X-ray scattering apparatus

Abstract

The present invention relates to an X-ray scattering apparatus (10), comprising: — a sample holder (16) for aligning and / or orienting a sample (17) for analysis by X-ray scattering; — a first X-ray beam delivery system (12) including a first X-ray source (18) and a first monochromator (20) and disposed upstream of the sample holder (16) for generating a first X-ray beam (22) along a beam path in the propagation direction (Y) and guiding it toward the sample holder (16); — a distal X-ray detector (14) disposed downstream of the sample holder (16) and particularly The device is movable along the propagation direction (Y) in a motorized manner to detect a first X-ray beam (22) and X-rays scattered from the sample (17) at different scattering angles; wherein the first X-ray beam delivery system (12) is configured to focus the first X-ray beam (22) on or near a focal point on a distal X-ray detector (14) when placed at its maximum distance from the sample holder (16), or is configured to generate a parallel beam; wherein the X-ray scattering device (10) further includes a second X-ray beam delivery system (28), which is configured to focus a second X-ray beam (42) on or near a focal point on the sample holder (16).

Description

Technical Field

[0001] This invention relates to an X-ray scattering device. Background Technology

[0002] Typically, X-ray scattering and X-ray diffraction instruments include:

[0003] 1) Source

[0004] 2) Wavelength selector (monochromatic device)

[0005] 3) Collimation section (defining the beam direction and removing residual background scattering or divergence)

[0006] 4) Sample area

[0007] 5) and detector area.

[0008] Since the adoption of X-ray analysis, various components have been greatly developed due to the need for faster measurements and better data quality, which in turn has provided characterization answers for an increasing number of structured and quasi-structured samples.

[0009] In addition, various highly specialized diffraction and scattering geometries have been developed to extract more specific information, such as:

[0010] 1) X-ray powder diffraction

[0011] a. Prague-Brentano Reflection

[0012] b. Genie Transmission

[0013] 2) Single-crystal diffraction (transmission)

[0014] 3) Laue method of back reflection

[0015] 4) Grazing incidence X-ray diffraction

[0016] 5) X-ray reflectivity

[0017] 6) Texture

[0018] 7) Small-angle X-ray scattering (transmission)

[0019] 8) Wide-angle X-ray scattering (transmission)

[0020] 9) Bunce-Hart Superintelligent Angular Scattering

[0021] To make the most of their instrument investment, some X-ray scattering apparatuses allow for easy switching between different configurations. As an example, one could mention switching wavelengths by changing the source anode material (e.g., Xenocs dual-source SAXS) or switching techniques by changing the collimation components. Thus, with only a small additional cost, the instrument can be re-optimized for entirely new scattering or diffraction applications.

[0022] Materials science and development require structural characterization on large length scales to study the hierarchical structural effects on material functionality. Complex materials will exhibit more or less structural solidity depending on their length scale. Furthermore, the development of new materials will require in-situ characterization based on external parameters or structural characterization during operation. Nanostructured materials with structures typically ranging from 1 to 150 nm in length can be characterized by small-angle X-ray scattering (SAXS) by analyzing the intensity of the X-ray beam elastically scattered by the sample at scattering angles typically between 0.05° and 10°, where two phases with sufficient electron density contrast exist. This technique has been widely used for the characterization of flexible materials, for example, in the fields of polymers, colloids, or proteins in solution.

[0023] Characterizing new materials requires combining wide-angle X-ray scattering (WAXS) with crystal structure characterization, and most SAXS characterization instruments combine SAXS / WAXS and USAXS (ultra-small angle X-ray scattering) to detect commonly used... Structures down to several micrometers can be used, for example, with the USAXS Buns-Hart configuration to measure the scattering profile in only one direction.

[0024] In other words, while wide-angle X-ray scattering (WAXS) typically provides information about the crystallinity and crystal phase of the sample being analyzed, small-angle X-ray scattering (SAXS) typically provides information about the nanoscale sample structure (nanostructure). Since both crystal phase and nanostructure affect material properties, it is of interest to perform SAXS and WAXS simultaneously on the same sample and on the same instrument.

[0025] However, while most of the X-ray techniques of interest mentioned above are best configured in fairly compact instruments suitable for benchtop applications or in smaller laboratory instruments with a footprint of less than 2m x 2m, this is not the case for SAXS instruments, where longer instruments (3m to 10m) consistently offer a better combination of resolution and intensity. Shorter instruments offer lower intensity at the highest resolution required for SAXS, thus resulting in longer instrument lifespans.

[0026] However, recent developments have begun to combine traditional SAXS with other configurations, such as Bonshart ultra-small angle X-ray scattering, grazing incidence diffraction, wide-angle X-ray scattering, and powder and texture analysis. Summary of the Invention

[0027] To perform SAXS and WAXS measurements on the same sample and instrument, an X-ray scattering apparatus is provided, comprising:

[0028] - Sample holder, which is used to align and / or orient the sample for analysis by X-ray scattering;

[0029] - A first X-ray beam delivery system, which includes a first X-ray source and a first monochromator and is arranged upstream of a sample holder to generate a first X-ray beam along the beam path in the propagation direction and guide it toward the sample holder;

[0030] - A distal X-ray detector, which is arranged downstream of the sample holder and can move along the propagation direction, particularly in a motorized manner, to detect the first X-ray beam and X-rays scattered from the sample at different scattering angles;

[0031] The first X-ray beam delivery system is configured to focus the first X-ray beam onto or near the focal point of the distal X-ray detector when placed at its maximum distance from the sample holder, or is configured to produce a parallel beam, and is commercially available from the applicant under the name "Xeuss 3.0".

