20 nm.

Further, in the case where the physical property to be evaluated is a crystalline type and / or an amorphous type (component), the specific wavelength is derived from a reference sample having a known constituent of the crystalline type and / or the amorphous type. Two emission peak wavelengths 1 and 2, and a correspondence relationship between the ratio of the light emission amount at the emission peak wavelengths 1 and 2 and the constituents composed of the crystalline type and / or the amorphous type is obtained in advance. Alternatively, the ratio of the luminescence amount at the emission peak wavelengths 1 and 2 of the sample to be measured whose constituent components are of an amorphous type is unknown was measured, and the ratio of the luminescence amount of the obtained sample to be measured and the reference sample were obtained. By comparing the correspondence, the constituent components of the sample to be measured, that is, the crystalline form and / or the amorphous form, and the content thereof can be evaluated. At that time, when the measurement sample is a semiconductor material made of titanium oxide TiO ₂ , the two emission peak wavelengths 1 and 2 are in a wavelength range of 560-580 nm and 620-640 nm.

  Furthermore, according to the present invention, there is provided a physical property evaluation apparatus used in the physical property evaluation method, comprising a light irradiation means having a specific wavelength and a weak light emission measurement means.

  Further, according to the present invention, there is provided a physical property evaluation apparatus used in the physical property evaluation method for irradiating light to a sample cell, a sample chamber for storing the sample cell, and a sample to be stored in the sample cell. There is provided a physical property evaluation apparatus comprising: a light irradiation means; a light emission intensity measuring means for measuring light emission intensity generated from the sample; and a spectroscopic mechanism provided between the sample chamber and the light emission intensity measuring means. Is done.

  In this embodiment, in one aspect, an optical filter, a spectroscope, or a light receiving element is used as the spectroscopic mechanism, and a grating or the like is preferably used as the spectroscope.

  In another aspect, the sample cell and / or the sample chamber is formed of a material that does not include a substance that is excited by irradiated light.

  In another aspect, the sample chamber includes a gas inlet and a gas outlet for replacing the atmosphere of the sample to be accommodated in the sample cell with an inert gas atmosphere.

  Moreover, in another aspect, a laser light source is used as a light irradiation means, and this laser light source can be 300-450 nm.

According to the present invention, in selecting a material used for a product using a semiconductor material made of metal oxide particles or metal sulfide particles, for example, a solar cell having a semiconductor electrode made of TiO ₂ or a product having a photocatalytic effect, It has become possible to provide a simple quality evaluation technique that can be carried out in a short time by destruction.

Hereinafter, the present invention will be described in detail.
As described above, the physical property evaluation method according to the present invention includes a light emission amount at a specific wavelength generated by irradiation of excitation light to a semiconductor material, a crystal defect amount, crystallinity, crystal type and / or non-crystal in the material. Developed on the basis of the knowledge that there is a correlation with the constituent components of the mold, and evaluates the physical properties by irradiating the material with excitation light and measuring the amount of light emitted at the specific wavelength generated by the irradiation of the excitation light Is the method.

  First, for a plurality of materials (reference samples) whose physical properties to be evaluated are known, such as crystal defects, crystallinity, or constituents composed of crystalline and / or amorphous types, emission spectra generated by irradiation with excitation light are calculated. The correspondence between the physical properties of the reference sample and the light emission amount at the specific wavelength is obtained in advance by measuring the light emission amount at the specific wavelength. Next, the amount of luminescence at the same specific wavelength is measured for a material (sample to be measured) whose physical properties to be evaluated are unknown, and the physical properties of the sample to be measured are compared with the corresponding relationship obtained for the reference sample. That is, the degree of crystal defects and the degree of crystallinity, or the constituents composed of crystalline and / or non-crystalline types and the contents thereof are measured. In the present invention, the crystallinity can be evaluated by measuring the specific surface area. That is, for example, when the specific surface area is small, the particle size is large and the crystallinity is high.

The material whose physical properties are evaluated in the present invention is mainly a powder or solid semiconductor material, for example, metal oxide particles such as titanium oxide (TiO ₂ ), zinc oxide (ZnO), or magnesium oxide (MgO). And semiconductor materials made of metal sulfide particles.

  As a result of intensive studies by the present inventors, according to one aspect of the present invention, when titanium oxide is used as the material and the physical property to be evaluated is the amount of crystal defects or the degree of crystallinity, the specific wavelength is 1270 nm ± Light having a central wavelength at 20 nm (1250 to 1290 nm) or 620 nm ± 20 nm (600 to 640 nm) may be measured. Specifically, Examples 1 to 3 and 5 described later can be referred to.

