JP2006071321A - X-ray detection apparatus and x-ray analysis apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reliably prevent the adhesion of foreign matter to the surface of a semiconductor light receiving element, an X-ray detection surface, in the case of using an X-ray direct detection type semiconductor sensor. <P>SOLUTION: This X-ray detection apparatus has a CCD module 32 formed by packaging a CCD sensor 42 in a package 40. The CCD sensor 42 is formed by aligning a plurality of CCD elements and directly receive X-rays with the CCD elements. An area of the CCD sensor 42 opposed to an X-ray reception surface in the package 40 is a protective film 43. The protective film 43 is made of an X-ray permeable material. The protective film 43 prevents foreign matter from adhering to the X-ray reception surface of the CCD sensor 42. The periphery of the protective film 43 is surrounded with a film support member 44. Since the film support member 44 is made of an X-ray attenuating material such as glass, it is possible to prevent X-rays from directly hitting a wire 47. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an X-ray detection apparatus that detects X-rays. The present invention also relates to an X-ray analysis apparatus using the X-ray detection apparatus.

  An X-ray analyzer generally includes an X-ray generator that generates X-rays irradiated on a sample and an X-ray detector that detects X-rays emitted from the sample. In this X-ray analyzer, when a sample is irradiated with X-rays, the incident X-ray is diffracted by the sample when the incident angle of the X-ray incident on the sample becomes a specific angle with respect to the sample. In other words, diffracted X-rays are emitted from the sample. This diffracted X-ray is detected by an X-ray detector.

  As an X-ray detection apparatus, conventionally, a zero (zero) -dimensional X-ray detection apparatus, a one-dimensional X-ray detection apparatus, and a two-dimensional X-ray detection apparatus are known. A zero-dimensional X-ray detection apparatus is an X-ray detection apparatus having a structure for receiving X-rays in a dot shape. As this zero-dimensional X-ray detection apparatus, for example, a PC (Proportional Counter / proportional counter) and an SC (Scintillation Counter) are known.

  The one-dimensional X-ray detection apparatus is an X-ray detection apparatus having a structure for receiving X-rays in a linear shape. As this one-dimensional X-ray detection device, for example, a PSPC (Position Sensitive Proportional Counter) having a linear signal line that generates an electric signal at the place where the X-ray is received, A one-dimensional CCD sensor formed by linearly arranging CCD (Charge Coupled Device) elements is known.

  The two-dimensional X-ray detection apparatus is an X-ray detection apparatus having a structure for receiving X-rays in a planar shape. As this two-dimensional X-ray detection device, for example, an X-ray detector known by the name of an imaging plate, that is, a detector plate provided with a storage phosphor on the X-ray receiving surface, or a plurality of CCD elements arranged in a plane There is known a two-dimensional CCD sensor formed by the above.

  The CCD sensor used as the one-dimensional CCD sensor or the two-dimensional CCD sensor is one type of semiconductor position detection sensor. In recent years, various X-ray analysis apparatuses having a structure using a semiconductor position detection sensor such as a CCD sensor as an X-ray detection apparatus have been proposed. According to the X-ray analysis apparatus having this structure, it is expected that high-speed measurement can be performed as compared with the case where a 0-dimensional X-ray detection apparatus, a one-dimensional X-ray detection apparatus, or the like is used.

  Conventionally, there is known an X-ray analyzer that uses a two-dimensional CCD sensor and an optical fiber to acquire a two-dimensional diffraction image having a larger area than the two-dimensional CCD sensor (for example, Patent Document 1). reference). The two-dimensional diffraction image is a two-dimensional or planar diffraction image. In the conventional apparatus disclosed in the above publication, as shown in FIG. 11, a phosphor 102 is provided behind the sample S when viewed from the X-ray source 101, and the light emitting side surface of the phosphor 102 (FIG. 11). A bundle of a plurality of tapered optical fibers 103 is provided on the right surface), and a two-dimensional CCD sensor 104 is provided at the light emitting end of these optical fibers 103 (the right end in FIG. 11).

  In this conventional X-ray analyzer, the phosphor 102 is exposed by diffracted X-rays emitted from the sample S to form a light image corresponding to the diffracted X-ray in the phosphor 102, and the light image is converted into light. The light is guided to the two-dimensional CCD sensor 104 by the fiber 103 and accumulated as charges in a plurality of light receiving elements in the CCD sensor 104. According to the X-ray analyzer of this structure, it is expected that high-speed measurement can be performed as compared with the case where a zero-dimensional counter or a one-dimensional counter is used.

  Each of the plurality of optical fibers 103 used in this conventional X-ray analyzer is tapered so that the diameter on the phosphor 102 side is large and the diameter on the CCD sensor 104 side is small. A CCD sensor using a tapered optical fiber 103 is sometimes called a tapered CCD sensor. This type of CCD sensor 104 is normally used while being cooled.