[0032] The first X-ray beam delivery system of this conventional X-ray scattering apparatus includes a first X-ray source (e.g., a source having a Cu or Mo anode for generating X-rays) and an optical and collimating system; the optical and collimating system includes a first monochromator for guiding and adjusting the generated first X-ray beam along a generally horizontal propagation direction toward and around a sample holder, which may include a motorized translational and / or rotary stage or other types of sample stages known in the field of X-ray scattering and may be located in a vacuum chamber.

[0033] This conventional X-ray scattering device includes at least one X-ray detector arranged downstream of the sample holder, i.e., arranged on the side of the sample holder, which is opposite to the side of the first X-ray beam delivery system.

[0034] Distal X-ray detectors are typically mounted on a detector stage that allows translation over a large horizontal distance from the sample holder along the direction of the direct beam propagation, typically in the range of 50 mm to 1000 mm or greater, for example, up to 5000 mm. Depending on the location details of the distal X-ray detector and the scale of its sensor, it is generally capable of detecting X-rays scattered from the sample at a scattering angle relative to the direct X-ray beam, ranging from as small as approximately 2θ = 0.05° to as large as 60° to 70°. Therefore, distal X-ray detectors are suitable for small-angle X-ray scattering (SAXS) to provide information about the nanoscale structure of the sample, and for wide-angle X-ray scattering (WAXS) to provide information about the crystallinity of the sample.

[0035] However, the X-ray optics schemes used for optimal SAXS do not provide optimal conditions for WAXS measurements. For example, long collimation provides a low-divergence beam; and in some cases, focusing is planned at typical SAXS distances of 3m to 8m from the first X-ray source, equivalent to 1m to 5m from the sample. However, for WAXS, the detector is much closer, so the beam outside the focal point is substantially larger than the beam at the focal point. Furthermore, even for a focused beam, the focal size SF follows the lens equation SF = M * S; M = P2 / P1, where M is the magnification factor, S is the source size, P1 is the distance between the source and the optics or monochromator, and P2 is the distance between the optics and the focal point. For long SAXS, the collimation M is typically >10, and achieving a small focal size is impossible unless the aperture is very small, which significantly reduces the intensity. Similar problems occur with collimators, which typically utilize 0.5 to 1mm... 2 The beam size is adjusted to achieve sufficient intensity and resolution in SAXS.

[0036] Similar challenges exist in scattering applications that require small exposed areas on the sample while tolerating lower resolution, such as applications where the sample is being scanned or where the sample volume needs to be small due to the sample environment (e.g., the inside of a channel in a microfluidic novel). Here, the long collimation length and lens equation again set an insufficient lower limit for the beam size, which can be achieved without reducing most of the intensity by the aperture.

[0037] Given the time required for reconfiguration and realignment of the system, mechanically and manually reconfiguring the X-ray scattering equipment to change components and relative distances (such as moving the first X-ray source closer to the sample) is problematic.

[0038] Therefore, the object of the present invention is to provide an improved X-ray scattering device of the above type, which allows for optimal conditions for SAXS and WAXS measurements, respectively.

[0039] According to the present invention, this objective is achieved by the aforementioned conventional type of X-ray scattering apparatus, characterized in that the X-ray scattering apparatus further includes a second X-ray beam delivery system configured to focus a second X-ray beam onto or near a focal point on the sample holder. This configuration allows the first X-ray beam generated by the first X-ray beam delivery system to be used for SAXS measurements; however, the second X-ray beam obtained by the second X-ray beam delivery system is used for WAXS measurements (including high-resolution WAXS measurements) or for scattering applications over small sample exposure areas (hereinafter referred to as high spatial resolution applications).

[0040] When the distal X-ray detector is positioned close to the sample, WAXS measurements can be performed at a specific maximum scattering angle; however, this requires moving the distal detector along the propagation direction (Y). For applications requiring simultaneous SAXS and WAXS measurements (e.g., in-situ measurements) or for WAXS applications requiring measurements at maximum angles up to 90°, the X-ray scattering apparatus according to the invention preferably further includes a proximal X-ray detector arranged downstream of the sample holder, such as to allow the first X-ray beam to pass through and detect X-rays scattered from the sample. The proximal X-ray detector can be a fixed detector (fixed at a distance of approximately 80 mm to 150 mm along the propagation direction (Y) of the first X-ray beam) or a motorized detector, such that the detector can be moved along the surface of the Ewald sphere to measure the scattering pattern scattered at a wide angle in the incident plane (YZ) or in the lateral direction. When motorized, the proximal X-ray detector may also be equipped with an additional rotating stage to keep its surface perpendicular to the direction of the incoming beam.

[0041] In a first embodiment of the invention, the second X-ray beam delivery system includes a second X-ray source and a second monochromator. These allow the generation of a second X-ray beam completely independently of the first X-ray beam and its focusing onto or near a sample holder.

[0042] In a preferred embodiment of this first embodiment, the X-ray scattering apparatus further includes an insertion module configured to move the second X-ray beam delivery system to the first X-ray beam at a location upstream of the sample holder. The insertion module then allows computer-controlled movement of the second X-ray beam delivery system, thereby eliminating any manual interaction by the user.

