CN104374788A - Synchrotron-radiation high-pressure monocrystalline diffraction method - Google Patents
Synchrotron-radiation high-pressure monocrystalline diffraction method Download PDFInfo
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- CN104374788A CN104374788A CN201410079911.8A CN201410079911A CN104374788A CN 104374788 A CN104374788 A CN 104374788A CN 201410079911 A CN201410079911 A CN 201410079911A CN 104374788 A CN104374788 A CN 104374788A
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Abstract
A disclosed synchrotron-radiation high-pressure monocrystalline diffraction method comprises limiting and intensity monitoring of incident light, sample positioning and rotation, data acquisition by using a two-dimension detector, indexing of detection data, diffraction intensity correction, and other steps. The experiment method is capable of obtaining accurate strength information of a monocrystalline sample under a pressure condition, and provides good conditions for subsequent research works such as structure determination and refining, high-pressure phase transition research, commensurability-free structure determination, charge density measure and the like.
Description
Technical field
The present invention relates to a kind of single crystal diffraction experimental technique, particularly relate to a kind of synchrotron radiation high pressure single crystal diffraction method, the method is based on synchrotron radiation experiment porch, utilize diamond anvil cell press chamber technology complete single crystal samples ray data collection with and the experimental technique of aftertreatment.
Background technology
The laboratory facilities commonly used the most crystal structure determination under elevated pressure conditions are at present method of X-ray diffraction.The X-ray diffraction signal of sample contains two aspect information, diffraction peak information and diffracted intensity information.The former, determine, and the latter determines primarily of the chemical composition of crystal and Atomic Arrangement (crystal structure) primarily of cell parameter, space group kind.Current most x-ray diffraction experiment adopts powder diffraction techniques.This is because powder diffraction methods itself possesses skills, mature and reliable, device simply, to sample condition loosely require, data processing is quick, operation is easy to the series of advantages such as grasp.But powdery diffractometry also exists the inherent shortcomings such as diffraction data overlap, preferred orientation problem be serious, and often cannot obtain strength information accurately.Comparatively speaking, high pressure single crystal diffraction experimental technique can avoid some inherent shortcomings of powdery diffractometry, obtains diffraction patterns more accurately, comprises position and strength information.
Relative to laboratory X source, synchrotron radiation light source has the advantage of high brightness, high-energy, high monochromaticity, low divergence, can obtain more diffraction information, and significantly can improve conventional efficient.Synchrotron radiation high pressure diffraction experiment method has become research means very important and the most common in high pressure research.
Do not carry out synchrotron radiation high pressure single crystal diffraction experimental study before domestic, mainly because relative to powdery diffractometry, System's composition more complicated, Sample location accuracy requirement is higher.Data Post aspect requires also higher simultaneously, needs to carry out special process and just can recover diffracted intensity accurately.
Summary of the invention
Synchrotron radiation high pressure single crystal diffraction experimental technique of the present invention is to obtain single crystal samples accurate strength information under stress, for follow-up study as structure determination and refine, phase transition under high pressure research, incommensurability structure determination, determining charge density etc. create conditions.
Synchrotron radiation high pressure single crystal diffraction experimental technique of the present invention comprises the steps:
(1) incident light limit light and intensity monitoring
Wherein, in experiment porch, limit light and intensity monitoring is carried out by arranging and adjust shutter, one-level slit, secondary slit and light-intensity test diode pair incident light;
Wherein, shutter is for controlling the break-make of incident synchrotron radiation light;
One-level slit is limited by four edges of a knife and forms, and every sheet edge of a knife has step motor control; The vertical two panels edge of a knife can independently move up and down separately, and the horizontal two panels edge of a knife can independently move left and right separately; With the movement of Electric Machine Control four edges of a knife, the horizontal and vertical aperture of slit can be set, and spindle central will be passed through through synchrotron radiation light; The length and width of one-level slit are preferably dimensioned to be 50 μm × 50 μm;
Secondary slit is the logical optical slits of fixed measure, controls locus by three tunnel translation motor; Being completed after through synchrotron radiation light-seeking by one-level slit, with motor, secondary slit is moved in light path; The size of secondary slit is preferably fixed on 50 μm × 50 μm;
Intensity monitor element should photodiode between secondary slit and DAC, and preferably, the luminescent material of photodiode is Si, its thickness preferably 5 microns;
(2) Sample location and rotation
The platform carrying out Sample location and rotation comprises a D translation platform and combines and a turntable, and this platform can complete the gesture stability of X, Y, Z, ω four dimensions, and the repetitive positioning accuracy of X, Y, Z translation stage can reach 1 μm;
The method of Sample location and rotation is that two-dimensional detector adds sample one-dimensional rotation ω method, and concrete steps are as follows:
(i) according to DAC diffraction window angle initialization two-dimensional detector and sample distance; Be preferably set to about 185mm.