  The CCD sensor 104 does not detect X-rays directly but detects visible light. In front of the light receiving surface of the CCD sensor 104, a glass protective plate is often provided in order to protect a plurality of CCD elements forming the light receiving surface from dust and metal pieces. In general, it is difficult for glass to pass through X-rays without attenuation, but visible light can pass through without attenuation. Therefore, in the X-ray analysis apparatus shown in FIG. 11, the CCD sensor 104 having a glass protective plate can be used without any trouble.

Japanese Patent Laid-Open No. 2002-116158 (pages 3 to 6, FIG. 1)

  By the way, instead of the above-described CCD sensor that converts X-rays into visible light using a fluorescent screen and receives the light, a system that directly receives X-rays and outputs a signal corresponding to the intensity of the X-rays. It is conceivable to use this CCD sensor as an X-ray detection apparatus. Such an X-ray direct detection type CCD sensor basically includes a plurality of CCD elements that form a light receiving surface by removing a glass protective plate provided in front of the light receiving surface in a conventional CCD sensor. It can be formed by exposing to the outside.

  However, when the CCD element is exposed in this way, dust and metal pieces adhere to the surface of the CCD element, the X-ray detection accuracy of a part of the light receiving surface is lowered, and highly reliable X-ray detection is achieved. There is a risk that it will not be possible. In general, when producing an X-ray detection apparatus using a CCD sensor, the work of housing the CCD sensor in a housing or mounting an accessory on the CCD sensor is performed in a clean room. Initially, dust or the like may hardly adhere to the surface of a plurality of CCD elements. However, after actually operating the X-ray detector, dust or the like may be deposited on the surface of the CCD element according to the situation of the operation site. May adhere.

  The present invention has been made in view of the above-described problems, and is a semiconductor sensor such as a CCD sensor, and in the case of using an X-ray direct detection type semiconductor sensor, the surface of a semiconductor light receiving element such as a CCD element. An object of the present invention is to reliably prevent dust and metal pieces from adhering to the surface over a long period of time.

  An X-ray detection apparatus according to the present invention is formed by arranging a plurality of semiconductor light receiving elements, and a semiconductor sensor that directly receives X-rays by these semiconductor light receiving elements; And a package having wiring connected to the terminals, and a protective film having good X-ray permeability is provided on the X-ray receiving surface of the semiconductor sensor in the package.

  In the above configuration, the “semiconductor light receiving element” refers to an element that can directly detect X-rays using a semiconductor, for example, one CCD element. The “semiconductor sensor” is a sensor in which an X-ray light receiving surface is formed by arranging a plurality of semiconductor light receiving elements linearly or planarly, for example, a CCD sensor. The “protective film” can be formed of a material having a mechanical strength that has good X-ray permeability and can prevent foreign substances such as dust, dust, and metal pieces from entering. As such a material, for example, Kapton (trade name made by DuPont) which is a polyimide resin and Mylar (trade name made by DuPont) which is a polyester resin can be used.

  According to the X-ray detection apparatus according to the present invention described above, the entry of foreign matter into the semiconductor light receiving element is blocked by the protective film, so that it is possible to reliably prevent foreign matter from adhering to the surface of the semiconductor light receiving element over a long period of time. Therefore, the reliability of the X-ray detection apparatus of the X-ray direct detection type can be favorably maintained over a long period.

  Next, in the X-ray detection apparatus according to the present invention, it is preferable that a part or all of the surrounding region surrounding the outer peripheral edge of the protective film in the package is formed of a material that attenuates X-rays. In general, wiring and other accessory elements are often provided around the semiconductor sensor. Some of these attachment elements are not desired to be directly exposed to X-rays. If a protective film capable of transmitting the above X-rays is provided in a region facing the X-ray light receiving surface of the semiconductor sensor and a material for attenuating X-rays is provided in the peripheral region of the protective film as described above, the semiconductor The X-ray attenuating material described above can be placed against elements that are attached to the sensor and do not like X-rays, and therefore various elements attached to the semiconductor sensor are normally held for a long time. it can. The “material for attenuating X-rays” can be glass, for example. Glass is a material that can transmit visible light and attenuates X-rays.

  Next, in the X-ray detection apparatus according to the present invention, it is desirable that a part or all of the surrounding area formed of the material that attenuates the X-ray is an area that covers the wiring. The wiring is one of a plurality of elements constituting the package, one end of which is connected to the input / output terminal of the semiconductor sensor in the package, and the other end is connected to the external terminal outside the package. It is. In general, the wiring is formed of a conductive metal such as copper. When X-rays directly hit this wiring, there is a possibility that noise is generated due to the influence of the photoelectric effect. If the material for attenuating X-rays as described above is disposed opposite to the wiring, it is possible to prevent strong X-rays from directly hitting the wiring, thus preventing noise from occurring.