[0043] In this configuration, the X-ray scattering apparatus preferably further includes a primary collimator extending along the beam path from downstream of the first X-ray beam delivery system to upstream of the sample holder. The insertion module includes a motorized platform configured to alternatively position the second X-ray beam delivery system or collimator extension into the beam path between the primary collimator and the sample holder. For SAXS measurements, the collimator extension is then positioned in the beam path, allowing the first X-ray beam to be used as a direct beam striking the sample mounted on the sample holder. However, for WAXS or high spatial resolution scattering measurements, the second X-ray beam delivery system is positioned in the beam path via the motorized platform. The control system of the X-ray scattering apparatus can then activate a gate in the first X-ray beam delivery system to block the first X-ray beam while simultaneously activating a gate in the second X-ray beam delivery system, causing the second X-ray beam to be focused onto or near the sample holder by a second monochromator.

[0044] Preferably, the downstream end of the main collimator and the upstream end of the collimator extension are provided with corresponding connecting elements for a tight vacuum connection. This allows the beam path to be maintained essentially as a vacuum from the first X-ray beam delivery system to the sample holder while the collimator extension is in the beam path during SAXS measurements.

[0045] Preferably, the collimator extension is provided with a retraction / extension mechanism. The collimator extension can then be retracted and extended via the telescopic mechanism. In the retracted state, by reducing friction and contact with mechanical components during movement of the motorized platform (which holds the collimator extension), the collimator extension can be easily inserted between the main collimator and the sample holder with reduced friction. Once the collimator extension reaches its final position in the beam path, it can extend until it contacts the main collimator and / or the vacuum chamber; the sample holder is located in this vacuum chamber, or any other optical components are arranged upstream of this vacuum chamber.

[0046] In a second embodiment of the invention, the second X-ray beam delivery system includes an optical module and a positioning module. The positioning module is configured to position the optical module upstream of the sample holder to the first X-ray beam, wherein the optical module is configured to convert the first X-ray beam into a second X-ray beam focused on or near the sample holder. However, in the first embodiment of the invention, when the second X-ray beam delivery system is used, the first X-ray beam is substantially blocked by the first X-ray beam delivery system; the second embodiment of the invention converts the first X-ray beam into a second X-ray beam with a different focal point, i.e., a focal point on or near the sample holder.

[0047] In a preferred embodiment of the second embodiment, the positioning module includes a vacuum-fitted motorized retainer configured to hold the optical module. This allows the positioning module to be positioned inside a main collimator that extends substantially from the first X-ray beam delivery system.

[0048] In a particularly general version of this preferred embodiment, the positioning module is configured to alternatively position the optical module or channel-cutting monochromator upstream of the sample holder relative to the first X-ray beam. The channel-cutting monochromator may be part of a Bunshart module that also includes an additional channel-cutting analyzer positioned downstream of the sample holder.

[0049] In a preferred embodiment of the first or second embodiment, the X-ray scattering apparatus according to the invention further includes first and second slit modules located upstream of the sample holder, wherein the second slit module is located downstream of the second X-ray beam delivery system, and the distance between the second slit module and the second X-ray beam delivery system is 5 cm or less. The first and second slit modules can be used in combination to shape the first X-ray beam. The second slit module can also be used to shape the second X-ray beam. Attached Figure Description

[0050] Preferred embodiments of the X-ray scattering apparatus according to the present invention will be described below with reference to the accompanying drawings, wherein:

[0051] Figure 1a A schematic top view of a first embodiment of an X-ray scattering apparatus according to the invention, in a configuration for SAXS measurement, is shown;

[0052] Figure 1b The configuration for WAXS measurement is shown. Figure 1a A schematic top view of an X-ray scattering device;

[0053] Figure 2a The upstream of the sample holder is shown Figure 1a A perspective view of a portion of an X-ray scattering device;

[0054] Figure 2b The upstream of the sample holder is shown Figure 1b A perspective view of a portion of an X-ray scattering device;

[0055] Figure 3a It shows Figure 2a A top view of the X-ray scattering device;

[0056] Figure 3b It shows Figure 2b A top view of the X-ray scattering device;

[0057] Figure 4a It shows Figure 1a An enlarged perspective view of the second X-ray beam delivery system of the X-ray scattering device;

[0058] Figure 4b It shows Figure 1b An enlarged perspective view of the second X-ray beam delivery system of the X-ray scattering device;

[0059] Figure 5 A schematic diagram of a first monochromator and optical module used in a second embodiment of the present invention is shown;

[0060] Figure 6A schematic side view of the positioning module used in a second embodiment of the present invention is shown;

[0061] Figure 7 A schematic top view of another example of the invention utilizing an additional X-ray microscope is shown; and

[0062] Figure 8 A top view of a modified version of the first embodiment equipped with two second X-ray sources is shown. Detailed Implementation

[0063] Figure 1a A schematic top view of a first embodiment of an X-ray scattering apparatus 10 in a configuration for SAXS measurement according to the present invention is shown. The apparatus 10 is shown from its upstream end at the first X-ray beam delivery system 12 down to its downstream end at the distal X-ray detector 14. Figure 2a A perspective view of a portion of the device 10 upstream of the sample holder 16 is shown, and Figure 3a It shows Figure 2a A top view of the X-ray scattering device 10.

[0064] Figure 1b , Figure 2b and Figure 3b A perspective view is shown, in which a first embodiment of the X-ray scattering apparatus 10 is positioned for WAXS measurements. This configuration is particularly suitable for high-resolution WAXS measurements, and also for high spatial resolution SAXS measurements.

[0065] In all the top views shown in the figures, the upstream end of the X-ray scattering device 10 is on the left and the downstream end is on the right. The propagation direction Y of the first and second X-ray beams is therefore from left to right.

