Crystal Block Research Articles

Functional organogelators formed by liquid-crystal carbazole-containing bis-MPA dendrimers

Functional organogels based on carbazole-containing liquid crystal block codendrimers that show an increased fluorescence emission and redox properties.

Unravelling the Key Driving Forces of the Spin Transition in π-Dimers of Spiro-biphenalenyl-Based Radicals.

Spiro-biphenalenyl (SBP) boron radicals constitute an important family of molecules for the preparation of functional organic materials. The building blocks of several SBP-based crystals are π-dimers of these radicals, in which two phenalenyl (PLY) rings face each other and the other two PLYs point away from the superimposed PLYs. The dimers of ethyl-SBP and butyl-SBP undergo a spin transition between a diamagnetic and a paramagnetic state upon heating, while other dimers exhibit paramagnetism at all temperatures. Here, we present a computational study aimed at establishing the driving forces of the spin-transition undergone by ethyl-SBP at ∼140 K. The ground state of the π-dimers below 140 K is a singlet state in which the SBP unpaired electrons are partially localized in the superimposed PLYs. Above 140 K, the unpaired electrons are localized in the nonsuperimposed PLYs. These high-temperature structures are exclusively governed by the ground triplet state because the open-shell singlet with the unpaired electrons localized in the nonsuperimposed PLYs does not feature any minimum in the potential energy surface of the system. Furthermore, we show that the electrostatic component of the interaction energy between SBP radicals in the π-dimers is more attractive in the triplet than in the singlet, thereby partially counteracting the bonding and dispersion components, which favor the singlet. This electrostatic stabilization of the triplet state is a key driving force of the spin transition of ethyl-SBP and a key factor explaining the paramagnetic response of the π-dimers of other SBP-based crystals.

Molecular approach to hexagonal and cubic diamond nanocrystals

In the present work, we propose a molecule (C₁₄H₁₄) that can be used as a building block of hexagonal diamond-type crystals and nanocrystals, including wurtzite structures. This molecule and its combined blocks are similar to diamondoid molecules that are used as building blocks of cubic diamond crystals and nanocrystals. The hexagonal part of this molecule is included in the C₁₂ central part of this molecule. This part can be repeated to increase the ratio of hexagonal to cubic diamond and other structures. The calculated energy gap of these molecules (called hereafter wurtzoids) shows the expected trend of gaps that are less than that of cubic diamondoid structures. The calculated binding energy per atom shows that wurtzoids are tighter structures than diamondoids. Distribution of angles and bonds manifest the main differences between hexagonal and cubic diamond-type structures. Charge transfer, infrared, nuclear magnetic resonance and ultraviolet-visible spectra are investigated to identify the main spectroscopic differences between hexagonal and cubic structures at the molecular and nanoscale. Natural bond orbital population analysis shows that the bonding of the present wurtzoids and diamondoids differs from ideal sp³ bonding. The bonding for carbon valence orbitals is in the range (2s^0.982p^3.213p^0.02)-(2s^0.942p^3.313p^0.02) for wurtzoid and (2s^0.932p^3.293p^0.01)-(2s^0.992p^3.443p^0.01) for diamantane.

Broadband sound blocking in phononic crystals with rotationally symmetric inclusions.

This paper investigates the feasibility of broadband sound blocking with rotationally symmetric extensible inclusions introduced in phononic crystals. By varying the size of four equally shaped inclusions gradually, the phononic crystal experiences remarkable changes in its band-stop properties, such as shifting/widening of multiple Bragg bandgaps and evolution to resonance gaps. Necessary extensions of the inclusions to block sound effectively can be determined for given incident frequencies by evaluating power transmission characteristics. By arraying finite dissimilar unit cells, the resulting phononic crystal exhibits broadband sound blocking from combinational effects of multiple Bragg scattering and local resonances even with small-numbered cells.

Depth-of-interaction measurement in a single-layer crystal array with a single-ended readout using digital silicon photomultiplier