  Next, in the X-ray detection apparatus according to the present invention, the package includes a deep recess for accommodating the semiconductor sensor, and a shallow recess provided around the deep recess and in which the wiring is formed. The region formed by the material that attenuates the line is preferably opposed to the shallow recess. In this way, it is possible to reliably prevent the wiring from being deteriorated by the X-ray hitting the wiring.

  Next, the X-ray detection apparatus according to the present invention can include a housing having a recess that accommodates the package, and a housing film that covers the opening of the recess. In this case, it is desirable that the casing film is formed of a material that can transmit X-rays, and the concave portion is in a vacuum state or a reduced pressure state close to a vacuum.

  This structure is a desirable shape as an external shape of the X-ray detection apparatus. A semiconductor sensor such as a CCD sensor is first accommodated in a recess of a package, and then the package is accommodated in a housing of the X-ray detection device. Thus, the semiconductor sensor is placed in a predetermined position in the X-ray detection device. Installed. There is a possibility that foreign matters such as dust and metal pieces may adhere to the wall surface of the recess provided in the housing of the X-ray detection apparatus. Then, the foreign matter may move away from the wall surface and enter the semiconductor sensor after the X-ray detection apparatus enters the operating state. However, if the X-ray light receiving surface of the semiconductor sensor is covered with a protective film as in the present invention, such foreign matter can be reliably prevented from entering.

  Although foreign matter may adhere to the protective film, even if foreign matter adheres to the protective film, the protective film can be easily replaced. Considering that foreign matter adheres to the surface of the CCD element, in that case, for example, a very troublesome work of removing the foreign matter using air tweezers or the like while observing the surface with a microscope is required. At that time, the surface of the CCD element may be damaged. Since the CCD element is expensive, it should be avoided as much as possible to damage the CCD element. On the other hand, if only the protective film needs to be replaced, the protective film is inexpensive, which is very advantageous. In addition, the work of replacing the protective film is much easier than the work of cleaning the CCD sensor.

  Next, in the X-ray detection apparatus according to the present invention, it is desirable that the protective film provided on the X-ray light receiving surface of the semiconductor sensor in the package is a polymer film that is not fibrous. If a protective film having such characteristics is used, the attenuation of X-rays toward the semiconductor sensor can be suppressed as much as possible.

  Next, an X-ray analyzer according to the present invention includes an X-ray source that generates X-rays, a sample support unit that supports a sample, and an X-ray detection device that detects X-rays diffracted by the sample, The X-ray detection apparatus is an X-ray detection apparatus having the above-described configuration. By using the X-ray detection apparatus according to the present invention, the entry of foreign matter into the semiconductor light receiving element is blocked by the protective film, so that it is possible to reliably prevent foreign matter from adhering to the surface of the semiconductor light receiving element over a long period of time. Therefore, the reliability of the X-ray detection apparatus of the X-ray direct detection type can be favorably maintained over a long period. Therefore, an X-ray analysis apparatus using this X-ray detection apparatus can perform highly reliable X-ray analysis over a long period of time.

  Now, the semiconductor sensor used in the present invention is not limited to a special type of semiconductor sensor, but it is preferable that the semiconductor sensor is constituted by a CCD sensor. In particular, it is not a system that detects X-rays by converting them into visible light through a phosphor, but a CCD sensor having a structure that receives X-rays directly and converts them into electrical signals, so-called X-ray direct detection type CCD A sensor is desirable.

  In general, a CCD sensor is a sensor using a CCD (Charge Coupled Device) which is a device for transferring signal charges collected in a plurality of potential wells (potential wells) in a semiconductor. A region corresponding to one potential well constitutes one pixel, that is, one light receiving element. The plurality of potential wells are arranged one-dimensionally (that is, linearly) or two-dimensionally (that is, planarly) on the X-ray receiving surface. In order to achieve high speed and high sensitivity, it is desirable to arrange a plurality of pixels two-dimensionally. Each potential well receives X-rays and generates electrons. The number of electrons generated at this time is proportional to the incident photon energy.

  For example, as shown in FIG. 8, the potential well has a voltage different from that of one of the electrodes 1 in a plurality of metal oxide semiconductor (MOS) structures including a metal electrode 1, an oxide insulating layer 2, and a semiconductor layer 3. This is realized by partially applying a different potential under the electrode. The signal charges confined in the potential well are sequentially transferred through the semiconductor layer 3 and sent to the output section. Thus, the signal applied to the CCD sensor when the signal charge is transferred in the semiconductor layer 3 is the charge transfer signal.

