JPH0132459B2 - - Google Patents
Info
- Publication number
- JPH0132459B2 JPH0132459B2 JP54133103A JP13310379A JPH0132459B2 JP H0132459 B2 JPH0132459 B2 JP H0132459B2 JP 54133103 A JP54133103 A JP 54133103A JP 13310379 A JP13310379 A JP 13310379A JP H0132459 B2 JPH0132459 B2 JP H0132459B2
- Authority
- JP
- Japan
- Prior art keywords
- sample
- rays
- ray
- sspa
- spectroscopic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000005259 measurement Methods 0.000 claims description 21
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 238000000862 absorption spectrum Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000000691 measurement method Methods 0.000 claims description 2
- 230000003094 perturbing effect Effects 0.000 claims 1
- 238000001514 detection method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 4
- 238000000441 X-ray spectroscopy Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
- G01N23/06—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption
- G01N23/083—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption the radiation being X-rays
Landscapes
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Description
【発明の詳細な説明】
この発明は、Ｘ線分光測定に於いて試料の状態
変化を追つて測定することのできるＸ線分光吸収
の動的時間分解測定方法及びその装置に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method and apparatus for dynamic time-resolved measurement of X-ray spectroscopic absorption, which can follow changes in the state of a sample in X-ray spectrometry.
物質の物理的又は化学的な状態変化を追跡する
手段としてはその物質のＸ線分光吸収を調べその
吸収端付近に生ずるEXAFS（Extended
Absorption Fine Structure）を解析することが
有効である。しかしながら、物質のEXAFSを測
定するにはＸ線の各波長に於ける吸収係数を高精
度に測定しなければならずそのためには長時間の
データの蓄積や高輝度のＸ線源、高感度の検出器
を必要とし、従来のゴニオメータ角度掃引による
Ｘ線分光測定ではＸ線源から照射されるＸ線の一
部の波長しか利用されないので無駄が多く各波長
毎に順に測定を行うので測定全波長領域を測定す
るのにかなりの長時間を要し物質の状態変化を追
う測定は到底不可能であつた。また、位置有感Ｘ
線検出器として一次元位置検出ガス比例計数管を
使用した場合は、検出器を移動させることなく一
次元Ｘ線吸収スペクトル像の測定全波長領域を同
時に測定することができるので測定時間の短縮が
ある程度可能であり、物質の状態変化の測定のた
めの時間サンプリングによる動的時間分解測定も
可能ではあるが、この一次元位置検出ガス比例計
数管はその計数管としての性質上不感時間を有し
誤差を生じるので高輝度のＸ線源が使用できず位
置検出分解能にも限界があるので高い精度が要求
されるEXAFSの測定には不向きであり、また、
光子計数のデジタル測定なのでデータ処理が面倒
であり測定装置自体も複雑であるという欠点を有
していた。 EXAFS (Extended
It is effective to analyze the Absorption Fine Structure. However, to measure the EXAFS of a material, the absorption coefficient at each wavelength of X-rays must be measured with high precision, which requires long-term data accumulation, a high-brightness X-ray source, and a highly sensitive Conventional X-ray spectroscopic measurement using a goniometer angle sweep requires a detector, and is wasteful because only a portion of the wavelengths of the X-rays emitted from the X-ray source are used, and each wavelength is measured in turn. It took a considerable amount of time to measure the area, and it was impossible to measure changes in the state of matter. Also, position sensitive
When a one-dimensional position detection gas proportional counter is used as a radiation detector, the entire wavelength range of the one-dimensional X-ray absorption spectrum image can be measured simultaneously without moving the detector, reducing measurement time. Although it is possible to some extent and dynamic time-resolved measurement using time sampling to measure changes in the state of substances is also possible, this one-dimensional position detection gas proportional counter has a dead time due to its nature as a counter. It is not suitable for EXAFS measurements, which require high accuracy, because it causes errors, so a high-brightness X-ray source cannot be used, and there is a limit to the position detection resolution.
Since it is a digital measurement of photon counting, data processing is troublesome and the measuring device itself is complicated.
