Next Issue
Previous Issue

Table of Contents

Crystals, Volume 8, Issue 6 (June 2018)

  • Issues are regarded as officially published after their release is announced to the table of contents alert mailing list.
  • You may sign up for e-mail alerts to receive table of contents of newly released issues.
  • PDF is the official format for papers published in both, html and pdf forms. To view the papers in pdf format, click on the "PDF Full-text" link, and use the free Adobe Readerexternal link to open them.
Cover Story (view full-size image) Multinary transition metal nitrides and nitridometalates constitute a fairly unexplored family that [...] Read more.
View options order results:
result details:
Displaying articles 1-27
Export citation of selected articles as:
Open AccessArticle Manipulation of Si Doping Concentration for Modification of the Electric Field and Carrier Injection for AlGaN-Based Deep-Ultraviolet Light-Emitting Diodes
Crystals 2018, 8(6), 258; https://doi.org/10.3390/cryst8060258
Received: 19 May 2018 / Revised: 7 June 2018 / Accepted: 12 June 2018 / Published: 20 June 2018
PDF Full-text (2360 KB) | HTML Full-text | XML Full-text
Abstract
Electron overflow is one of the key factors that limit the quantum efficiency for AlGaN-based deep-ultraviolet light-emitting diodes. In this work, we report a numerical study to improve the electron injection efficiency by manipulating the electric field profiles via doping the n-Al0.60
[...] Read more.
Electron overflow is one of the key factors that limit the quantum efficiency for AlGaN-based deep-ultraviolet light-emitting diodes. In this work, we report a numerical study to improve the electron injection efficiency by manipulating the electric field profiles via doping the n-Al0.60Ga0.40N electron source layer with different concentrations and reveal the physical mechanism of the Si doping effect on the electron and the hole injection. By utilizing the appropriate doping concentration, the electric field will reduce the electron drift velocity and, thus, the mean free path. Therefore, a higher electron capture efficiency by the multiple quantum wells (MQWs) and an increase of the hole concentration in the active region can be realized, resulting in an improved radiative recombination rate and an optical output power. Full article
(This article belongs to the Special Issue GaN-Based Optoelectronic Materials and Light Emitting Devices)
Figures

Figure 1

Open AccessReview Dislocation-Free SiGe/Si Heterostructures
Crystals 2018, 8(6), 257; https://doi.org/10.3390/cryst8060257
Received: 5 June 2018 / Revised: 14 June 2018 / Accepted: 16 June 2018 / Published: 19 June 2018
PDF Full-text (4007 KB) | HTML Full-text | XML Full-text
Abstract
Ge vertical heterostructures grown on deeply-patterned Si(001) were first obtained in 2012 (C.V. Falub et al., Science2012, 335, 1330–1334), immediately capturing attention due to the appealing possibility of growing micron-sized Ge crystals largely free of thermal stress and hosting dislocations
[...] Read more.
Ge vertical heterostructures grown on deeply-patterned Si(001) were first obtained in 2012 (C.V. Falub et al., Science2012, 335, 1330–1334), immediately capturing attention due to the appealing possibility of growing micron-sized Ge crystals largely free of thermal stress and hosting dislocations only in a small fraction of their volume. Since then, considerable progress has been made in terms of extending the technique to several other systems, and of developing further strategies to lower the dislocation density. In this review, we shall mainly focus on the latter aspect, discussing in detail 100% dislocation-free, micron-sized vertical heterostructures obtained by exploiting compositional grading in the epitaxial crystals. Furthermore, we shall also analyze the role played by the shape of the pre-patterned substrate in directly influencing the dislocation distribution. Full article
(This article belongs to the Special Issue Crystal Dislocations: Their Impact on Physical Properties of Crystals)
Figures