  As described above, the following inference can be made for measuring the light having the center wavelength of 1270 nm ± 20 nm as the specific wavelength. That is, titanium oxide absorbs light having energy of about 3 eV or more, which is the forbidden band width, and electrons in the valence band are excited to the conduction band, resulting in generation of excited electrons and holes. Next, excited electrons and holes are considered to take the following three processes (for example, 1) Yoshio Nosaka and Atsuko Nosaka, “Introductory Photocatalyst”, Tokyo Book, 2004, Chapter 3, “Photocatalytic Reaction Mechanism”) . First, the process in which excited electrons and holes recombine to release heat, second, the process in which excited electrons and holes recombine to emit light, and third, The process of reacting with chemical substances. Of these, the first process is likely to occur in crystal defects and non-crystallized portions, and therefore occurs in a sample having a large amount of crystal defects and low crystallinity over other processes. The second process is known to be almost negligible when the titanium oxide is placed at room temperature, and the light emission is actually so small that it cannot be detected in an inert gas atmosphere. Various processes are known for the third process, but in normal air, the main reaction is that excited electrons react with oxygen molecules. The resulting superoxide anion radical is known to react with holes to become singlet oxygen with greater energy than normal oxygen molecules (triplet state) unless a particularly reactive chemical is added. . As mentioned above, the second process is negligible, so the smaller the amount of crystal defects and the higher the degree of crystallinity, the lower the proportion of excited electrons and holes that take the first process, resulting in the third process. Increases the amount of singlet oxygen produced by. Singlet oxygen mainly emits light having a wavelength of 1270 nm when it loses its energy and is converted into triplet oxygen. It is this luminescence that is detected in one embodiment of the present invention.

  Further, according to another aspect of the present invention, when the physical property to be evaluated is a constituent component consisting of a crystalline type and / or an amorphous type and its content, two emission peak wavelengths 1 as the specific wavelength And 2, specifically, in the emission spectrum obtained by excitation light irradiation, by measuring the emission amount in each of the emission peaks 1 and 2 seen in the wavelength range of 560-580 nm and 620-640 nm, and measuring the ratio between them, It is possible to measure a constituent component consisting of a crystalline form and / or an amorphous form and the content thereof. Specifically, Example 4 described later can be referred to.

In the physical property evaluation method according to the present invention, it is necessary to measure the emission spectrum generated by the excitation light irradiation to the material with high sensitivity, and the physical property evaluation that can be suitably used in the implementation of the physical property evaluation method according to the present invention. As the apparatus, there is provided a physical property evaluation apparatus including a light irradiation unit having a specific wavelength and a weak emission measuring unit capable of observing an emission spectrum with low noise and high sensitivity. FIG. 1 shows an embodiment of a physical property evaluation apparatus according to the present invention, which is used for irradiating light to a sample cell 1, a sample chamber 2 for storing the sample cell, and a sample to be stored in the sample cell 1. Light irradiation means 10, light emission measurement means 11 for measuring the light emission intensity generated from the sample, optical filter 12 provided between the light emission measurement means 11, and heating means 13 provided below the sample chamber The sample chamber 2 further includes a gas inlet 3 and a gas outlet 4 for replacing the atmosphere in the sample chamber with an inert gas atmosphere. The optical filter 12 is an example of a spectroscopic mechanism. The sample cell 1 and / or sample chamber 2 is preferably formed of a material that does not contain a substance excited by irradiated light, that is, a high-purity substance. For example, SiO ₂ , high-purity glass Specific examples include high-purity quartz glass, stainless steel, Si, and SiC. Further, a laser light source can be used as the light irradiation means 10.

(Example 1) Relationship between light emission amount of 1270 nm ± 20 nm and crystal defect amount Chemiluminescence detection (CL-detection) is a book in which emission spectrum can be observed with high sensitivity and low noise as shown in FIG. Using the physical property evaluation apparatus of the invention, it was performed while irradiating with a laser.

In the present embodiment, in the apparatus shown in FIG. 1, a light emission detector chemiluminescence analyzer model CLA-310 (detection wavelength region 300-1400 nm) is used as the light emission measuring means 11, a laser light source is used as the light irradiation means 10, and a spectral filter is further used. A device in which a 1270 ± 21.6 nm band-pass filter and an ND filter (10 ⁻³ ) for adjusting the light emission amount were set for measuring 1270 nm emission was used.