この発明はこのような事情に鑑みなされたもの
であつて、物質のＸ線分光吸収特にEXAFSの測
定を高精度且つ短時間で行えるようにしこの測定
を連続的に繰り返すことによつて、物質の状態変
化を追跡することができるＸ線分光吸収の動的時
間分解測定方法及びその装置を得ることを目的と
する。つまり、この発明は、Ｘ線分光測定の検出
器として、一次元Ｘ線吸収スペクトル像の測定全
波長領域を同時に測定することができる高感度で
且つ位置検出分解能に優れた位置有感Ｘ線検出器
であつて、しかも、測定をアナログ量で行うこと
によつて計数管のような不感時間が無く高輝度の
Ｘ線源を使用しても数え落しによる誤差が生じな
い検出素子であるSSPA（Self―Scanning
Photodiode Array）を使用し、短時間に一次元
Ｘ線吸収スペクトル像を高精度に測定し得るよう
にして、Ｘ線源によるＸ線の試料への照射を高輝
度且つパルス状とすることを可能にし、このパル
ス状のＸ線の照射を連続的に繰り返すことによつ
て刻々と変化する物質の状態を時間分解測定によ
り動的に追跡し得ることを可能にしている。 This invention was made in view of the above circumstances, and it is possible to measure the X-ray spectroscopic absorption of substances, especially EXAFS, with high precision and in a short time, and by continuously repeating this measurement, it is possible to The object of the present invention is to obtain a method and apparatus for dynamic time-resolved measurement of X-ray spectroscopic absorption that can track state changes. In other words, the present invention provides a position-sensitive X-ray detector with high sensitivity and excellent position detection resolution that can simultaneously measure the entire measurement wavelength range of a one-dimensional X-ray absorption spectrum image as a detector for X-ray spectrometry. SSPA is a detection element that does not have dead time like a counter and does not cause errors due to counting errors even when using a high-intensity X-ray source because it measures analog quantities. Self-Scanning
Using a photodiode array, it is possible to measure a one-dimensional X-ray absorption spectrum image with high precision in a short time, making it possible to irradiate the sample with high-intensity X-rays from the X-ray source in a pulsed manner. By continuously repeating this pulsed X-ray irradiation, it is possible to dynamically track the ever-changing state of a substance by time-resolved measurement.
この発明の実施例を図面の記載に基づいて説明
する。この発明のＸ線分光吸収の動的時間分解測
定装置１は、第１図に示すように、発散Ｘ線を用
い位置有感Ｘ線検出器で測定を行う角度分散同時
計測法による光学系で構成され、Ｘ線管２から照
射される発散Ｘ線３が試料ホルダ４の試料内を通
過し分光結晶５によつて分散されSSPA検出器６
の受光部に測定全波長領域が達するように配置さ
れている。Ｘ線管２は、パルス状の印加電圧を発
生するパルス電源７によつて励起されパルス状の
連続波長Ｘ線を複数の異なる波長を含み且つ適当
な開き角を有して発散する発散Ｘ線３として試料
ホルダ４に向けて照射する。分光結晶５は、分解
能の良いLiF等の単結晶を使用し、試料ホルダ４
の試料内を通過した発散Ｘ線３をその入射角に応
じてブラツグ条件で定まるそれぞれの波長に角度
分散させ一次元Ｘ線吸収スペクトル像として
SSPA検出器６の受光部に送る。このようにする
と、SSPA上の位置の異なる点に異なる波長のＸ
線が入射することになる。SSPA検出器６は、
MOS半導体素子であるSSPAを受光部に使用し
た位置有感Ｘ線検出器であり、分光結晶５で分散
された一次元Ｘ線吸収スペクトル像をこのSSPA
の各波長に対応する位置に在る各単一ホトダイオ
ードに電荷量として、所定時間内でパルス毎に蓄
積した後、走査回路によつてアナログ量として読
み取るものである。SSPA検出器６で読み取られ
た一次元Ｘ線吸収スペクトル像の測定データは、
コントロール回路８を経てデータ処理装置９に送
られ一旦記憶されて演算処理が施される。試料ホ
ルダ４には、ストツプトフロー法、パルスフラツ
シユ光照射、温度ジヤンプ、圧力ジヤンプ又は変
動電場印加等の物理的又は化学的な摂動を試料に
為すための試料条件コントロール装置１０を設け
てある。また、パルス電源７、データ処理装置９
及び試料条件コントロール装置１０はタイミング
回路１１によつて制御されていて、試料に為す摂
動に同期してＸ線管２からパルス状の発散Ｘ線３
を所定の時間内に繰り返し照射し試料の摂動によ
る化学変化の過程や物理的状態の変化を時間分解
測定しこの測定データを処理し得るようになつて
いる。 Embodiments of the invention will be described based on the drawings. As shown in FIG. 1, the dynamic time-resolved measurement device 1 for X-ray spectroscopic absorption according to the present invention is an optical system using a simultaneous angular dispersion measurement method that uses a position-sensitive X-ray detector to measure divergent X-rays. The divergent X-rays 3 emitted from the X-ray tube 2 pass through the sample in the sample holder 4, are dispersed by the spectroscopic crystal 5, and are sent to the SSPA detector 6.
