Multilayer Kirkpatrick-Baez focusing mirrors with phase compensation for sub-20 nm focusing at the hard X-ray nanoprobe beamline of SSRF.

The hard X-ray nanoprobe beamline is the first beamline to take advantage of the full coherent beam to attain the nanoscale focusing at the Shanghai Synchrotron Radiation Facility (SSRF). Here we introduce the beamline and specially go over the features of the multilayer Kirkpatrick-Baez focusing system and its supporting phase compensator system. The performance and stability of the phase compensator are also put to the test. By using the speckle scanning metrology, the wavefront of a focused beam was characterized and intensity distribution near the focus was reconstructed. The focusing performance was greatly enhanced by two phase compensations based on a global optimization technique, and a two-dimensional focal spot of 26 nm × 17 nm was achieved and maintained with good stability.

An active piezoelectric plane X-ray focusing mirror with a linearly changing thickness.

X-ray mirrors for synchrotron radiation are often bent into a curved figure and work under grazing-incidence conditions due to the strong penetrating nature of X-rays to most materials. Mirrors of different cross sections have been recommended to reduce the mirror's slope inaccuracy and clamping difficulty in order to overcome mechanical tolerances. With the development of hard X-ray focusing, it is difficult to meet the needs of focusing mirrors with small slope error with the existing mirror processing technology. Deformable mirrors are adaptive optics that can produce a flexible surface figure. A method of using a deformable mirror as a phase compensator is described to enhance the focusing performance of an X-ray mirror. This paper presents an active piezoelectric plane X-ray focusing mirror with a linearly changing thickness that has the ability of phase compensation while focusing X-rays. Benefiting from its special structural design, the mirror can realize flexible focusing at different focusing geometries using a single input driving voltage. A prototype was used to measure its performance under one-dimension and two-dimension conditions. The results prove that, even at a bending magnet beamline, the mirror can easily achieve a single-micrometre focusing without a complicated bending mechanism or high-precision surface processing. It is hoped that this kind of deformable mirror will have a wide and flexible application in the synchrotron radiation field.

Valorization of waste Fe-rich sludge as erdite/KFeS2 rods under atmosphere condition and evaluation of their mutual transformation.

Pilot scale production of one-dimensional (FeS2)nn- rods was performed by using an automatic 20 L vessel at 80 °C under atmosphere condition with the resource utilization of Fe-rich sludge. The sludge was simulated at lab-scale with chemical pure of ferric trichloride. After the sludge treatment, the corresponding rods were not formed at room temperature. But by heating at 80 °C, erdite rod was well-crystallized after 0.5 h by only adding Na halite, and KFeS2 rod was crystallized weakly after 2 h and highly at 10 h with the addition of K halite. After 48 h heating, the rods grow radially to 300 nm for erdite, but to 5 µm for KFeS2. However, at room temperature, erdite rod was converted to high crystallized KFeS2 in KOH water or ethanol solution, whilst the conversion of KFeS2 rod to erdite also occurred in NaOH water solution, but terminated in NaOH ethanol solution, without any morphology change. It is also noted that with the presence of both Na and K halite, the rod was an intermediate of erdite to KFeS2 with 1 µm length after heating at 100 °C but converted to 10-µm-length KFeS2 crystal at the temperature of > 120 °C. The thermodynamic results confirmed that during the rod polymerization, the Fe(OH)3HS- formation was the sole rate-limiting step and showed a positive Gibbs value of 6.45 kJ/mol at room temperature and negative values at the temperature of > 48 °C. In summary, this method not only enabled the vaporization of waste Fe-rich sludge as value-added rods without generating any secondary waste but also showed a new route for the in situ conversion of erdite/KFeS2 rods at room temperature.

DPP-based polymers with linear/branch side chain for organic field-effect transistors.