[0066] Furthermore, the propagation direction Y is horizontal in the laboratory system. The horizontal direction perpendicular to Y is called the X direction, and the vertical direction perpendicular to both X and Y is called the Z direction.

[0067] The first X-ray beam delivery system 12 includes a first X-ray source 18 and a first monochromator 20. (As shown by...) Figure 1a As indicated by the dashed line, the first monochromator 20 selects and is configured to collect X-rays generated by the first X-ray source 18 and focus them as the first X-ray beam 22 onto or near the focal point of the distal X-ray detector 14, which is positioned at its maximum distance from the sample holder 16 in the Y direction. In this context, "near" means that the distance between the focal point of the first X-ray beam 22 and the distal X-ray detector 14 is approximately the distance P2 between the focal point and the first monochromator 20 (via...). Figure 1aThe focal point is 20% of the area indicated by the double arrows in the diagram. The focal point can be located before (i.e., upstream) or after (i.e., downstream) the distal X-ray detector 14. Alternatively, it is also possible for the first monochromator 22 to produce a substantially parallel beam.

[0068] The first X-ray source 18 is preferably a focal point source, and the first monochromator 20 is preferably a focal point monochromator.

[0069] The beam shape can also be defined by the slit module 24, which is preferably of the "low scattering" or "no scattering" type. Figure 1a The image shows two such slit modules 24, one immediately downstream of the first monochromator 20 and the other immediately upstream of the vacuum chamber 26. The vacuum chamber 26 houses a sample holder 16, which may include a motorized translational and / or rotary stage, as well as other typical sample stages known in the field of X-ray scattering.

[0070] Upstream and near the second slit module 24, the X-ray scattering device 10 includes a second X-ray beam delivery system 28, which includes a second X-ray source 30, an associated second monochromator 32, and a collimator extension. The distance between the second slit module 24 and the second X-ray beam delivery system 28 is typically several centimeters, preferably 5 cm or less. The second X-ray source 30, the second monochromator 32, and the collimator extension 34 are mounted on an insertion module having a motorized platform 36. Figure 1a The dotted lines in the diagram are used to indicate the meaning.

[0071] In the SAXS configuration of the first embodiment of the X-ray scattering device 10, as Figure 1a , Figure 2a and Figure 3a As shown, the motorized platform 36 moves to a position such that the collimator extension 34 is aligned with the main collimator 38, which extends downstream of the first slit module 24. Then, a first X-ray beam 22 propagates along the Y direction through the main collimator 38 and subsequently the collimator extension 34, both of which are evacuated as known in the field of X-ray scattering. The first X-ray beam 22 enters a vacuum chamber 26, preferably in the same evacuated environment as the main collimator 38, and impacts the sample mounted on the sample holder 16. The first X-ray beam 22, transmitted as a direct beam, and the SAXS signal generated by the sample exit the vacuum chamber 26 through corresponding exit ports and are detected by a distal X-ray detector 14 located near the distal end of another evacuation tube 40 downstream of the vacuum chamber 26.

[0072] In order to be able to measure sample structures with dimensions greater than 200 nm, the distal X-ray detector 14 is typically placed at a distance of at least 1 m from the sample holder 16, preferably more than 1.5 m and up to 4 m or 6 m.

[0073] The first monochromator 20 is typically a multilayer X-ray monochromator, preferably adapted to adjust the beam in two directions to focus it at a large distance at the furthest position of the distal X-ray detector 14 (when positioned in the SAXS measurement position), thereby allowing for the highest resolution, i.e., to measure the largest feature size or detect the smallest scattering angle. Alternatively, the first monochromator 20 focuses at an even greater distance, resulting in extremely low divergence; or produces a parallel beam (equivalent to infinite focusing), i.e., residual divergence <0.2 mradian. The shape of the first monochromator 20 is configured to produce 2D beam adjustment, i.e., its shape is configured as an ellipse of revolution (if focusing the beam) or a paraboloid of revolution (if collimating the beam), or it is made of two 1D mirrors cross-connected in a so-called Montel mirror configuration. Alternatively, if the X-ray source 18 is a linear focal source, then the first monochromator 20 is a mirror that is bent in one direction to produce 1D beam adjustment.

[0074] exist Figure 1a In the top view, it can be seen that the first monochromator 20 is curved into an ellipse in the XY plane to focus the beam in that plane onto the distal X-ray detector 14, where it is positioned at its SAXS measurement location with the longest sample-to-detector distance, which can be greater than 1 m and at most 6 m to 8 m. Therefore, the X-ray beam regulated by the first monochromator 20 is also collimated by two low-scattering slit modules 24, which eliminate any parasitic scattering and attenuate the beam edge intensity to achieve good beam size control at the distal X-ray detector 14. To prevent the generation of parasitic slit scattering, each of the slit modules 24 has blades made of a crystalline material (Si for copper Ka radiation, Ge or GaAs for Ka radiation or higher energies). The two slit modules 24 are spaced far apart, typically in the range of 80 cm to 1 m or 2 m, depending on the maximum sample-to-detector distance of the system.

[0075] Furthermore, in this configuration, some WAXS signals can be measured by moving the distal X-ray detector 14 closer to the sample holder 16 along the Y direction inside the vacuum chamber 26.

[0076] On the other hand, in the dedicated WAXS configuration of the first embodiment of the X-ray scattering device 10, such as Figure 1b , Figure 2b and Figure 3bAs shown, the motorized platform 36 moves to a position such that the second X-ray source 30 and the associated second monochromator 32 are aligned with the main collimator 38.