  As the CCD sensor used as the semiconductor sensor in the present invention, a one-dimensional CCD sensor or a two-dimensional CCD sensor can be considered. However, preferably a two-dimensional CCD sensor is used. There are various types of two-dimensional CCD sensors. For example, there are two-dimensional CCD sensors such as an FT (Frame Transfer / Frame Transfer) type, an FFT (Full Frame Transfer / Full Frame Transfer) type, and an IT (Interline Transfer / Interline Transfer) type.

Hereinafter, these two-dimensional CCD sensors will be described. The terms “horizontal blanking period” and “vertical blanking period” used in the description are image data for one frame by scanning a reading point. Is a term generally used when reading or writing. Specifically, in FIG. 10, the time from one horizontal scan S _H before moving to the next horizontal scanning S _H is the horizontal blanking interval. The time from one vertical scanning before moving to the next vertical scan, i.e., the time from the end point P _E of one frame before returning to the starting point P _S is the vertical blanking interval.

  For example, as shown in FIG. 5, the FT type two-dimensional CCD sensor includes a light receiving unit 6 configured by a vertical shift register, a storage unit 7 configured by another vertical shift register, and one horizontal shift register 8. And an output unit 9. The vertical shift register is sometimes called a parallel register. Further, the horizontal shift register is sometimes called a serial register, a read register, or the like. The metal electrode 1 (see FIG. 8) in the light receiving unit 6 is formed of a transparent conductive material such as polysilicon.

  When light enters the semiconductor layer 3 through the metal electrode 1, photoelectric conversion is performed and signal charges are generated. This signal charge is collected in the potential well below the electrode 1 during a certain time. Thereafter, this signal charge is transferred to the storage unit 7 at a high speed for each frame during the vertical blanking period, that is, during the time from one vertical scan to the next vertical scan. As described above, in the FT type CCD sensor, the vertical shift register of the light receiving unit 6 functions as a photoelectric conversion device in the signal accumulation period. While photoelectric conversion and signal accumulation are performed in the light receiving unit 6, the signal charge accumulated in the accumulation unit 7 is in the horizontal blanking period, that is, during the time from one horizontal scan to the next horizontal scan. Each line is transferred to the horizontal shift register 8 and further transferred to the output unit 9 by the horizontal shift register 8.

  Next, the FFT type two-dimensional CCD sensor basically has a configuration in which the storage unit 7 is removed from the FT type CCD sensor of FIG. 5 as shown in FIG. Since there is no storage unit 7, a shutter mechanism is usually attached to the light receiving unit 6. In this FFT type CCD sensor, charges are collected in the potential well of the light receiving unit 6, that is, the pixels, that is, the light receiving elements during the signal accumulation period, and the signal charges are transferred to the output unit 9 through the horizontal shift register 8 during the closing period of the shutter mechanism. . Since the FFT type CCD sensor does not have a storage part, it can have the same size as the FT type and can have a large number of pixels, or the light receiving part 6 can have a large area.

  Next, for example, as shown in FIG. 7, the IT CCD sensor includes a light receiving unit 6 constituted by a photodiode 6a, a vertical shift register 7 arranged so as to sandwich the photodiode 6a, and a photodiode 6a. A transfer gate 11 provided as a switch between the shift register 7, a horizontal shift register 8, and an output unit 9 are provided.

  Signal charges generated by photoelectric conversion in the photodiode 6a are collected in the junction capacitance of the photodiode 6a itself. The collected signal charges are transferred to the vertical shift register 7 through the transfer gate 11 during the vertical blanking period. Unlike the FT CCD sensor (see FIG. 5), this transfer operation is performed simultaneously for all pixels from the photodiode 6a to the vertical shift register 7. Thereafter, the signal charge is transferred to the horizontal shift register 8 line by line during the horizontal blanking period, and is further output to the output unit 9 by the horizontal shift register 8.

  Hereinafter, the present invention will be described by taking as an example an embodiment in which the present invention is applied to an X-ray diffraction apparatus which is an example of an X-ray analysis apparatus and is preferably used for analysis of a powder sample. Of course, the present invention is not limited to this embodiment.

  FIG. 1 shows an X-ray diffraction apparatus which is an embodiment of an X-ray analysis apparatus according to the present invention. The X-ray diffractometer 16 shown here has an X-ray generator 19 incorporating an X-ray focal point 18 as an X-ray source, and regulates the divergence of the X-rays emitted from the X-ray generator 19 and leads it to the sample S. It has a divergence regulation slit 21 and a goniometer 17 that is a measuring device. The goniometer 17 has a θ rotation system 24 and a 2θ rotation system 26, the sample S is supported by the θ rotation system 24, and the X-ray detection device 27 is supported by the 2θ rotation system 26.