For polymer semiconductors, the packing ability and molecular weight of polymers play a very critical role in their optoelectronic properties and carrier transport properties. In this work, two polymers, named linear and branch, are designed and synthesized with donor-acceptor (D-A) structure, based on diketopyrrolopyrrole as an electron acceptor and carbazole as an electron donor, and applied these two polymers in organic field-effect transistors. Linear and branch have similar conjugated backbones but different molecular weights and alkyl chains. The effects of molecular weight and molecular aggregation ability on the carrier transfer efficiency are investigated. As a result, linear exhibits better aggregation ability, but due to its smaller molecular weight than branch molecule, the hole transfer efficiency of linear (1.1 × 10-2 cm2 V -1 s-1) is slightly lower than that of branch (2.3 × 10-2 cm2 V -1 s-1). This work proves that molecular weight is more important than molecular aggregation ability when designing organic field-effect transistors for polymer semiconductors.

Pyrrolopyrrole-Based Aza-BODIPY Small Molecules for Organic Field-Effect Transistors.

Diketopyrrolopyrrole (DPP), due to its good planarity, π-conjugate structure, thermal stability, and structural modifiability, has received much attention from the scientific community as an excellent semiconductor material for its applications in the field of optoelectronics, such as organic solar cells, organic photovoltaics, and organic field effect transistors. In this study, a new small molecule, pyrrolopyrrole aza-BODIPY (PPAB), based on the thiophene-substituted DPP structure was developed using the Schiff-base formation reaction of DPP and heteroaromatic amines. Absorption spectroscopy, electrochemistry, X-ray diffraction, molecular theoretical simulation calculation were performed, and organic field-effect transistor properties based on PPAB were investigated. It was found that PPAB exhibits a broad absorption range in the visible and near-infrared regions, which is attributed to its long-range conjugate structure. In addition, it is worth noting that PPAB has multiple F atoms resulting in the low LUMO level, which is conducive to the injection and transportation of charge carriers between the semiconductor layer and the electrode. Meanwhile, its hole carrier mobility is up to 1.3 × 10-3 cm2 V-1 s-1 due to its large conjugate structure, good intramolecular charge transfer effect, and high degree of coplanarity. In this study, a new chromophore with electron-deficient ability for designing high-performance semiconductors was successfully synthesized.

Nanocrystalline erdite from iron-rich sludge: Green synthesis, characterization and utilization as an efficient adsorbent of hexavalent chromium.

A low-temperature hydrothermal process was developed to synthesize erdite adsorbent from a solid waste sludge contained 10.2% Fe, 6.2% Al and 1.4% Si, alongside 59.5% water content. At 90℃, adding Na2S and NaOH could convert it into erdite nanorods with a diameter of 80 nm and a length of 100 nm. In the sludge, only Fe oxyhydroxide was involved in the formation of erdite, and the other Al/Si-bearing compounds were dissolved in an alkaline medium. The dissolved Al/Si-bearing compounds were further removed, forming faujasite so that the used medium was purified and then entirely recycled into the next conversion stage. No secondary waste was generated in the pilot-scale conversion, and the adsorption efficiency of the prepared products to wastewater with a high initial Cr(VI) concentration of 1000 mg/L was more than 99.5%. The adsorption data complied with the pseudo-second-order kinetics. During the wastewater treatment, hexavalent chromium anion diffused to erdite surface and replaced OH/SH groups of adjacent structural Fe to form a stable complex ligand. In addition, the redox reaction between hexavalent chromium and the -SH group occurred to generate a trivalent chromium complex on the Fe/S-bearing flocs surface.

Dopant-Free π-Conjugated Hole Transport Materials for Highly Stable and Efficient Perovskite Solar Cells.

Current high-efficiency hybrid perovskite solar cells (PSCs) have been fabricated with doped hole transfer material (HTM), which has shown short-term stability. Doping applied in HTMs for PSCs can enhance the hole mobility and PSCs' power conversion efficiency, while the stability of PSCs will be significantly decreased due to inherent hygroscopic properties and chemical incompatibility. Development of dopant-free HTM with high hole mobility is a challenge and of utmost importance. In this review, a series of selected and typical π-conjugated dopant-free hole transport materials, mainly regarding small molecules, are reviewed, which could consequently help to further design high-performance dopant-free HTMs. In addition, an outline of the molecular design concept and also the perspective of ideal dopant-free HTMs were explored.