We present the first experimental evaluation of a depth-of-interaction (DOI) positron emission tomography (PET) detector using a digital silicon photomultiplier (dSiPM). To measure DOI information from a mono-layer array of scintillation crystals with a single-ended readout, our group has previously proposed and developed a new method based on light spread using triangular reflectors. Since this method relies on measurement of the light distribution, dSiPM, which has a fully digital interface, has several merits for our DOI measurement. The DOI PET detector comprised of a dSiPM sensor (DPC-3200-22-44) coupled with a 14 × 14 array of 2 mm × 2 mm × 20 mm unpolished LGSO crystals. All crystals were covered with triangular reflectors. To obtain a good performance of the DOI PET detector, several parameters of detector were selected as a preliminary experiment. Detector performance was evaluated with the selected parameters and the optimal experimental setup, and a DOI measurement was conducted by irradiating the crystal block at five DOI positions spaced at intervals of 4 mm. Maximum-likelihood estimation was employed for DOI positioning and the optimal DOI estimation scheme was also investigated in this study. As a result, the DOI PET detector showed clear crystal identification. The energy resolution (full-width at half-maximum (FWHM)) averaged over all depths was 10.21% ± 0.15% at 511 keV, and time resolution averaged over all depths was 1198.61 ± 39.70 ps FWHM. The average DOI positioning accuracy for all depths was 74.22% ± 6.77%, which equates to DOI resolution of 4.67 mm. Energy and DOI resolutions were uniform over all crystal positions except for the back parts of the array. Furthermore, additional simulation studies were conducted to verify the results of our DOI measurement method that is combined with dSiPM technology. In conclusion, our continuous DOI PET detector coupled with dSiPM is a promising PET/MRI detector with DOI-encoding capability.

Phase Separation and Crystallization in High Hard Block Content Polyurethane Thin Films

Following studies of bulk behavior, the morphological evolution in thin films of linear TPUs with a high content of hard segment (HS) (from 70 to 100 wt %) on annealing is investigated. In contrast to melt-quenched bulk samples, a mixed phase was obtained for as-spin-cast films, and then, on annealing, a phase-separated mesophase domain, as previously observed by scattering and TEM in bulk samples, was observed by AFM to form directly from the mixed phase. In addition to this overall phase behavior, a crystallization behavior unique to thin films was observed: samples of thickness less than 120 nm and annealed at sufficiently high temperature developed large lamellar crystal blocks. Similar crystal blocks have also been found in thin films of a TPU with a more flexible chain extender, although in this case, with the greater HS/SS compatibility of this material, the phase separation behavior was not observed at all.

Capped ZnO (3, 0) nanotubes as building blocks of bare and H passivated wurtzite ZnO nanocrystals

In the present work we propose building blocks of hexagonal type crystals and nanocrystals of zinc oxide including wurtzite structure that are called wurtzoids. These molecules are ZnO (3,0) nanotubes capped at their two terminals with Zn or O atoms. Hexagonal part of these molecules is included in the central part of these molecules. This part can be repeated to increase hexagonal structure ratio. Hydrogen passivated and bare ZnO wurtzoids are investigated. Results show bare wurtzoids have shorter and stronger surface sp2 bonds than H passivated sp3 bonded wurtzoids. The calculated energy gap of these molecules shows the expected trend of gaps. Calculated binding energy per atom shows that wurtzoids are tight and stable structures which are not the case of ZnO diamondoids. Vibrational frequencies manifest the expected trends of hexagonal type structures. Reduced mass and force constant of these vibrations are investigated to illustrate the sp2 and sp3 bonding effects of bare and H passivated ZnO nanocrystals respectively.

Parameter Optimization of a Digital Photon Counter Coupled to a Four-Layered DOI Crystal Block With Light Sharing

We have developed four-layered depth-of-interaction (DOI) detectors based on light sharing. Reflectors, which are inserted in every two lines of crystal segments and shifted differently depending on each layer, project 3-D crystal positions to a 2-D position histogram without any overlapping after applying the Anger-type calculation. The DOI measurement itself has the potential to improve time resolution because the depth-dependent timing delay can be corrected. However, light sharing tends to increase variance of light paths inside the crystal block, thus resulting in worsened time resolution. Although we have reported advantages of our DOI detectors in terms of position and energy resolutions, we had not evaluated their potential for time resolution. In this paper, therefore, we measured timing performance with the help of a digital photon counter (DPC), which offers precise control of event triggering. There are several studies that have reported one-to-one coupling of the scintillator to the DPC pixel, but DPCs have not been studied well for light-sharing detectors. Therefore, in this work, we optimized measurement parameters of the DPCs for our four-layered DOI detector. The DOI detector consists of 256 LGSO crystals which are arranged in four layers of 8 ×8 arrays, coupled to the DPC array. Each crystal element is 2.9×2.9 ×5 mm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sup> . Each die of the DPC array provides an individual timestamp. Crystal identification performance largely depended on the dark count rate of the DPC array, which can be reduced by means of cell inhibition. We measured several conditions of the inhibition rate of microcells and temperature. For increased inhibition rate, we observed degraded time resolution, although positioning performance and energy resolution were improved. Regarding the temperature dependency within 10 to - 7 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">°</sup> C, we found that time resolution was insensitive. At 10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">°</sup> C and 20% inhibition rate, average time resolution over all crystals was 267 ±32 ps (full width half maximum). Better positioning performance and energy resolution were obtained for colder temperatures.