The sensor is arranged so that the entire measurement wavelength range reaches the light receiving section of the sensor. The X-ray tube 2 is excited by a pulsed power supply 7 that generates a pulsed applied voltage, and converts pulsed continuous wavelength X-rays into diverging X-rays that include a plurality of different wavelengths and diverge at an appropriate opening angle. 3, the sample holder 4 is irradiated. The spectroscopic crystal 5 uses a single crystal such as LiF with good resolution, and the sample holder 4
The divergent X-rays 3 that have passed through the sample are angularly dispersed into respective wavelengths determined by bragging conditions according to the incident angle, and a one-dimensional X-ray absorption spectrum image is created.
It is sent to the light receiving section of the SSPA detector 6. In this way, X of different wavelengths can be placed at different points on the SSPA.
A line will be incident. The SSPA detector 6 is
This is a position-sensitive X-ray detector that uses an SSPA, which is a MOS semiconductor element, in the light receiving section.
After each single photodiode located at a position corresponding to each wavelength accumulates a charge as an amount for each pulse within a predetermined time, it is read as an analog amount by a scanning circuit. The measurement data of the one-dimensional X-ray absorption spectrum image read by the SSPA detector 6 is
The data is sent via the control circuit 8 to the data processing device 9, where it is temporarily stored and subjected to arithmetic processing. The sample holder 4 is provided with a sample condition control device 10 for applying physical or chemical perturbations to the sample such as a stop flow method, pulsed flash light irradiation, temperature jump, pressure jump, or application of a varying electric field. In addition, a pulse power source 7, a data processing device 9
The sample condition control device 10 is controlled by a timing circuit 11 to generate pulsed divergent X-rays 3 from the X-ray tube 2 in synchronization with perturbations made to the sample.
By repeatedly irradiating the sample within a predetermined period of time, it is possible to time-resolve the process of chemical change and change in physical state due to perturbation of the sample, and process this measurement data.
尚、パルス状の発散Ｘ線３を得るＸ線源として
は、実施例のようにパルス電源７を使用するので
はなく、Ｘ線管２のターゲツトの先に機械的チヨ
ツパーを設けこの機械的チヨツパーによる発散Ｘ
線３の照射のタイミングをタイミング回路１１で
制御するようにしてもよい。また、測定装置の光
学系は、実施例では試料を分光結晶５よりもＸ線
管２側に配置したが、試料を分光結晶５よりも
SSPA検出器６側に配置することも可能であり、
試料その他の条件により適宜定め得るものであ
る。 As an X-ray source for obtaining pulsed divergent X-rays 3, instead of using the pulse power source 7 as in the embodiment, a mechanical chopper is provided at the tip of the target of the X-ray tube 2. Divergence by
The timing of irradiation of the line 3 may be controlled by the timing circuit 11. In addition, although the optical system of the measuring device placed the sample closer to the X-ray tube 2 than the spectroscopic crystal 5 in the example, the sample was placed closer to the X-ray tube 2 than the spectroscopic crystal 5.
It is also possible to place it on the SSPA detector 6 side,
It can be determined as appropriate depending on the sample and other conditions.
以上説明したようにこの発明のＸ線分光吸収の
動的時間分解測定方法及びその装置は、Ｘ線分光
測定に於いてパルス状のＸ線源とSSPA検出器を
組み合わせることにより摂動を為した試料の状態
変化を高精度に動的時間分解測定することを可能
にすると共に、SSPAが一次元Ｘ線吸収スペクト
ル像を一旦蓄積しその後走査回路によつてアナロ
グ量として読み取るので測定データの処理が容易
にできるという効果を有する。 As explained above, the method and apparatus for dynamic time-resolved measurement of X-ray spectroscopic absorption of the present invention can be applied to a perturbed sample by combining a pulsed X-ray source and an SSPA detector during X-ray spectrometry. In addition to making it possible to perform dynamic time-resolved measurement of state changes with high precision, SSPA once accumulates a one-dimensional X-ray absorption spectrum image and then reads it as an analog quantity using a scanning circuit, making it easy to process the measurement data. It has the effect of being able to
第１図はこの発明のＸ線分光吸収の動的時間分
解測定装置の構成を示す説明図である。
１…Ｘ線分光吸収の動的時間分解測定装置、２
…Ｘ線管、４…試料ホルダ、５…分光結晶、６…
SSPA検出器、９…データ処理装置、１０…試料
条件コントロール装置、１１…タイミング回路。
FIG. 1 is an explanatory diagram showing the configuration of a dynamic time-resolved X-ray absorption measurement apparatus according to the present invention. 1...Dynamic time-resolved measurement device for X-ray spectroscopic absorption, 2
...X-ray tube, 4...sample holder, 5...spectroscopy crystal, 6...