  The θ rotation system 24 is driven by the θ rotation driving device 22 to rotate the sample S around the ω axis. Hereinafter, this rotation is referred to as θ rotation. Here, the ω-axis is an axis that passes through the X-ray incident surface of the sample S and extends in the direction perpendicular to the paper surface of FIG. The 2θ rotation system 26 is driven by the 2θ rotation drive device 23 to rotate the X-ray detection device 27 around the ω axis. Hereinafter, this rotation is referred to as 2θ rotation. The 2θ rotation is the same rotation direction as the θ rotation, and is a rotation at twice the angular velocity.

  It should be noted that the θ rotation and the 2θ rotation can be set as rotations having the same angular velocity and opposite rotation directions. Even in this case, it is possible to realize the same angle measurement operation as in the above case in which the 2θ rotation is the same rotation direction at an angular velocity twice that of the θ rotation.

  As shown in FIG. 2, the X-ray detection device 27 includes a housing 31, a CCD module 32, a Peltier element 33 as a cooling element, and a film 34. The housing 31 has a recess 36 on the side facing the sample S in FIG. 1, and the CCD module 32 and the Peltier element 33 are accommodated in the recess 36. The Peltier element 33 is in contact with the back surface of the CCD module 32. The film 34 is made of a material that can transmit X-rays, for example, beryllium (Be). This film 34 is fixed to the wall surface of the housing 31 at the opening of the recess 36 by an adhesive or other fixing means. As is well known, the Peltier element 33 is an element in which one surface is cooled by energization and the other surface is heated. In this embodiment, the surface to be cooled is in contact with the CCD module 32.

  FIG. 3 shows a planar structure of the CCD module 32. FIG. 4 shows a cross-sectional structure of the CCD module 32 according to the line AA in FIG. In these drawings, the CCD module 32 has a CCD sensor 42 as a semiconductor sensor and a package 40 for packaging the CCD sensor 42. Here, packaging means that the CCD sensor 42 is surrounded by a container so as to protect the CCD sensor 42 and to achieve a conductive connection with an external electric circuit.

  In order to achieve the above packaging, the package 40 includes a housing 41 that functions as a substrate on which the CCD sensor 42 is mounted, a rectangular ring-shaped film support member 44, and a protective film supported by the film support member 44. 43, a plurality of wirings 47, and a plurality of external terminals 49. The housing 41 is formed of, for example, ceramic, synthetic resin, or the like, and has a recess 46 including a deep recess 46a and a shallow recess 46b. The recess 46 has an opening toward the sample S in FIG. The CCD sensor 42 is accommodated in the deep recess 46a, and the wiring 47 is connected to the external terminal 49 through the shallow recess 46b. One end of the wiring 47 is connected to the input / output terminal of the CCD sensor 42 by a predetermined bonding technique, and the other end of the wiring 47 is connected to the external terminal 49 by a predetermined bonding technique.

  The membrane support member 44 is fixed to the housing 41 at the opening of the recess 46 by an adhesive or other fixing means. The center portion of the membrane support member 44 is a square or rectangular opening 48, and the periphery of the protective film 43 is fixed to the periphery of the membrane support member 44 by an adhesive or other fixing means so as to cover the opening 48. Yes. The opening 48 has a size corresponding to the X-ray light receiving area of the CCD sensor 42 and is at least wider than the X-ray light receiving area.

  The protective film 43 is made of, for example, Kapton, Mylar (both are trade names of products manufactured by DuPont), or the like. By using these materials, the protective film 43 is a film having a good X-ray transmission line, and has a mechanical strength capable of preventing entry of foreign matters such as dust, dust, and metal pieces. The protective film 43 protects the CCD sensor 42 by preventing entry of foreign matter. The protective film 43 is provided in the vicinity of the X-ray light receiving surface of the CCD sensor 42. The membrane support member 44 is made of, for example, glass. For this reason, the membrane support member 44 can transmit visible light and has a characteristic of attenuating X-rays. That is, in the present embodiment, the surrounding region surrounding the outer peripheral edge of the protective film 43 is formed by glass that is a material that attenuates X-rays. In FIG. 3, the entire peripheral region surrounding the outer peripheral edge of the protective film 43 is formed of glass. However, if necessary, a part of the peripheral region may be formed of glass.

  In the case of this embodiment, the CCD sensor 42 uses the FFT type CCD sensor shown in FIG. The CCD sensor 42 is driven for reading X-rays by a CCD driving circuit 28 as shown in FIG. The CCD drive circuit 28 drives the CCD sensor 42 so as to perform a so-called TDI (Time Delay Integration) operation. This TDI operation will be described later.