Desalination of seawater through progressive freeze concentration using a coil crystallizer

In this century, the shortage of clean water supply is an issue of concern and the problem is expected to become more serious in the future. Consequently, researchers are trying to find the best solution to address this problem by introducing new desalination technologies that are able to accommodate the increasing demand for clean water. One of the new technologies introduced is desalination of seawater through freeze concentration. In this study, progressive freeze concentration (PFC) was implemented to produce pure water in the form of an ice crystal block, leaving behind higher concentration seawater using a coil crystallizer. The effect of operating parameters such as initial concentration and coolant temperature were investigated. Meanwhile, the efficiency of the system was reviewed based on the value of the effective partition constant K which is defined by the ratio of solute in ice and liquid phase. A low value of K indicates when the system is most efficient. In addition, the results for the overall heat transfer coefficient are also presented to observe the heat transfer involved in the system.

Control of Air-Interface-Induced Perpendicular Nanocylinder Orientation in Liquid Crystal Block Copolymer Films by a Surface-Covering Method

A liquid crystalline block copolymer, composed of poly(ethylene oxide) (PEO) and polymethacrylate (PMA)-bearing azobenzene (Az) mesogen side chains, uniquely forms perpendicularly oriented PEO cylinders in a film on various substrates, independent of the substrate surface energy. In this paper, it is revealed that the perpendicular cylinders are formed at the air interface of the block copolymer film, as the perpendicular cylinders and liquid crystal structures were observed only in the vicinity of the air interface for a block copolymer film annealed for a short period of 5 s. On the basis of this mechanism of air-interface-induced perpendicular cylinder formation, we developed a surface covering method to prevent the perpendicular cylinder formation and instead induce parallel cylinder formation. Moreover, uniaxial cylinder films were fabricated by a combination of the surface covering and substrate rubbing methods. The surface covering layer for controlling cylinder orientation can be removed to utilize the block copolymer film for templating.

Magnetization reversal using excitation of collective modes in nanodot matrices.

The large arrays of magnetic dots are the building blocks of magnonic crystals and the emerging bit patterned media for future recording technology. In order to fully utilize the functionalities of high density magnetic nanodots, a method for the selective reversal of a single nanodot in a matrix of dots is desired. We have proposed a method for magnetization reversal of a single nanodot with microwave excitation in a matrix of magneto-statically interacting dots. The method is based on the excitation of collective modes and the spatial anomaly in the microwave power absorption. We perform numerical simulations to demonstrate the possibility of switching a single dot from any initial state of a 3 by 3 matrix of dots, and develop a theoretical model for the phenomena. We discuss the applicability of the proposed method for introducing defect modes in magnonic crystals as well as for future magnetic recording.

Mutual compensation property of electrooptic and magnetooptic effects and its application to sensor

Mutual compensation property between electrooptic and magnetooptic modulations in a crystal with electrooptic and magnetooptic effects and its application to magnetooptic sensor are investigated theoretically and experimentally. Under the condition of light intensity modulation, electrooptic and magnetooptic modulation effects can compensate for each other, so that the transmitted light intensity through the crystal can be kept at a certain fixed value. Based on this mutual compensation property, a novel optical current (or magnetic field) sensor is proposed and demonstrated experimentally by use of a single bismuth germanate (Bi4Ge3O12, BGO) crystal. The optical sensing unit is composed mainly of two polarizers and a block of BGO crystal with the shape of parallelogram. The BGO crystal itself can produce an optical phase bias of π/2, and it can be used as both a current sensing element and an electrooptic compensator. The change of magnetooptic rotation angle through the crystal can be compensated in real time by the change of electrooptic phase retardation caused by the applied voltage, thus the closed-loop optical measurement of current (or magnetic field) can be achieved. The 50 Hz ac current within 5 A is measured experimentally. The required compensating ac voltage is about 21.2 V/A in root-mean-square value. Experimental data show a good linear relationship between measured current and compensating voltage, and the nonlinear error is less than 1.7%.