Microscale Investigation into Selenium Distribution and Speciation in Se-Rich Soils from Enshi, China.

In this study, we investigated the distribution and chemical speciation of Se in Se-rich soil by using micro-focused X-ray absorption near-edge structure (µ-XANES) spectroscopy coupling with X-ray fluorescence (µ-XRF) mapping. The microscale distribution showed that Se is heterogeneously distributed in the soil from seleniferous areas in Enshi, China. Se K-edge µ-XANES analysis suggested that Se is mainly present as Se(IV), organic Se(-II) or Se(0) species in Se-rich agricultural soil. The findings from this study would help improve the understanding of the fate, mobility, bioavailability, and biogeochemical cycling of Se in the seleniferous soil environment.

High-precision speckle-tracking X-ray imaging with adaptive subset size choices.

Speckle-tracking imaging has the advantages of simple setup and high-sensitivity to slowly varying phase gradients. Subset size choice is regarded as a trade-off problem for speckle-tracking X-ray imaging where one needs to balance the spatial resolution and accuracy, where the subset was defined as the region of interest of windowing choice for digital image correlation algorithm. An adaptive subset size choice method based on a Fourier transform for effectively detecting sample phase information without foreknowledge of the sample structure is presented in this study. The speckle-tracking phase-contrast and the form of dark-field imaging based on this method have the advantages of (i) high resolution and time saving compared to large subset choice and (ii) partially improvement the influence from experimental noises, background fluctuations, and false signals compared to small subset choice at the same time. This method has proven to be particularly robust in the experimental condition of poor signal-to-noise ratio. The proposed method may be expanded to all speckle-based imaging methods and other imaging techniques based on the subset or window matching.

Influence of diffuser grain size on the speckle tracking technique.

The speckle-based X-ray imaging technique (SBT), which includes the three imaging modalities of absorption, phase contrast and dark field, is widely used in many fields. However, the influence of the grain size of the diffuser, the coherence of the X-ray source and the pixel size of the detector on the multi-mode imaging quality of SBT is still woefully unclear. In this paper, the whole SBT process is simulated and the influence of these three factors on image quality is discussed. Based on this discussion, the grain size of the diffuser for SBT applications should be limited by the pixel size of the detector and the coherence length of the X-ray source. According to analysis of the noise signal and correlation map, a suitable grain size is an indispensable condition for high-quality SBT images, because an excessively small or large grain size degrades the resolution of the imaging results and generates false signals. In addition, the power spectral density of the measured raw speckle patterns demonstrates that a smaller grain can better retain high-frequency information from an imaged sample. The simulated and experimental results verify these conclusions. The conclusions of this work will be helpful in designing suitable experimental setups for SBT applications and have the potential to promote the performance of SBT in other applications, such as X-ray optics metrology and coherence measurement.

A piezoelectric deformable X-ray mirror for phase compensation based on global optimization.

As a strong tool for the study of nanoscience, the synchrotron hard X-ray nanoprobe technique enables researchers to investigate complex samples with many advantages, such as in situ setup, high sensitivity and the integration of various experimental methods. In recent years, an important goal has been to push the focusing spot size to the diffraction limit of ∼10 nm. The multilayer-based Kirkpatrick-Baez (KB) mirror system is one of the most important methods used to achieve this goal. This method was chosen by the nanoprobe beamline of the Phase-II project at the Shanghai Synchrotron Radiation Facility. To overcome the limitations of current polishing technologies, the use of an additional phase compensator was necessary to decrease the wavefront distortions. In this experiment, a prototype phase compensator has been created to show how to obtain precise wavefront compensation. With the use of finite-element analysis and Fizeau interferometer measurements, some important factors such as the piezoresponse, different actuator distributions, stability and hysteresis were investigated. A global optimization method based on the measured piezoresponse has also been developed. This method overcame the limitations of the previous local algorithm related to the adjustment of every single actuator for compact piezoelectric layouts. The mirror figure can approach a target figure after several iterations. The figure difference can be reduced to several nanometres, which is far better than the mirror figure errors. The prototype was also used to successfully compensate for the real wavefront errors from upstream and for its own figure errors, measured using the speckle scanning technique. The residual figure error was reduced to a root-mean-square value of 0.7 nm.