  In FIG. 1, the X-ray diffraction device 16 has a control device 51. The control device 51 includes a CPU (Central Processing Unit) 52, a storage medium, that is, a memory 53, and a bus 54 that transmits various signals. The memory 53 includes a semiconductor memory such as a ROM (Read Only Memory) and a RAM (Random Access Memory), a mechanical memory such as a hard disk, a CD (Compact Disc), and an MO (Magnet Optical) disk, and other arbitrary structures. Consists of. The X-ray diffractometer 16 has a display device 56. The display device 56 includes, for example, a video display unit such as a CRT (Cathode Ray Tube) or an LCD (Liquid Crystal Device), a printing unit such as a printer.

  The memory 53 includes a file 57 for storing pixel data output from the CCD sensor 42 in the X-ray detector 27 and a file 58 in which a program for executing X-ray diffraction measurement is stored. It is.

  The X-ray diffraction measurement program stored in the file 58 controls the operations of the θ rotation driving device 22 and the 2θ rotation driving device 23. Specifically, the X-ray diffraction measurement program 58 rotates the θ rotation system 24 supporting the sample S around the ω axis, and rotates the sample S at a predetermined angular velocity, so-called θ rotation. By this θ rotation, the incident angle of X-rays emitted from the X-ray source 18 and incident on the sample S is changed. The X-ray diffraction measurement program 58 rotates the 2θ rotation system 26 supporting the X-ray detection device 27 around the ω axis to rotate the X-ray detection device 27 in the same direction as the θ rotation at a double angular velocity. Rotate so-called 2θ. By this 2θ rotation, the X-ray diffracted by the sample S can be detected by the X-ray detector 27.

  Instead of rotating the sample S by θ, the X-ray generator 19 and the divergence regulating slit 21 are rotated by θ around the ω axis, and at the same time, the X-ray detector 27 is rotated at the same angular velocity in the opposite direction to the θ rotation. Similar results can be obtained by rotating 2θ.

  In the present embodiment, the X-ray diffraction measurement program 58 gives an instruction to the CCD drive circuit 28 to cause the X-ray detector 27 to perform a TDI (Time Delay Integration) operation. Moreover, when executing the TDI operation, the X-ray diffraction measurement program 58 synchronizes the charge transfer process in the X-ray detection device 27 with the angular velocity of the 2θ rotation of the X-ray detection device 27 performed by the 2θ rotation drive device 23. I am doing so.

Hereinafter, the TDI operation will be described. Assuming that the FFT type CCD sensor shown in FIG. 6 is used, the CCD sensor 42 moves in the direction of arrow A in FIG. 6 at a constant movement speed “v”. Further, the charge transfer pulse signal has a frequency “f”, and the transfer charge moves in the direction opposite to that of the X-ray detection apparatus as indicated by an arrow B. Further, one pixel width of the CCD sensor 42, that is, one light receiving element width is defined as “d”. Under the above conditions,
v = f × d
The movement speed of the CCD sensor 42 and the charge transfer process are synchronized so that the above relationship is satisfied.

  In FIG. 6, when the CCD sensor 42 moves in the direction of arrow A at a speed v, the input of the first column (that is, the rightmost column) of the M column (the column is the vertical direction) is the second column after 1 / f time. Move to position. In accordance with this, if the charge in the first column is transferred to the second column, data of the same part of the subject in the second column is again accumulated as a charge by photoelectric conversion. If such an operation is continuously performed to the end of the M columns, as a signal charge, M times the charge in a normal case where the TDI operation is not performed is accumulated in each pixel. These accumulated signal charges are output continuously and continuously from the horizontal shift register 8 of the CCD sensor 42 for each column, whereby data for a two-dimensional image can be obtained. Thus, weak diffracted X-rays can be detected by the TDI operation.

  Since the X-ray analyzer of the present embodiment is configured as described above, in FIG. 1, when the X-ray diffraction measurement is started, the sample S rotates by θ, and at the same time, the X-ray detector 27 rotates by 2θ. Further, X-rays emitted from the X-ray source 18 enter the sample S. If the Bragg diffraction condition is satisfied while the incident angle of the X-ray incident on the sample S changes according to the θ rotation, the sample S generates a diffracted X-ray. It proceeds in the direction of the diffraction angle (2θ). The diffracted X-rays are received by the corresponding pixels in the light receiving unit 6 of the CCD sensor 42 in FIG. 6, and electric charges are generated and further accumulated in the pixels.