Quasifision timescale: Zeptosecond versus attosecond

Recently a controversy has developed regarding the timescales of quasifission and fission processes of highly excited (EX > 50 MeV) transuranium and uranium-like nuclei. The mass-angle distributions of quasifission fragments indicate exponential decay law giving timescale of the order of 10-21 sec for the quasifission process, whereas for the similar reactions, timescale of the order of 10-18 sec were obtained from the crystal blocking technique. In the case of fission of highly excited uranium-like and transuranium nuclei, X-ray-fission fragment coincidence technique gives similar timescales ~10-18 sec, contradicting much shorter timescales obtained from nuclear techniques. We think the quantum decoherence time of the quasifission/fission decay process could be of the order of 10-18 sec and present a quantum mechanical explanation to resolve the puzzle.

Luminescence in medical image science

Radiation detection in Medical Imaging is mostly based on the use of luminescent materials (scintillators and phosphors) coupled to optical sensors. Materials are employed in the form of granular screens, structured (needle-like) crystals and single crystal transparent blocks. Storage phosphors are also incorporated in some x-ray imaging plates. Description of detector performance is currently based on quality metrics, such as the Luminescence efficiency, the Modulation Transfer Function (MTF), the Noise Power Spectrum (NPS) and the Detective Quantum Efficiency (DQE) can be defined and evaluated. The aforementioned metrics are experimental evaluated for various materials in the form of screens. A software was designed (MINORE v1) to present image quality measurements in a graphical user interface (GUI) environment. Luminescence efficiency, signal and noise analysis are valuable tools for the evaluation of luminescent materials as candidates for medical imaging detectors.

Recent progress of MPPC-based scintillation detectors in high precision X-ray and gamma-ray imaging

The multi-pixel photon counter (MPPC) is a promising light sensor for various applications, not only in physics experiments but also in nuclear medicine, industry, and even high-energy astrophysics. In this paper, we present the current status and most recent progress of the MPPC-based scintillation detectors, such as (1) a high-precision X-ray and gamma-ray spectral image sensor, (2) next-generation PET detectors with MRI, TOF, and DOI measurement capabilities, and (3) a compact gamma camera for environmental radiation surveys. We first present a new method of fabricating a Ce:GAGG scintillator plate (1 or 2mm thick) with ultra-fine resolution (0.2mm/pixel), cut using a dicing saw to create 50μm wide micro-grooves. When the plate is optically coupled with a large-area MPPC array, excellent spatial resolution of 0.48mm (FWHM) and energy resolution of 14% (FWHM) are obtained for 122keV gamma rays. Hence, the detector can act as a convenient “multi-color” imaging device that can potentially be used for future SPECT and photon-counting CT. We then show a prototype system for a high-resolution MPPC-based PET scanner that can realize ≃1mm (FWHM) spatial resolution, even under a strong magnetic field of 4.7T. We develop a front-end ASIC intended for future TOF-PET scanner with a 16-channel readout that achieves a coincidence time resolution of 489ps (FWHM). A novel design for a module with DOI-measurement capability for gamma rays is also presented by measuring the pulse height ratio of double-sided MPPCs coupled at both ends of scintillation crystal block. Finally, we present the concept of a two-plane Compton camera consisting of Ce:GAGG scintillator arrays coupled with thin MPPC arrays. As a result of the thin and compact features of the MPPC device, the camera not only achieves a small size (14×14×15cm3) and light weight (1.9kg) but also excellent sensitivity, compared to the conventional PMT-based pinhole camera used in Fukushima. Finally, we briefly describe a new product recently developed in conjunction with Hamamatsu Photonics K.K. that offers improved sensitivity and angular resolution of Δθ~8° (FWHM) at 662keV, by incorporating DOI-segmented scintillator arrays.

Effect of Coolant Temperature on Desalination Process via Progressive Freeze Concentration

The world is still suffering from a shortage of clean water supply and the problem is expected to become more serious in the future. Consequently, researchers have been trying to find the best solution to address this problem by introducing new desalination technologies that are able to accommodate the demand for clean water which is increasing from time to time. One of the new technologies introduced is the desalination of seawater through freeze concentration. In this study, progressive freeze concentration (PFC) is implemented to produce pure water in the form of ice crystal block and leave behind a higher concentration solution. The effect of coolant temperature was investigated and the efficiency of the system was reviewed based on the value of effective partition constant, K which is defined by the ratio of solute in ice and liquid phase. The low value of K leads to the best efficiency for the system. Apart from that, the efficiency, E% and salinity reduction were also calculated in order to determine the system performance.

Development of 1.45-mm resolution four-layer DOI-PET detector for simultaneous measurement in 3T MRI.