[0077] The second monochromator 32 selects and sets the focus of the X-rays generated by the second X-ray element 30 as the second X-ray beam 42 onto or near the focal point of the sample holder 16. The WAXS signal scattered or diffracted from the sample is then detected by a near-side X-ray detector 44 located inside the vacuum chamber 26. In an embodiment of the invention, when placed close to the sample after movement along the propagation direction (Y), the WAXS signal scattered or diffracted from the sample can be collected by a far-side X-ray detector 14.

[0078] In many cases, the sample holder 16 is positioned the same in the WAXS configuration as in the SAXS configuration. However, this is not mandatory, as the invention only requires that the second X-ray beam 42 be focused on or near the sample holder 16, which also covers cases where the sample holder 16 moves between the SAXS and WAXS positions within the vacuum chamber 26. Such movement of the sample holder 16 may be substantially along the Y direction, but may also have X and / or Z components.

[0079] The second X-ray source 30 may be a point focal source, and the second monochromator 32 may be adapted to focus the second X-ray beam 42 in two directions to produce a small focal point on or near the sample. Proximal generally means a distance of 100 mm or less from the sample in the Y direction (before or after the sample), preferably less than 50 mm (before or after the sample), and more preferably less than 25 mm (before or after the sample).

[0080] The second X-ray beam delivery system 28 is adapted to generate a small focal spot on the sample because it is positioned close to the sample, immediately before the final (less scattering) slit module 24. As an example, the second X-ray source 30 may be located at a distance (P'1+P'2) less than 700 mm from the sample, where P'1 is the distance from the second X-ray source 30 to the second monochromator 32, and P'2 is the distance from the second monochromator 32 to the focal spot generated by the second X-ray beam 42 on or near the sample holder 16. P'1 and P'2 are generated by... Figure 1b The corresponding arrows in the diagram indicate this. This arrangement allows for the positioning of secondary multilayer optics with a small magnification factor, given by the factor P'2 / P'1.

[0081] Thus, when using a micro-focused sealed tube source, it is possible to achieve a focal size in the range of 200 μm or smaller, which has an intensity of an order of magnitude higher than that achieved by the first monochromator 20.

[0082] Utilizing this collinear SAXS / WAXS configuration of the X-ray scattering apparatus 10 according to the invention, the second X-ray beam delivery system 28 generates a second X-ray beam 42 aligned with the beam path of the first X-ray beam 22. This provides the advantage of having the same propagation direction toward the sample, which allows the application of the same distal X-ray detector 14 or detector configuration of the distal X-ray detector 14 and the proximal X-ray detector 44 without the need for detector orientation on a goniometer or motor arm. This also allows the use of the same sample orientation for 2D applications in which a specific scattering direction is studied, for example, when stretching a sample using a stretching stage inside the vacuum chamber 26, without any need for a second rotary stage with the sample. Furthermore, maintaining the same tilt ensures an equivalent X-ray beam footprint on the sample, which is important for plotting or small-focus applications (e.g., microfluidics), as additional tilt of the sample stage and orientation of the distal X-ray detector 14 would otherwise be required to ensure that the direct beam strikes the distal X-ray detector 14 in the case of focused beam measurement.

[0083] If different sample positions are used in the apparatus 10 for scattering measurements (i.e., when the sample-to-detector distance is partially altered by moving the sample), then a collinear SAXS / WAXS design is also more advantageous. This simplifies the insertion module, requiring only translation to insert the second X-ray beam delivery system 28, without the need for synchronized translation and movement of the sample. In any case, it is preferable to achieve the change in sample-to-detector distance by moving the distal X-ray detector 14, so that the sample position is predetermined and fixed for all experiments.

[0084] Furthermore, by using a collinear SAXS / WAXS setup, the second slit module 24 can be used in the beam path of the first X-ray beam to adjust the divergence of the focused second X-ray beam 42 generated by the second X-ray beam delivery system 28. The second slit module 24 can also be used with the distal X-ray detector 14 to control intensity when switching from one configuration to another and to detect any potential need for realignment. A 1D scan of the slit module 24 parallel to the translation direction can also be used to realign the slit module 24 and re-center the beam path of the second X-ray beam 42 to realign the beamline for focusing measurements.

[0085] In some cases, the primary collimator 38 may include a Bonschart monochromator module that includes a motorized retainer to position the channel-cutting monochromator within or outside the X-ray beam when performing USAXS or SAXS measurements, respectively. This motorized Bonschart monochromator is associated with a Bonschart analyzer that includes a channel-cutting monochromator positioned behind the sample, which can be positioned within or outside the beam when performing USAXS or SAXS measurements, respectively. The Bonschart monochromator module may be located upstream of the second X-ray beam delivery system 28 to ensure that the second X-ray beam delivery system 28 is on the nearest side of the second slit module 24.

[0086] Figure 4a It shows that it is in Figure 1a , Figure 2a and Figure 3a An enlarged perspective view of the second X-ray beam delivery system 28 of the X-ray scattering device 10 according to the invention in a SAXS configuration; in this SAXS configuration, the first X-ray beam 22 propagates through the main collimator 38 and the collimator extension 34 before reaching the second slit module 24.

[0087] Figure 4b It shows that it is in Figure 1b , Figure 2b and Figure 3b An enlarged perspective view of the WAXS-configured X-ray beam delivery system 28. In this WAXS configuration, the motorized platform 36 has positioned the second X-ray beam delivery system 28, including the second X-ray source 30 and the second monochromator 32, in the beam path downstream of the main collimator 38 and upstream of the second slit module 24. The second X-ray beam delivery system 28 is effective in that it generates a second X-ray beam 42 focused on or near the focal point of the sample holder 16.