  As described above, the X-ray detection device 27 is driven by the TDI operation, and in this TDI operation, the charge transfer processing is controlled so as to be synchronized with the 2θ movement speed of the X-ray detection device 27. Signal charges relating to the same diffraction angle (2θ) are accumulated. For this reason, even if the moving speed of the X-ray detector 27 is set to a high speed, accurate diffraction X-ray data can always be stored in each pixel. The signal charges thus accumulated in each pixel are transferred from the light receiving unit 6 to the horizontal shift register 8 for each column, and further stored in the pixel data file 57 of FIG. Such data collection operation ends after the X-ray detection device 27 scans a desired diffraction angle range, for example, an angle range of 20 ° to 100 ° in FIG. Data of diffraction X-ray intensity at each diffraction angle position within an angle range of 20 ° to 100 ° is stored.

  Thereafter, the CPU 52 obtains the diffraction pattern Z of FIG. 9 by calculation based on the measured pixel data 57 in accordance with the X-ray diffraction measurement program 58 of FIG. The calculated diffraction pattern Z is displayed as an image or print on the display surface of the display device 56 of FIG. 1 as necessary.

  In the X-ray analysis apparatus of the present embodiment, as shown in FIG. 4, a protective film 43 is provided in a region corresponding to the X-ray light receiving surface of the CCD sensor 42 in the package 40 in which the CCD sensor 42 is stored. Since the X-ray light receiving surface of the CCD sensor 42 is covered by 43, the protective film 43 prevents foreign matters such as dust, dust and metal pieces from entering the CCD element which is a semiconductor light receiving element. For this reason, it is possible to reliably prevent foreign matter from adhering to the surface of the CCD element over a long period of time, and therefore, the reliability of the CCD sensor 42 can be favorably maintained over a long period of time.

  3 and 4, a plurality of wirings 47 are provided around the CCD sensor 42 in the package 40. These wirings 47 are made of, for example, copper. If foreign matter adheres to these wirings 47, there is a possibility that a short circuit or disconnection may occur. Further, if these wirings 47 directly receive X-rays, noise may occur and accurate data transfer may not be possible. In this regard, in this embodiment, since the film support member 44 and the protective film 43 supported by the film support member 44 are provided on the front surface of the wiring 47, it is possible to prevent foreign matter from adhering to the wiring 47. Further, since the film support member 44 having the characteristic of attenuating X-rays is disposed in the region facing the wiring 47, it is possible to prevent the X-ray from hitting the wiring 47 in advance.

  In the present embodiment, as shown in FIG. 4, the CCD sensor 42 and the wiring 47 are accommodated in a recess 46 formed in the housing 41. The membrane support member 44 is attached to the opening of the recess 46. With this configuration, the wiring 47 or other elements attached to the CCD sensor 42 can be neatly arranged. Further, the protective film 43 can be positioned accurately in alignment with the light receiving surface of the CCD sensor 42.

  In the present embodiment, the recess 46 is formed by a deep recess 46a and a shallow recess 46b. And the shallow recessed part 46b is provided in the circumference | surroundings of the deep recessed part 46a. The CCD sensor 42 is accommodated in the deep recess 46a, and the wiring 47 is formed in the shallow recess 46b. The membrane support member 44 made of a material that attenuates X-rays is disposed to face the shallow recess 46b. With this configuration, since the wiring 47 is protected from being hit by X-rays by the film support member 44 at a position close to itself, it is possible to reliably prevent the X-ray from hitting the wiring 47.

  In FIGS. 1 and 2, the X-ray detection device 27 has a casing 31, and a recess 36 is formed in the casing 31. The CCD module 32 including the CCD sensor 42 is housed in the recess 36 together with the Peltier element 33. The opening of the recess 36 is covered with a film 34 that can transmit X-rays. Usually, the inside of the recess 36 is set to a vacuum state or a reduced pressure state close to a vacuum.

  In this structure, foreign matter such as dust and metal pieces may adhere to the wall surface of the recess 36 provided in the housing 31. Then, the foreign substance may leave the wall surface and enter the CCD sensor 42 after the CCD sensor 42 enters the operating state. However, in this embodiment, as shown in FIG. 4, the X-ray light receiving surface of the CCD sensor 42 is covered with the protective film 43 that is a component of the package 40, so that entry of such foreign matters can be reliably prevented. .

  Next, in this embodiment, the protective film 43 of FIG. 4 was formed by Kapton (trade name made by DuPont) which is a polyimide resin or Mylar (trade name made by DuPont) which is a polyester resin. These resins are polymer membranes and are not fibrous. By using a film having such characteristics, attenuation of X-rays toward the CCD sensor 42 can be suppressed as much as possible.

(Other embodiments)
The present invention has been described with reference to the preferred embodiments. However, the present invention is not limited to the embodiments, and various modifications can be made within the scope of the invention described in the claims.
For example, in the embodiment of FIG. 4, the protective film 43 is attached to the housing 41 via the film support member 44, but the protective film 43 may be directly attached to the housing 41 without using the film support member 44. In this case, an X-ray attenuating member such as glass or the like is not provided around the protective film 43 that is an X-ray transmissive member. Even in this case, the protective film prevents foreign matter from adhering to the CCD sensor 42. The main effect of preventing by 43 can be achieved.