Then, ₂ g each of anatase-type and rutile-type titanium oxide particles TiO ₂ were prepared as samples to be measured (reference samples) (see FIG. 2, Table 1 below). The reference sample was weighed in a 50 mmφ sample cell 1 (stainless steel petri dish) and set in the sample chamber 2. The wavelength of the laser light was 408 nm, the irradiation output was 6 mW, the measurement time of chemiluminescence was 30 seconds, and the average value was obtained.

2A and 2B are plots of the relationship between the amount of luminescence at 1270 nm of the titanium oxide particles TiO ₂ (reference sample) detected in the above measurement and the reciprocal of the amount of crystal defects. FIG. 2A shows anatase-type titanium oxide. FIG. 2B relates to a rutile type titanium oxide. Here, the amount of crystal defects is a method of measuring the amount of electrons accumulated in a sample by a photochemical reaction, and is obtained according to the measurement method described in Non-Patent Document 4 mentioned in the section of the background art.

  From FIG. 2A and FIG. 2B, in both anatase type titanium oxide and rutile type titanium oxide, there is a correlation between the light emission amount at 1270 nm and the crystal defect amount, and the higher the 1270 nm light emission amount, the smaller the crystal defect amount. It was confirmed. Then, the amount of light emission at a specific wavelength is measured for a small number of reference samples whose degree of crystal defects is known, and the correspondence between the degree of crystal defects in the reference sample and the amount of light emission as seen in FIGS. 2A and 2B. If it is obtained, it becomes possible to evaluate the amount of crystal defects of a sample to be measured whose degree of crystal defects is unknown by a simple method called light emission measurement by comparison with this. In addition, since the production efficiency of the superoxide anion radical is different depending on the difference between the crystal form of the anatase type and the rutile type, when comparing FIG. 2A and FIG. 2B, it is presumed that there is a difference in the slope of the straight line. If the absolute value of the crystal defect amount is measured by the method described in Non-Patent Document 4 for a small number of reference samples and the inclination is obtained for each crystal, the absolute value of the crystal defect amount is obtained by the evaluation method according to the present invention. I can know.

(Example 2) Relationship between 1270 nm emission amount and crystallinity (specific surface area) The specific surface area of the sample to be measured (reference sample) used in Example 1 was determined by the BET method (see Table 1). . 2C and 2D are plots of the relationship between the amount of emitted light at 1270 nm and the specific surface area. FIG. 2C relates to anatase-type titanium oxide, and FIG. 2D relates to a rutile-type titanium oxide. Here, the specific surface area was calculated based on the BET equation from the nitrogen adsorption amount at 77K.

From FIG. 2C and FIG. 2D, there is no correlation between the emission amount at 1270 nm and the specific surface area for the anatase type titanium oxide, but there is a correlation between the emission amount of 1270 nm and the specific surface area for the rutile type titanium oxide. It was confirmed that the higher the 1270 nm emission amount, the smaller the specific surface area (that is, the larger the particle size and the higher the crystallinity). Therefore, if the light emission amount at a specific wavelength is measured for a small number of reference samples whose specific surface area is known, and the correspondence between the specific surface area of the reference sample and the light emission amount as seen in FIGS. 2C and 2D is obtained, By comparison with this, it is possible to evaluate the specific surface area of the sample to be measured whose degree of specific surface area is unknown, and hence the degree of crystallinity, by a simple method of luminescence measurement.

(Example 3) Relationship between 1270 nm luminescence amount with time and crystallinity (specific surface area) The luminescence amount detected in the luminescence measurement varies depending on the measurement time, and the variation in the luminescence amount varies depending on the measurement sample. Thus, in this example, the amount of change in the amount of emitted light at 1270 nm 150 seconds after the start of measurement was measured (FIG. 3A, Table 2), and the relationship between the amount of change and the specific surface area (BET) was determined (FIG. 3B). ). Luminescence measurement was performed under the same measurement conditions as in Example 1 except that the physical property evaluation apparatus according to the present invention used in Example 1 was used and the irradiation output was changed to 10 mW.

From FIG. 3B, in the titanium oxide particles, there is a negative correlation between the amount of change in the amount of emitted light at 1270 nm and the specific surface area, and the larger the specific surface area (that is, the lower the degree of crystallinity), the more the amount of emitted light changes. It was confirmed to be small. Therefore, the change in the amount of luminescence for a predetermined time at a specific wavelength is measured for a small number of reference samples whose specific surface area is known, and the correspondence between the specific surface area of the reference sample and the amount of change over time of the luminescence amount as seen in FIG. 3B. Thus, by comparison with this, it is possible to evaluate the specific surface area of the sample to be measured whose degree of specific surface area is unknown, and thus the degree of crystallinity, by a simple method of luminescence measurement.