(ii) set ω rotation angle range, rotary step and rotating speed, input control system; Preferably set rotating range-25 °-25 °, step-length preferably 2 °, rotating speed preferably 0.05 °/s-0.1 °/s;
(iii) start scanning and adopt spectrum; Sample is angle from setting, is preferably-25 °, is scanned up to the angle at the end of setting by above-mentioned setting step-length and rotating speed, is preferably 25 °;
Detector continuous exposure in each step-length, until this step scan terminates, after then the diffraction data obtained being stored, then starts the scanning of next step-length.
(3) two-dimensional detector data acquisition
Two-dimensional imaging partitioned detector is placed in the position of distance sample 180 ~ 190mm, the diffraction data of sample is gathered; Preferably, two-dimensional imaging partitioned detector has 3450 × 3450 pixels, and each Pixel Dimensions is 100 μm × 100 μm, dynamic range 16;
4) detection data indexing
After the data collection task of previous step terminates, the substep collection that this module can utilize system to generate completes the indexing work of monocrystalline point diffraction under this spot pressure condition.
5) diffracted intensity corrects
After hitting the target process, need to carry out extracting diffracted intensity and correcting, obtain single crystal diffraction data.
Embodiment
The method utilizes based on synchrotron radiation high pressure diffraction experiment platform carries out, sample is being loaded in diamond anvil cell pressure chamber, after single crystal samples provides hyperbaric environment, synchrotron radiation high pressure single crystal diffraction experimental technique of the present invention can be utilized under synchrotron radiation light beam to obtain the diffracting spectrum of single crystal samples.
Synchrotron radiation high pressure single crystal diffraction experimental technique of the present invention comprises the steps:
1) incident light limit light and intensity monitoring
By arranging and adjust shutter, one-level slit, secondary slit and light-intensity test diode pair incident light limit light and intensity monitoring in experiment porch.
Wherein, shutter is for controlling the break-make of incident synchrotron radiation light, and it has the response speed of microsecond time scale, can strictly control the crystal time shutter.Regulate the position of one-level slit and secondary slit can control the spindle central of incident synchrotron radiation light through sample ω turntable; Regulate the size of one-level slit and secondary slit can complete the control of the size to incident synchrotron radiation light beam, to obtain the spot size that experiment needs.The change of monitoring incident intensity is responsible for by diode, is convenient to recover more accurately intensity data in post-processing stages.
One-level slit is made up of four edges of a knife, and every sheet edge of a knife has step motor control.The vertical two panels edge of a knife can independently move up and down separately, and the horizontal two panels edge of a knife can independently move left and right separately.With the movement of Electric Machine Control four edges of a knife, the horizontal and vertical aperture of slit can be set, and spindle central will be passed through through synchrotron radiation light.The size of general one-level slit is set in ~ and 50 μm × 50 μm.
Secondary slit is the logical optical slits of fixed measure, has three tunnel translation motor to control locus.Being completed after through synchrotron radiation light-seeking by one-level slit, with motor, secondary slit is moved in light path.This secondary slit can block to fall synchrotron radiation light at the diffraction occurred after one-level slit and diverging light, to reduce experiment back end noise.The size of secondary slit is generally fixed on 50 μm.
In the experiment of synchrotron radiation high pressure single crystal diffraction, incident intensity monitoring detects no less important with the time shutter, and they are used in point diffraction intensity normalized, plays key effect for recovery crystal diffraction point real information.In order to obtain the true light intensity of incident sample position, we monitoring element are located at secondary slit and adamas bears down on one between anvil (DAC).
In traditional synchrotron radiation experiment, intensity monitor mainly utilizes gas ionization chamber to complete.But because space is very narrow and small between the secondary slit of single crystal diffraction system and DAC, and incident synchrotron radiation luminous energy higher (ionizing power is weak), small size gas ionization chamber is very insensitive to incident intensity change, cannot effectively monitor intensity.For this reason, we adopt photodiode as intensity monitor element, and photodiode material is the Si of thickness 5 microns.Meeting generation current during synchrotron radiation light transmission photodiode, also can not there is significant change in intensity simultaneously, can accurate measurements system light intensity change while not reducing light intensity.