  In the embodiment of FIG. 1, the FFT type CCD sensor shown in FIG. 6 is used as the CDD sensor 42, but a CCD sensor having another structure may be used as necessary. In the embodiment shown in FIG. 1, the present invention is applied to a θ-2θ type X-ray diffractometer. However, the present invention can also be applied to an X-ray diffractometer having other structures, and further, if necessary. Accordingly, the present invention can be applied to an X-ray analyzer other than the X-ray diffractometer.

  The X-ray detection apparatus according to the present invention can be applied to an X-ray diffraction apparatus, a fluorescent X-ray apparatus, an X-ray small angle scattering apparatus, a micro X-ray measurement apparatus, and other various X-ray analysis apparatuses. The X-ray analyzer according to the present invention is suitably used when it is desired to perform X-ray analysis such as X-ray diffraction measurement and fluorescent X-ray measurement at high speed and accurately.

It is a figure which shows one Embodiment of the X-ray detection apparatus and X-ray analyzer which concern on this invention. It is a plane sectional view expanding and showing the X-ray detection device of Drawing 1. It is a top view which shows the CCD module used with the X-ray detection apparatus of FIG. It is sectional drawing according to the AA line of FIG. It is a figure which shows an example of a CCD sensor. It is a figure which shows another example of a CCD sensor. It is a figure which shows another example of a CCD sensor. It is sectional drawing which shows the cross-section of the CCD element which is a semiconductor light receiving element. It is a figure which shows the diffraction line figure obtained as a result of the measurement using the X-ray analyzer of FIG. It is a figure for demonstrating the function of a CCD sensor. It is a figure which shows an example of the conventional X-ray analyzer.

Explanation of symbols

1. 1. metal electrode, 2. an oxide insulating layer; Semiconductor layer, 6. Light receiving section,
6a. 6. photodiode, Storage section, 8. Horizontal shift register,
9. 10. output unit; Transfer gate, 16. X-ray diffractometer (X-ray analyzer),
17. Goniometer, 18. X-ray focus (X-ray source), 19. X-ray generator,
21. Divergence regulation slit, 24. θ rotation system, 26.2θ rotation system,
27. X-ray detection device 31. Housing, 32. CCD module,
33. Peltier element (cooling element), 34. Membrane, 36. Recess, 40. Package, 41. Housing, 42. CCD sensor (semiconductor sensor), 43. Protective film,
44. 46. Membrane support member Recess, 46a. 1st recessed part, 46b. A second recess,
47. Wiring, 48. Opening, 49. Terminal, S.M. sample

Claims (9)

A semiconductor sensor formed by arranging a plurality of semiconductor light receiving elements and receiving X-rays directly by the semiconductor light receiving elements;
A package that houses the semiconductor sensor and includes wiring connected to terminals of the semiconductor sensor;
An X-ray detection apparatus comprising: a protective film having good X-ray permeability on an X-ray receiving surface of the semiconductor sensor in the package.   2. The X-ray detection apparatus according to claim 1, wherein a part or all of a surrounding region surrounding an outer periphery of the protective film in the package is formed of a material that attenuates X-rays. .   The X-ray detection apparatus according to claim 2, wherein a part or all of the surrounding area formed of a material that attenuates the X-ray is an area that covers the wiring. 4. The X-ray detection apparatus according to claim 3, wherein the package includes a deep recess for accommodating the semiconductor sensor, and a shallow recess provided around the deep recess and in which the wiring is formed. An X-ray detection apparatus characterized in that a region formed of a material to be attenuated faces the shallow recess. In the X-ray detection apparatus according to any one of claims 1 to 4,
A housing having a recess for accommodating the package;
A housing film covering the opening of the recess,
The housing membrane can pass X-rays,
The X-ray detection apparatus, wherein the concave portion is in a vacuum state or a reduced pressure state close to a vacuum.   6. The X-ray detection apparatus according to claim 2, wherein a material that attenuates X-rays that forms part or all of a peripheral region surrounding the outer peripheral edge of the protective film in the package is glass. An X-ray detection apparatus characterized by The X-ray detection apparatus according to any one of claims 1 to 6,
The X-ray detection apparatus, wherein the protective film provided on the package is a polymer film and is not a fibrous film.   8. The X-ray detection apparatus according to claim 1, wherein the semiconductor light receiving element is a CCD element. An X-ray source for generating X-rays, a sample support means for supporting a sample, and an X-ray detection device for detecting X-rays diffracted by the sample, wherein the X-ray detection device is defined in claims 1 to 8. An X-ray analyzer according to any one of the above.

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