SSPA detector, 9...data processing device, 10...sample condition control device, 11...timing circuit.
Claims (1)
として所定の時間内に繰り返し試料に照射し、こ
の試料内を通過するＸ線を分光結晶で一次元吸収
スペクトル像に分散させまたは分光結晶で一次元
吸収スペクトル像に分散させた後前記試料内を通
過させてSSPA（Self―Scanning Photodiode
Array）でそれぞれパルス毎に又は、数パルス積
算の後に検出することによつて摂動を為した試料
の状態変化を測定するＸ線分光吸収の動的時間分
解測定方法。 ２ パルス状の連続波長Ｘ線を高輝度の発散Ｘ線
として所定の時間内に繰り返し照射することので
きるＸ線源と、発散Ｘ線を波長毎の一次元吸収ス
ペクトル像に角度分散させる分光結晶と、試料に
摂動を為すために試料条件コントロール装置が設
けられた試料ホルダと、前記発散Ｘ線が試料内を
通過して前記分光結晶によつて角度分散され又は
分光結晶によつて角度分散されて前記試料内を通
過した前記Ｘ線の全波長領域が達するように配置
されたSSPA検出器と、該SSPA検出器からのア
ナログ量としての測定データを処理するデータ処
理装置と、該データ処理装置の動作と前記Ｘ線源
の照射及び前記試料条件コントロール装置との動
作を同期させるタイミング回路とを具備してなる
Ｘ線分光吸収の動的時間分解測定装置。[Claims] 1. A sample is repeatedly irradiated with pulsed continuous wavelength X-rays as high-intensity divergent X-rays within a predetermined period of time, and a one-dimensional absorption spectrum image of the X-rays passing through the sample is obtained using a spectroscopic crystal. SSPA (Self-Scanning Photodiode)
A dynamic time-resolved measurement method for X-ray spectroscopic absorption that measures changes in the state of a perturbed sample by detecting each pulse or after integrating several pulses. 2. An X-ray source that can repeatedly irradiate pulsed continuous wavelength X-rays as high-intensity divergent X-rays within a predetermined time, and a spectroscopic crystal that angularly disperses the divergent X-rays into one-dimensional absorption spectrum images for each wavelength. a sample holder provided with a sample condition control device for perturbing the sample; and the divergent X-rays passing through the sample and being angularly dispersed by the spectroscopic crystal or angularly dispersed by the spectroscopic crystal. an SSPA detector arranged so that the entire wavelength range of the X-rays that have passed through the sample reach the SSPA detector, a data processing device that processes measurement data as an analog quantity from the SSPA detector, and the data processing device A dynamic time-resolved measurement device for X-ray spectroscopic absorption, comprising a timing circuit that synchronizes the operation of the X-ray source, the irradiation of the X-ray source, and the operation of the sample condition control device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13310379A JPS5655845A (en) | 1979-10-15 | 1979-10-15 | Method and device for dynamic time resolving measurement of xxray spectral absorption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13310379A JPS5655845A (en) | 1979-10-15 | 1979-10-15 | Method and device for dynamic time resolving measurement of xxray spectral absorption |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5655845A JPS5655845A (en) | 1981-05-16 |
| JPH0132459B2 true JPH0132459B2 (en) | 1989-06-30 |
Family
ID=15096880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13310379A Granted JPS5655845A (en) | 1979-10-15 | 1979-10-15 | Method and device for dynamic time resolving measurement of xxray spectral absorption |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5655845A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49106393A (en) * | 1973-02-09 | 1974-10-08 | ||
| JPS5180277A (en) * | 1975-01-06 | 1976-07-13 | Kogyo Gijutsuin | KEIKOSUPEKUTORUBUNPUJIDOKOSOKUDOSOKUTEISOCHI |
| JPS522538A (en) * | 1975-06-16 | 1977-01-10 | Ibm | Spectrum analyzer |
-
1979
- 1979-10-15 JP JP13310379A patent/JPS5655845A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49106393A (en) * | 1973-02-09 | 1974-10-08 | ||
| JPS5180277A (en) * | 1975-01-06 | 1976-07-13 | Kogyo Gijutsuin | KEIKOSUPEKUTORUBUNPUJIDOKOSOKUDOSOKUTEISOCHI |
| JPS522538A (en) * | 1975-06-16 | 1977-01-10 | Ibm | Spectrum analyzer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5655845A (en) | 1981-05-16 |
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