2) Sample location and rotation
In the laboratory single crystal diffractometer of routine, dimension (the ω in Kappa geometry is rotated in usual employing three, φ and 2 θ) in conjunction with two-dimensional detector (imaging plate, CCD), or four are rotated dimension (ω, φ, 2 θ and χ) mode of binding site detector, in space, 360 ° of rotary samples obtain the data of high integrity degree and High redundancy.But in the experiment of high pressure single crystal diffraction, because single crystal samples is loaded in pressure vessel (DAC), blocking of DAC causes declining to a great extent of angle of diffraction on the one hand, three circles that another aspect is sample or four circles rotate and add very large positioning difficulty.
In order to solve DAC block on experiment affect problem, we have employed two-dimensional detector and add the mode of sample one-dimensional rotation (ω) to obtain single crystal diffraction data.Concrete steps are as follows:
(1) according to DAC diffraction window angle initialization two-dimensional detector and sample distance, about 185mm is preferably set to.
(2) ω rotation angle range, rotary step and rotating speed is set, input control program.Preferably set rotating range-25 °-25 °, step-length 2 °, rotating speed 0.05 °/s-0.1 °/s.
(3) start scanning and adopt spectrum.Sample is angle from setting, is preferably-25 °, is scanned up to the angle at the end of setting by above-mentioned setting step-length and rotating speed, is preferably 25 °.
In each step-length (2 °), detector continuous exposure is until this step scan terminates, and then the diffraction data obtained is outputted in computing machine, then starts the scanning of next step-length.Above-mentioned two-dimensional detector adds Sample location and the diffraction that sample one-dimensional rotation (ω) well achieves high pressure single crystal samples.
In order to complete the work of conventional crystalline structure elucidation, in structure elucidation process, we have used for reference method (the structure determination of powder diffraction of powder diffraction experiment Data Analysis crystal structure, SDPD), crystal structure refine work has been carried out.
Sample location and spinfunction are combined by a D translation platform and a turntable builds.It can complete the gesture stability of X, Y, Z, ω four dimensions.The repetitive positioning accuracy of X, Y, Z translation stage can reach 1 μm, the sample in DAC accurately can be placed in the rotation center rotating shaft of ω turntable.Under normal circumstances, D translation platform can realize Sample location precision and is better than 5 μm.ω turntable slewing area is generally subject to DAC diffraction window limit, between-30 ° to+30 °.
3) two-dimensional detector data acquisition
Two-dimensional detector is arranged on the station acquisition diffraction light apart from the position of the about 180 ~ 190mm of sample, preferably 185mm, this detector collectable diffraction data d value scope
.Above-mentioned position is suitable for the diffraction light accepting sample of maximum magnitude.
Preferably, two-dimensional imaging partitioned detector has 3450 × 3450 pixels, and each Pixel Dimensions is 100 μm × 100 μm, dynamic range 16.In single crystal diffraction experiment, the time shutter of detector is accurately controlled by slit.
4) detection data indexing.After the data collection steps of previous step terminates, substep is utilized to gather the indexing of monocrystalline point diffraction under this spot pressure condition.In the middle of high pressure single crystal diffraction experimentation, along with pressure increases, be easy to cause sample broke.Strictly speaking, be no longer just at this moment single crystal diffraction.Once there is this situation, because existing single crystal diffraction indexing method will lose efficacy, and cell parameter cannot being measured, testing premature termination to causing.For this reason, we propose combining powder diffraction index technology and now measure cell parameter, and the technology of recycling genetic algorithm compute location matrix, has developed a set of new indexing technology.
5) diffracted intensity corrects
After hitting the target process, need to carry out extracting diffracted intensity and correcting.After completing diffracted intensity correction work, control system generates * .hkl formatted file the most frequently used in crystallography and carries out follow-up study for user, comprises crystallographic structural analysis, the aspects such as crystal structure refine and charge density recovery.
Certainly; the present invention also can have other various embodiments; when not deviating from the present invention's spirit and essence thereof; those of ordinary skill in the art are when making various corresponding change and distortion according to the present invention, but these change accordingly and are out of shape the protection domain that all should belong to the claim appended by the present invention.