Example 4 Relationship between Crystal Component and Peak Ratio of Emission Spectrum ₂ g of anatase and rutile type titanium oxide particles TiO ₂ were prepared as samples to be measured (reference samples) (FIG. 4A, Table 1). Reference :), measurement similar to that of Example 1 except that the physical property evaluation mechanism according to the present invention used in Example 1 is used, a device in which detection devices having different measurement wavelengths are combined, and the spectral filter is changed. Luminescence was measured under the conditions (408 nm laser excitation) to obtain an emission spectrum shown in FIG.

  In each emission spectrum shown in FIG. 4, the emission peak at 420 nm is considered to be derived from the light source. As a feature, although the emission peaks derived from the sample are seen at 560 nm-580 nm and 620 nm-640 nm, It is mentioned that the ratio of the light emission amount at the 560 nm-580 nm peak and the 620 nm-640 nm peak differs depending on the sample.

  Regarding the emission spectrum of each measurement sample, the ratio of the emission amount of the 560 nm-580 nm peak and the emission amount of the 620 nm-640 nm peak was determined, and this ratio was shown in FIG. 5 together with the constituent components (crystal type) of the sample.

  From FIG. 5, there is a correlation between the crystal form of the titanium oxide particles and the light emission ratio at the 560 nm-580 nm peak and the 620 nm-640 nm peak of the emission spectrum, and the ratio of the anatase type between the rutile type and the anatase type It was confirmed that the ratio of 620-640 nm emission amount / 560 nm-580 nm emission amount increased as the value increased. Therefore, if the emission spectrum is detected for a small number of reference samples whose crystal types are known, and the correspondence between the crystal type of the reference samples and the emission amount ratio as shown in FIG. Thus, it is possible to evaluate the crystal component of the sample to be measured in which the constituent component of the crystal is unknown by a simple method of luminescence measurement.

(Example 5) Relationship between 620 nm light emission amount, crystal defect amount, and crystallinity (specific surface area) In this example, the light emission amount and crystal defect amount at a measurement wavelength of 620 nm with respect to the measurement wavelength of 1270 nm in Examples 1 and 2. As well as the relationship with crystallinity (specific surface area), luminescence measurement was performed. As the sample to be measured (reference sample), ₂ g each of the same anatase type and rutile type titanium oxide particles TiO ₂ as in Examples 1 and 2 were prepared (see FIG. 6 and Table 1), and the same book as in Examples 1 and 2 Using the physical property evaluation apparatus of the invention, the measurement was performed under the same measurement conditions as in Examples 1 and 2 except for the measurement wavelength.

  6A and 6C, in the case of anatase type titanium oxide, the emission characteristic at the measurement wavelength of 620 nm is positively correlated with the emission characteristic at the measurement wavelength of 1270 nm, and the crystal defect becomes higher as the emission amount of 620 nm is higher as in the case of the measurement wavelength of 1270 nm. It was confirmed that the specific surface area was smaller (that is, the degree of crystallinity was higher) as the amount was smaller and the light emission amount at 620 nm was higher.

  On the other hand, from FIGS. 6B and 6D, it was found that in the case of rutile type titanium oxide, the emission characteristics at the measurement wavelength of 620 nm are negatively correlated with the emission characteristics at the measurement wavelength of 1270 nm. Therefore, in the case of rutile-type titanium oxide, the emission at 620 nm is considered to originate from a factor different from single photooxygen. However, the higher the 620 nm emission amount, the more the crystal defect amount, while the higher the 620 nm emission amount, the higher the ratio. It was confirmed that the surface area was large (that is, the crystallinity was low).

  Therefore, for both the anatase type and the rutile type rutile oxide, a correspondence method as shown in FIGS. 6A to D is obtained from a minority reference sample at a measurement wavelength of 620 nm. Thus, it is possible to evaluate a sample to be measured whose crystal defect amount or crystallinity is unknown.

The figure which shows typically the one aspect | mode of the physical-material evaluation apparatus of the semiconductor material of this invention. Graph showing the relationship between 1270nm light emission amount of anatase TiO ₂ and the crystal defect amount. Graph showing the relationship between 1270nm light emission amount and the crystal defects of rutile TiO _2. Graph showing the relationship between 1270nm light emission amount and the specific surface area of the anatase type TiO _2. Graph showing the relationship between 1270nm light emission amount and the specific surface area of the rutile TiO _2. Graph showing the temporal change of the 1270nm light emission amount of TiO _2. Graph showing the relationship between specific surface area and the 1270nm light emission amount of the change amount of TiO ₂ (after 150 seconds). The figure which shows the emission spectrum at the time of 408 nm laser excitation of each titanium oxide. Graph showing the relationship between the crystal components of TiO ₂ and the peak ratio of the emission spectrum. Graph showing the relationship between 620nm emission amount of anatase TiO ₂ and the crystal defect amount. Graph showing the relationship between the crystal defect amount 620nm emission amount of rutile TiO _2. 620nm emission amount of anatase TiO ₂ and graph showing the relationship between the specific surface area. Graph showing the relationship between 620nm emission amount and the specific surface area of the rutile TiO _2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Sample cell, 2 ... Sample chamber, 3 ... Gas inlet, 4 ... Gas outlet, 10 ... Light irradiation means, 11 ... Luminescence measuring means, 12 ... Optical filter 13, heating means