[0088] As from Figure 4a and Figure 4b As can be seen, the downstream end of the main collimator 38 and the upstream end of the collimator extension 34 are provided with corresponding connecting elements for vacuum tight connection. These connecting elements include sliding plates with vacuum-tight O-rings. The same applies to the downstream end of the collimator extension 34, thereby allowing vacuum tight connection to the second slit module 24. This arrangement ensures that when the first X-ray beam delivery system 12 or the second X-ray beam delivery system 28 is active or during configuration changes, the inside of the collimator extension 34 is in the same evacuation environment as the inside of the main collimator 38.

[0089] Figure 4aA sliding plate 362 is shown, which forms a connection between the downstream end of the collimator extension 34 and the second slit module 24 via a connecting portion 364, ensuring a vacuum-tight connection. This sliding plate 362 also forms a connection between the second X-ray beam delivery system 28 and the second slit module 24 via the connecting portion 364, also under vacuum-tight connection conditions. The vacuum-tight connection is ensured by sliding seals 366 and 368, which slide along the flat and smooth surface of the connecting portion 364 to ensure that a vacuum is maintained at all times inside the collimator extension 34 and inside the second beam delivery system 28. The sliding seals 366 and 368 may comprise a stack of O-rings and flat washers, wherein, for example, a spring-loaded O-ring presses a low-friction washer against the connecting portion 364.

[0090] implement Figure 4a and Figure 4b The connection between the two connecting portions 364 shown (i.e., the first connecting portion 364 at the downstream end of the main collimator 38 and the second connecting portion 364 at the downstream end of the collimator extension 34) ensures a certain degree of flexibility, allowing the corresponding sliding plate 362 to move without friction while maintaining the rigidity of the connection between the components. For this purpose, the collimator extension 34 can be a rigid tube, or alternatively a more flexible system combining a bellows and a more rigid portion. Alternatively, the collimator extension 34 can be provided with a retraction / extension mechanism, allowing the collimator extension 34 or a portion thereof to then retract and extend to facilitate changes in configuration.

[0091] In an alternative embodiment of the invention (where the second X-ray beam delivery system 28 includes a second X-ray source 30 and a second monochromator 32), this second X-ray beam delivery system 28 may alternatively be positioned at a fixed location at the entrance of the vacuum chamber 26, preferably with the focal point of the second X-ray source 30 in the same horizontal plane XY as the first X-ray source 18. Such a configuration typically requires the second X-ray source 30 and the second monochromator 32 to be tilted relative to the direction of the first X-ray beam 22 along the Y direction. Such embodiments of the invention would be suitable for high-resolution WAXS measurements using a near-side X-ray detector 44, which is positioned in a manner that allows it to collect X-ray beams scattered from the sample at a wide angle. This dedicated measurement is preferably advantageous when the near-side X-ray detector 44 is a mobile detector (which can move along the surface of an Ewald sphere to measure the scattering pattern scattered at a wide angle in the incident plane (YZ) or in the lateral direction).

[0092] Figure 1b , Figure 2b and Figure 3bThe configuration shown is suitable for WAXS measurements (including high-resolution WAXS measurements) and also for high spatial resolution SAXS measurements.

[0093] Figure 5 A schematic diagram of a second embodiment of the X-ray scattering apparatus 10 according to the present invention is shown. In this second embodiment, the apparatus 10 utilizes only a single X-ray source, namely, a first X-ray source 18; and a second X-ray beam delivery system 28 includes an optical module and a positioning module configured to position the optical module upstream of the sample holder 16 toward the first X-ray beam 22. The optical module is configured to collect the first X-ray beam 22 and convert it into a second X-ray beam 42, which is focused on or near a focal point on the sample holder 16.

[0094] Figure 6 A schematic side view of the positioning module 46 and optical module 48 used in a second embodiment of the present invention is shown. The optical module 48 may be a multi-layer module, such as a multi-layer mirror.

[0095] Positioning module 46 includes a vacuum-fitted motorized retainer 50, which holds the optical module 48. The motorized retainer 50 is movable upwards and downwards along the vertical Z-direction, as if... Figure 6 As indicated by the dashed double arrow. When moved to its lowest position, the first X-ray beam 22 is unaffected by the positioning module 46, the optical module 48, or any other component of the second X-ray beam delivery system 28, and reaches the sample, such as Figure 1a , Figure 2a and Figure 3a As shown. Therefore, the lowest position of the motor retainer 50 corresponds to the SAXS configuration of the X-ray scattering device 10.

[0096] As the motor retainer 50 moves upward along the vertical Z direction, it reaches a position where the optical module 48 intercepts the first X-ray beam 22. The optical module 48 is selected and configured such that it converts the first X-ray beam 22 into a second X-ray beam 42 (e.g., by reflection or Bragg diffraction) and focuses it onto or near a focal point on the sample. This aspect is schematically shown in Figure 5 In the case of the first monochromator 20 having the shape of an ellipse of revolution, the shape of the optical module 48 can be set to a hyperboloid of revolution, wherein the ellipse and the hyperboloid share one of their foci, the second foci of the hyperboloid is located at the sample position, and the first foci of the ellipse is located at the position of the first X-ray source 18.