Recently, various types of PET-MRI systems have been developed by a number of research groups. However, almost all of the PET detectors used in these PET-MRI systems have no depth-of-interaction (DOI) capability. The DOI detector can reduce the parallax error and lead to improvement of the performance. We are developing a new PET-MRI system which consists of four-layer DOI detectors positioned close to the measured object to achieve high spatial resolution and high scanner sensitivity. As a first step, we are investigating influences the PET detector and the MRI system have on each other using a prototype four-layer DOI-PET detector. This prototype detector consists of a lutetium yttrium orthosilicate crystal block and a 4×4 multi-pixel photon counter array. The size of each crystal element is 1.45mm×1.45mm×4.5mm, and the crystals are arranged in 6×6 elements×4 layers with reflectors. The detector and some electric components are packaged in an aluminum shielding box. Experiments were carried out with 3.0 T MRI (GE, Signa HDx) and a birdcage-type RF coil. We demonstrated that the DOI-PET detector was normally operated in simultaneous measurements with no influence of the MRI measurement. A slight influence of the PET detector on the static magnetic field of the MRI was observed near the PET detector. The signal-to-noise ratio was decreased by presence of the PET detector due to environmental noise entering the MRI room through the cables, even though the PET detector was not powered up. On the other hand, no influence of electric noise from the PET detector in the simultaneous measurement on the MRI images was observed, even though the PET detector was positioned near the RF coil.

Effect of Length and Cross-Sectional Area on Ni&lt;sub&gt;3&lt;/sub&gt;Fe Alloy Plasticity

Molecular Dynamics (MD) simulations have been carried out on ultrathin Ni3Fe alloy with face-centered cubic (FCC) lattice upon application of uniaxial tension at nanolevel with a speed of 20 m/s. the deformation corresponds to the direction &lt;001&gt;. To the calculated block of crystal - free boundary conditions are applied in the directions &lt;100&gt;, &lt;010&gt;. Morse potential was employed to carry out three dimensional molecular dynamics simulations. A computer experiment is performed at a temperature corresponding to 300 K. MD simulation used to investigate the effect of long of ultrathin Ni3Fe alloy on the nature of deformation and fracture. The engineering stress–time diagrams obtained by the MD simulations of the tensile specimens of these ultrathin Ni3Fe alloy show a rapid increase in stress up to a maximum followed by a gradual drop to zero when the specimen fails by ductile fracture. The feature of deformation energy can be divided into four regions: quasi-elastic, plastic, flow and failure. The yield strength decreased with increasing long of alloy, but increases with increasing the cross sectional area. Plasticity disappear when the length of the allays is too large. The results showed that breaking position depended on the alloy length.

Optical Properties of 4-Bromobenzaldehyde Derivatives in Chloroform Solution

In this work we give a deeper insight into the electronic structure of a series of purely organic molecules that were recently employed as building blocks in crystals with very efficient phosphorescent emission. With this purpose, the low-lying excited states of a series of 4-bromobenzaldehyde derivatives in chloroform solution are explored by means of time-dependent density functional theory (TDDFT) calculations, together with the absorption, fluorescence, and phosphorescence experimental spectra. The optical properties of the studied molecular models are extensively discussed, in terms of the frontier molecular orbitals involved in the relevant electronic transitions, the recorded and simulated absorption profiles, and the molecular geometries and transition energies of the emitting states. The calculations eventually help in the assignment of the character of the lowest lying singlet and triplet emitting states for these compounds.

Development of a PET scanner for simultaneously imaging small animals with MRI and PET.

Recently, positron emission tomography (PET) is playing an increasingly important role in the diagnosis and staging of cancer. Combined PET and X-ray computed tomography (PET-CT) scanners are now the modality of choice in cancer treatment planning. More recently, the combination of PET and magnetic resonance imaging (MRI) is being explored in many sites. Combining PET and MRI has presented many challenges since the photo-multiplier tubes (PMT) in PET do not function in high magnetic fields, and conventional PET detectors distort MRI images. Solid state light sensors like avalanche photo-diodes (APDs) and more recently silicon photo-multipliers (SiPMs) are much less sensitive to magnetic fields thus easing the compatibility issues. This paper presents the results of a group of Canadian scientists who are developing a PET detector ring which fits inside a high field small animal MRI scanner with the goal of providing simultaneous PET and MRI images of small rodents used in pre-clinical medical research. We discuss the evolution of both the crystal blocks (which detect annihilation photons from positron decay) and the SiPM array performance in the last four years which together combine to deliver significant system performance in terms of speed, energy and timing resolution.