Claims (15)

  A sample physical property evaluation method for irradiating a sample with excitation light and measuring a light emission amount at a specific wavelength generated by the irradiation of the excitation light, the light emission amount at a specific wavelength of a reference sample whose physical property to be evaluated is known Measuring the luminescence amount at a specific wavelength of the sample to be measured whose physical property to be evaluated is unknown, obtaining the correspondence between the physical property of the reference sample and the measured luminescence amount in advance, A physical property evaluation method for a sample, characterized in that the physical property of the sample to be measured is evaluated by comparing a light emission amount of the measured sample with a correspondence relationship obtained for the reference sample.   The physical property evaluation of the sample according to claim 1, wherein the physical property to be evaluated is at least one of a crystal defect amount, a crystallinity, a constituent component composed of a crystalline type and / or an amorphous type, and a content ratio thereof. Method.   The method for evaluating physical properties of a sample according to claim 1 or 2, wherein the sample is a powder or solid semiconductor material. The sample physical property evaluation method according to claim 3, wherein the semiconductor material is titanium oxide TiO ₂ .   The physical property evaluation of the sample according to any one of claims 1 to 4, wherein the physical property to be evaluated is a crystal defect amount or crystallinity, and the specific wavelength is light having a central wavelength at 1250 to 1290 nm. Method.   The physical property evaluation of the sample according to any one of claims 1 to 4, wherein the physical property to be evaluated is a crystal defect amount or crystallinity, and the specific wavelength is light having a central wavelength at 600 to 640 nm. Method.   2. The physical property evaluation method for a sample according to claim 1, wherein the physical property to be evaluated is a structural component of a crystalline type and / or an amorphous type, and the specific wavelength is a structural component of a crystalline type and / or an amorphous type. Are the two emission peak wavelengths 1 and 2 derived from a reference sample, and the ratio of the light emission amount at the emission peak wavelengths 1 and 2, the constituent component consisting of the crystalline type and / or the amorphous type, and the content thereof, Is obtained in advance, and the ratio of the emission amounts at the emission peak wavelengths 1 and 2 of the sample to be measured in which the crystalline and / or amorphous components are unknown is measured. By comparing the ratio of the luminescence amount and the corresponding relationship obtained for the reference sample, the constituent component consisting of the crystal type and / or the amorphous type of the sample to be measured and the content thereof are characterized. Claim 1 Physical properties evaluation method. The physical property evaluation method according to claim 7, wherein the measurement sample is a semiconductor material made of titanium oxide TiO ₂ , and the two emission peak wavelengths 1 and 2 are in a wavelength range of 560-580 nm and 620-640 nm.   A physical property evaluation apparatus used in the physical property evaluation method according to claim 1, comprising a light irradiation unit having a specific wavelength and a weak light emission measurement unit.   A physical property evaluation apparatus used in the physical property evaluation method according to any one of claims 1 to 8, wherein the sample cell, a sample chamber for storing the sample cell, and a sample to be stored in the sample cell A light irradiating means for irradiating light, a luminescence intensity measuring means for measuring luminescence intensity generated from the sample, and a spectroscopic mechanism provided between the sample chamber and the luminescence intensity measuring means. Physical property evaluation device.   The physical property evaluation apparatus according to claim 9 or 10, comprising an optical filter, a spectroscope, or a light receiving element as the spectroscopic mechanism.   The physical property evaluation apparatus according to claim 9, wherein the sample cell and / or the sample chamber is formed of a material that does not include a substance excited by irradiated light.   The said sample chamber is equipped with the gas inlet and gas outlet for substituting the atmosphere of the sample which should be accommodated in the said sample cell with an inert gas atmosphere. Physical property evaluation device.   The physical property evaluation apparatus according to claim 10, wherein a laser light source is used as the light irradiation unit.   The physical property evaluation apparatus according to claim 14, wherein the laser light source is 300 to 450 nm.

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