Claims (8)
1. a synchrotron radiation high pressure single crystal diffraction method, is characterized in that, comprise the steps:
(1) incident light limit light and intensity monitoring
Limit light and intensity monitoring is carried out by arranging and adjust shutter, one-level slit, secondary slit and light-intensity test element on incident light;
Wherein, shutter is for controlling the break-make of incident synchrotron radiation light;
One-level slit is limited by four edges of a knife and forms, and every sheet edge of a knife has step motor control; The vertical two panels edge of a knife can independently move up and down separately, and the horizontal two panels edge of a knife can independently move left and right separately; With the movement of Electric Machine Control four edges of a knife, the horizontal and vertical aperture of slit can be set, and spindle central will be passed through through synchrotron radiation light;
Secondary slit is the logical optical slits of fixed measure, controls locus by three tunnel translation motor; Being completed after through synchrotron radiation light-seeking by one-level slit, with motor, secondary slit is moved in light path;
Intensity monitor element is the photodiode between secondary slit and DAC;
(2) Sample location and rotation
The platform carrying out Sample location and rotation comprises a D translation platform and combines and a turntable, and this platform completes the gesture stability of X, Y, Z, ω four dimensions, and the repetitive positioning accuracy of X, Y, Z translation stage is 1 μm;
The method of Sample location and rotation is that two-dimensional detector adds sample one-dimensional rotation ω method, and concrete steps are as follows:
(i) according to DAC diffraction window angle initialization two-dimensional detector and sample distance;
(ii) set ω rotation angle range, rotary step and rotating speed, input control system;
(iii) start scanning and adopt spectrum; Sample is angle from setting, is scanned up to the angle at the end of setting by above-mentioned setting step-length and rotating speed;
Detector continuous exposure in each step-length, until this step scan terminates, after then the diffraction data obtained being stored, then starts the scanning of next step-length;
(3) two-dimensional detector data acquisition
Two-dimensional imaging partitioned detector is placed in the position of distance sample 185mm, the diffraction data of sample is gathered;
(4) detection data indexing
After the data collection task of previous step terminates, the substep collection that this module can utilize system to generate completes the indexing work of monocrystalline point diffraction under this spot pressure condition;
(5) diffracted intensity corrects
After hitting the target process, need to carry out extracting diffracted intensity and correcting, obtain single crystal diffraction data.
2. synchrotron radiation high pressure single crystal diffraction experimental technique as claimed in claim 1, it is characterized in that, the length and width of one-level slit are of a size of 50 μm × 50 μm.
3. synchrotron radiation high pressure single crystal diffraction experimental technique as claimed in claim 1, it is characterized in that, the size of secondary slit is fixed on 50 μm × 50 μm.
4. synchrotron radiation high pressure single crystal diffraction experimental technique as claimed in claim 1, it is characterized in that, the luminescent material of photodiode is Si, and its thickness is 5 microns.
5. synchrotron radiation high pressure single crystal diffraction experimental technique as claimed in claim 1, it is characterized in that, two-dimensional detector and sample distance are 180 ~ 190mm.
6. synchrotron radiation high pressure single crystal diffraction experimental technique as claimed in claim 1, is characterized in that, set ω rotating range-25 °-25 ° in Sample location and spin step, step-length 2 °, rotating speed 0.05 °/s-0.1 °/s.
7. synchrotron radiation high pressure single crystal diffraction experimental technique as claimed in claim 1, is characterized in that, the beginning angle that sample in spectrum step is adopted in scanning is-25 °, and angle at the end is 25 °.
8. synchrotron radiation high pressure single crystal diffraction experimental technique as claimed in claim 1, it is characterized in that, two-dimensional imaging partitioned detector has 3450 × 3450 pixels, and each Pixel Dimensions is 100 μm × 100 μm, dynamic range 16.
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| CN104764761A (en) * | 2015-04-23 | 2015-07-08 | 中国工程物理研究院材料研究所 | Method for measuring phase transition of substance under high static pressure |
| CN111929336A (en) * | 2020-09-04 | 2020-11-13 | 合肥优纳珂科技有限公司 | High-pressure X-ray diffractometer |
| CN112611766A (en) * | 2020-11-26 | 2021-04-06 | 哈尔滨工业大学 | Method for realizing in-situ three-dimensional absorption imaging under extreme condition of more than 10 ten thousand atmospheric pressure |
| CN112763432A (en) * | 2020-12-25 | 2021-05-07 | 中国科学院上海高等研究院 | Control method for automatically collecting absorption spectrum experimental data |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104764761A (en) * | 2015-04-23 | 2015-07-08 | 中国工程物理研究院材料研究所 | Method for measuring phase transition of substance under high static pressure |
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| CN111929336A (en) * | 2020-09-04 | 2020-11-13 | 合肥优纳珂科技有限公司 | High-pressure X-ray diffractometer |
| CN112611766A (en) * | 2020-11-26 | 2021-04-06 | 哈尔滨工业大学 | Method for realizing in-situ three-dimensional absorption imaging under extreme condition of more than 10 ten thousand atmospheric pressure |
| CN112611766B (en) * | 2020-11-26 | 2023-07-18 | 哈尔滨工业大学 | Method for realizing in-situ three-dimensional absorption imaging under extreme condition of more than 10 ten thousand atmospheric pressure |
| CN112763432A (en) * | 2020-12-25 | 2021-05-07 | 中国科学院上海高等研究院 | Control method for automatically collecting absorption spectrum experimental data |
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