[0097] Alternatively and as Figure 5As shown, when the first monochromator 20 has the shape of a first paraboloid of revolution to produce a parallel or low-divergence beam, the optical module 448 may have the shape of a second paraboloid of revolution to collect such a parallel beam and convert it into a focused beam. The second X-ray beam 42 produces a focal size F2 given by the ratio M2 = (P"2 / P1)*S1, where P"2 is the distance between the center of the optical module 48 and the focal point of the second paraboloid of revolution (which defines the shape of the optical module 48), P1 is the distance between the first monochromator 20 and the focal point of the first paraboloid (which defines its shape), and S1 is the size of the first X-ray source located at the focal point of the first paraboloid. Considering the size of the slit module 24 and the position of the sample holder 16 inside the vacuum chamber 26, the optical module 48 may have a focal length different from that of the first monochromator 20, such as... Figure 5 It is emphasized that the schematic plane F2 x The focal size F2 is larger than the X-ray source size S1. x In a preferred embodiment of the invention, the X-ray scattering device 10 achieves a relatively short distance between the optical module 48 and the sample, typically in the range of 30 cm to 40 cm or less. This ensures that when the first X-ray source 18 is a micro-focusing sealed tube source (taking into account any optical aberrations), the magnification factor M2 is maximized in the range of a factor of 3 or 4, thereby providing a focal size of less than 200 micrometers.

[0098] To facilitate the alignment of the optical module 48, in addition to the motorized retainer 50, the positioning module 36 may also be equipped with an additional rotary stage for Bragg angle alignment and / or an additional rotational or horizontal translation stage for optical alignment purposes. However, the positioning module 46 is designed such that the movement of the motorized retainer (to select between a configuration with and without the optical module 48) does not affect the alignment settings of the optical module 48, which is typically performed only during installation or periodic maintenance verification.

[0099] exist Figure 6 In the example shown, positioning module 46 also supports a channel-cutting incident monochromator 52, which is part of the Bunshart USAXS module. Positioning module 46 is configured to place optical module 48 or channel-cutting incident monochromator 52 into the incoming first X-ray beam 22. Placing channel-cutting incident monochromator 52 into the first X-ray beam 22 requires further upward movement of the motor holder 50.

[0100] In a preferred embodiment of the invention, the motor retainer 50 is vacuum-tight, and the second X-ray beam delivery system 28 according to the second embodiment of the invention can be completely housed inside the main collimator 38, which can then always extend between the two slit modules 24.

[0101] Figure 7 A schematic side view of another embodiment of the invention is shown, wherein the X-ray scattering apparatus 10 is further equipped with an additional X-ray mirror, namely, a deflecting mirror provided upstream of the sample holder 16. This mirror 54 is preferably a plane X-ray mirror to deflect the first X-ray beam 22 by an angular deviation 2θ, where angle θ is the angle of incidence on the mirror 54, such as reaching the surface of the sample 17 to be analyzed under grazing incidence conditions in GISAXS, while the surface of the sample 17 remains horizontal. This is particularly advantageous when the sample to be analyzed in grazing incidence is liquid. When the mirror 54 is used in total internal reflection geometry, adjustments to the incidence control of the sample 17 are possible, with resolution given by the divergence of the incoming beam. This angle of incidence control range for copper radiation can be between >0° and ~0.4°, allowing modification of the angle of incidence or setting of a specific angle during experiments. In a preferred embodiment of the invention, as an additional optional optical option, the deflecting mirror 54 may be part of the motorized holder 50.

[0102] Figure 8 A top view of a modified embodiment of the first embodiment equipped with a third X-ray beam delivery system is shown, comprising an imaging X-ray source 55 coupled to a primary slit module 56, which is positioned on a motorized platform 36 to form an additional X-ray beam suitable for phase-contrast imaging of the sample. Phase-contrast X-ray imaging is particularly advantageous for imaging minute density differences on the inner surface of soft materials and for overcoming the contrast limitations of conventional absorption X-ray imaging.

[0103] To perform phase-contrast imaging, the imaging X-ray source 55 is a focal source that generates a multicolor beam and is coupled to the primary slit module 56 to form a conical X-ray beam in the direction of the sample holder 56, capable of illuminating the sample and the random structure object 57, which is typically located directly in front of the sample. The imaging X-ray source 55 may typically be a source with a tungsten or molybdenum anode that excites at up to 50 kV, or alternatively up to 70 kV, depending on the small focal size (i.e., 50 μm focal length or smaller, preferably 10 μm or smaller) of the material to be analyzed. Alternatively, the imaging X-ray source 55 may comprise a copper anode. The imaging characterization step typically involves measuring the speckle pattern generated by the random structure object 57 on a distal detector 14, which is positioned at a long distance with no sample in place interfering with the propagating X-ray beam 58, and performing additional exposures with the sample and random structure object 57 in place to record a sample-induced distorted image of the speckle pattern on the distal detector 14, which is maintained at the same distance. By correlating the speckle patterns with and without the sample, a two-dimensional phase map of the sample can be retrieved. The resolution depends on the size of the speckle (i.e., the resolution of the features of the random structure object 57), as well as the 14-pixel size of the distal detector 14 and its distance from the sample. The random structure object 57 is a sample made of random structures (with small features and high X-ray intensity contrast), and can be, for example, sandpaper or cardboard. Alternative characterization sequences for this speckle X-ray imaging may include scanning the speckle pattern at different lateral positions of the random structure object 57 with a step size smaller than the speckle size to increase spatial resolution.