A 1-m non-resonant inelastic x-ray scattering spectrometer at BL15U, Shanghai Synchrotron Radiation Facility.

We report the design, construction, and commissioning of a spectrometer for non-resonant inelastic x-ray scattering study installed at BL15U, Shanghai Synchrotron Radiation Facility. It features a 1-m vertical scattering arm. An energy resolution of 1.3 eV is achieved based on the 1 m Rowland circle and the diced Si(555) crystal analyzer with a fixed Bragg angle of about 88.8°. The inelastic squared form factors of 21S + 21P of helium with respect to the momentum transfer were measured and compared with the accurate and reliable theoretical calculations in order to verify the spectrometer. Furthermore, the spectrometer is designed to work in the momentum transfer region of 0 Å-1 < q < 8.68 Å-1 and to initially focus on the non-resonant inelastic x-ray scattering studies on gaseous samples.

[High accuracy sample positioning system for hard X-ray microprobe].

A novel sample offline positioning system was developed for hard X-ray micro-focus beamline (BL15U1) at Shanghai Synchrotron Radiation Facility (SSRF). The positioning system is composed of three parts: off-line sample microscope system, on-line sample experiment system, and high-precision positioning sample holder. It makes a potent combination of the on-line X-ray fluorescence imaging and the off-line microscopic examination in three steps: compiling of control program, positioning of sample holder, and conversion of the two coordinates. It's the first time in the domestic synchrotron radiation facilities to achieve sample offline positioning in micron scale. The system helps the researchers find the object of study in micro zone quickly and accurately, when they study the micro characteristics of materials using synchrotron radiation micro X-ray beam. The gold mesh was used as an object of study. By comparing the differences of coordinates of gold mesh nodes between pictures from offline microscope and pictures from X-ray fluorescence mapping, the accuracy of the offline positioning system was verified. The results showed that the average errors of X-axis and Z-axis were 1.3 and 2.5 microm respectively, using the positioning method. It was demonstrated that the sample offline positioning system not only is suitable for these applications with high efficiency, but also supply hard X-ray micro-focus beamline with the technical preparations of sample automatic focusing method.

Quantifying the influence of EDTA on polymer nanoparticle deposition and retention in an iron-oxide-coated sand column.

Ethylenediaminotetraacetic acid (EDTA) occurring in groundwater aquifers complicates the prediction of nanoparticle movement in the porous medium. This paper demonstrates an approach combining Triple Pulse Experiments (TPEs) and numerical modelling to quantify the influence of EDTA on the deposition and retention of polymer nanoparticles in a water-saturated column packed with iron-oxide-coated sand. TPEs injecting three successive pulses in the order of nanoparticle, EDTA, nanoparticle permit nanoparticle deposition in the absence and the presence of EDTA to be compared. Random Sequential Adsorption (RSA) modelling of the nanoparticle breakthrough curves combining mass balance calculation allows the influence of EDTA to be quantified. TPE results demonstrate that the injected EDTA eluted the oxide coatings (favorable deposition sites) from the sand surface and the resulting decline in sites led to enhanced nanoparticle mobility in the subsequent pulse. Quantification results suggest that at the experimental time-scale and under the controlled conditions, elution of one deposition site requires injection of 2.4 × 10(11) EDTA molecules. In total, 75 gram EDTA needs to be injected to remove all the column sites.