[0104] X-ray spot imaging is a particularly advantageous phase-contrast imaging method because it does not require complex analyzer structures and reduces the requirements for the spatial coherence of the source to be used. By using the imaging X-ray source 55 together with the interconversion insertion module as a whole for the second beam delivery system 28, as... Figure 8The described X-ray scattering apparatus can achieve both SAXS and X-ray imaging using the same detection scheme, i.e., utilizing a distal X-ray detector 14 suitable for easy and preferentially maneuverable variation of the sample-to-detector distance over long distances. Generally, X-ray imaging requires a smaller pixel detector compared to the hybrid pixel photon counting detector used in SAXS, typically with a pixel size in the range of a minimum pixel size of 75 μm or a maximum pixel size of 172 μm to accommodate detector size requirements, a high count rate (to enable measurement of direct beams or high dynamic range signals), and low noise. The configuration according to the invention achieves a high imaging magnification given by the ratio S2 / (S1), where S1 is the source-to-object distance and S2 is the source-to-imaging detector distance, S2 typically being greater than 10 times. In another embodiment of the invention (where the scattering device 10 includes phase-contrast imaging capability), the imaging X-ray source 55 and the primary slit module 56 are mounted on the sample chamber wall, for example, fixed to an additional incident beam port, located on top or bottom of the port for the beam path into the primary incident beamline, to shorten the distance to the sample for higher intensity and even larger imaging magnification. In this case, the change in measurement configuration from SAXS to phase-contrast imaging includes a change in the sample position along the Z direction, coupled with an equivalent change in the X-ray distal detector if desired. Alternatively, since the X-ray detector used for SAXS is a large detector (>70*70mm), 2 And it can be as large as >150*150mm 2 The vertical movement of the detector may be unnecessary.

[0105] Combining SAXS and / or USAXS with phase-contrast imaging is particularly useful for non-uniform soft materials (e.g., clay, fibers, heterogeneous nanocomposites), where non-uniformity can be detected first with the phase-contrast imaging measurements described herein, achieving a resolution of tens or several micrometers, and then further details of the nanostructure of the non-uniformity can be probed with SAXS or USAXS measurements.

[0106] The X-ray generators used in the first X-ray source 18 and the second X-ray source 30 may include a sealed tube X-ray source, preferably a micro-focused sealed tube source, or a rotating anode, preferably a point-focused anode, or a liquid jet anode.

[0107] The term "focal point" as used in the specification and claims is not necessarily point-like. It can be linear or generally have a 2D or 3D shape, depending on the sample and the intended X-ray scattering analysis.

Claims

1. An X-ray scattering apparatus (10) comprising: - a sample holder (16) for aligning and / or orienting a sample (17) for analysis by X-ray scattering; - a first X-ray beam delivery system (12) comprising a first X-ray source (18) and a first monochromator (20) and arranged upstream of the sample holder (16) for generating and directing a first X-ray beam (22) along a beam path in a propagation direction (Y) towards the sample holder (16); - a distal X-ray detector (14) arranged downstream of the sample holder (16) and movable along the propagation direction (Y) for detecting the first X-ray beam (22) and X-rays scattered from the sample (17) at different scattering angles; wherein the first X-ray beam delivery system (12) is configured to focus the first X-ray beam (22) on or near a focal point on the distal X-ray detector (14) when placed at its maximum distance from the sample holder (16), or to produce a parallel beam, characterized in that the X-ray scattering apparatus (10) further comprises a second X-ray beam delivery system (28) configured to focus a second X-ray beam (42) on or near a focal point on the sample holder (16), wherein the second X-ray beam delivery system (28) comprises a second X-ray source (30) and a second monochromator (32); an insertion module configured to move the second X-ray beam delivery system (28) into the first X-ray beam (22) at a position upstream of the sample holder (16); and a main collimator tube (38) extending along the beam path from a position downstream of the first X-ray beam delivery system (12) to a position upstream of the sample holder (16), wherein the insertion module comprises a motorized platform (36) configured to alternatively position the second X-ray beam delivery system (28) or a collimator extension (34) into the beam path at a position between the main collimator tube (38) and the sample holder (16).

2. The X-ray scattering apparatus (10) according to claim 1, further comprising a proximal X-ray detector (44) arranged downstream of the sample holder (16) to allow the first X-ray beam (22) to pass through and to detect X-rays scattered from the sample (17).

3. The X-ray scattering apparatus (10) according to claim 1, wherein the connection of the second X-ray beam delivery system (28) to the beam path comprises connection elements (362, 364, 366, 368) for vacuum tight connection.

4. The X-ray scattering device (10) according to claim 3, wherein the downstream end of the primary collimator (38) and the upstream end of the collimator extension (34) are provided with respective connection elements (362, 364, 366, 368) for vacuum tight connection.

5. The X-ray scattering device (10) according to claim 3 or 4, wherein the collimator extension (34) is provided with a retraction / extension mechanism.

6. The X-ray scattering device (10) according to claim 1 or 2, wherein the second X- ray beam delivery system (28) comprises an optical module (48) and a positioning module (46), the positioning module (46) being configured to position the optical module (48) at a position upstream of the sample holder (16) to the first X-ray beam (22), wherein the optical module (48) is configured to convert the first X-ray beam (22) into a second X-ray beam (42) focused on a focal point on or near the sample holder (16).

7. The X-ray scattering device (10) according to claim 6, wherein the positioning module (46) comprises a vacuum-tight motorized holder (50) configured to hold the optical module (48).

8. The X-ray scattering device (10) according to claim 1, further comprising first and second slit modules (24) upstream of the sample holder (16), the first and second slit modules (24) being used in combination for shaping the first X-ray beam (22), wherein the second slit module (24) is downstream of the second X-ray beam delivery system (28) for further shaping the second X-ray beam (42), wherein the distance between the second slit module (24) and the second X-ray beam delivery system (28) is 5 cm or less.

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