Figure 1

Open AccessArticle The Effects of Rare Earth Pr and Heat Treatment on the Wear Properties of AZ91 Alloy
Crystals 2018, 8(6), 256; https://doi.org/10.3390/cryst8060256
Received: 19 May 2018 / Revised: 11 June 2018 / Accepted: 14 June 2018 / Published: 19 June 2018
PDF Full-text (45924 KB) | HTML Full-text | XML Full-text
Abstract
This paper investigated the influences of Pr addition and heat treatment (T6) on the dry sliding wear behavior of AZ91 alloy. The wear rates and friction coefficients were measured by using a pin-on-disc tribometer under loads of 30, 60 and 90 N at
[...] Read more.
This paper investigated the influences of Pr addition and heat treatment (T6) on the dry sliding wear behavior of AZ91 alloy. The wear rates and friction coefficients were measured by using a pin-on-disc tribometer under loads of 30, 60 and 90 N at dry sliding speeds of 100 rpm, over a sliding time of 15 min. The worn surfaces were examined using a scanning electron microscope and was analyzed with an energy dispersive spectrometer. The experimental results revealed that AZ91-1.0%Pr magnesium alloy exhibited lower wear rate and friction coefficient than the other investigated alloys. As the applied load increased, the wear rate and friction coefficient increased. Compared with the as-cast AZ91-1.0%Pr magnesium alloy, the hardness and wear resistance of the alloy after solution treatment were reduced, and through the subsequent aging, the hardness and wear resistance of the alloy were improved and the hardness was 101.1 HB (compared to as-cast AZ91 magnesium alloy, it increased by 45%). The AZ91-1.0%Pr with T6 magnesium alloy exhibited best wear resistance. Abrasion was dominant at load of 30 N, delamination was dominant at load of 60 N and plastic deformation was dominant at load of 90 N. Oxidation was observed at all loads. Full article
Figures

Figure 1a

Open AccessReview Copper Delafossites under High Pressure—A Brief Review of XRD and Raman Spectroscopic Studies
Crystals 2018, 8(6), 255; https://doi.org/10.3390/cryst8060255
Received: 10 May 2018 / Revised: 13 June 2018 / Accepted: 16 June 2018 / Published: 19 June 2018
PDF Full-text (7195 KB) | HTML Full-text | XML Full-text
Abstract
Delafossites, with a unique combination of electrical conductivity and optical transparency constitute an important class of materials with their wide range of applications in different fields. In this article, we review the high pressure studies on copper based semiconducting delafossites with special emphasis
[...] Read more.
Delafossites, with a unique combination of electrical conductivity and optical transparency constitute an important class of materials with their wide range of applications in different fields. In this article, we review the high pressure studies on copper based semiconducting delafossites with special emphasis on their structural and vibrational properties by synchrotron based powder X-ray diffraction and Raman spectroscopic measurements. Though all the investigated compounds undergo pressure induced structural phase transition, the structure of high pressure phase has been reported only for CuFeO2. Based on X-ray diffraction data, one of the common features observed in all the studied compounds is the anisotropic compression of cell parameters in ambient rhombohedral structure. Ambient pressure bulk modulus obtained by fitting the pressure volume data lies between 135 to 200 GPa. Two allowed Raman mode frequencies Eg and A1g are observed in all the compounds in ambient phase with splitting of Eg mode at the transition except for CuCrO2 where along with splitting of Eg mode, A1g mode disappears and a strong mode appears which softens with pressure. Observed transition pressure scales exponentially with radii of trivalent cation being lowest for CuLaO2 and highest for CuAlO2. The present review will help materials researchers to have an overview of the subject and reviewed results are relevant for fundamental science as well as possessing potential technological applications in synthesis of new materials with tailored physical properties. Full article
(This article belongs to the Special Issue High-Pressure Studies of Crystalline Materials)
Figures

Figure 1

Open AccessArticle Amorphous Calcium Phosphate Formation and Aggregation Process Revealed by Light Scattering Techniques
Crystals 2018, 8(6), 254; https://doi.org/10.3390/cryst8060254
Received: 30 May 2018 / Revised: 8 June 2018 / Accepted: 15 June 2018 / Published: 17 June 2018
PDF Full-text (2485 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Amorphous calcium phosphate (ACP) attracts attention as a precursor of crystalline calcium phosphates (CaPs) formation in vitro and in vivo as well as due to its excellent biological properties. Its formation can be considered to be an aggregation process. Although aggregation of ACP
[...] Read more.
Amorphous calcium phosphate (ACP) attracts attention as a precursor of crystalline calcium phosphates (CaPs) formation in vitro and in vivo as well as due to its excellent biological properties. Its formation can be considered to be an aggregation process. Although aggregation of ACP is of interest for both gaining a fundamental understanding of biominerals formation and in the synthesis of novel materials, it has still not been investigated in detail. In this work, the ACP aggregation was followed by two widely applied techniques suitable for following nanoparticles aggregation in general: dynamic light scattering (DLS) and laser diffraction (LD). In addition, the ACP formation was followed by potentiometric measurements and formed precipitates were characterized by Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The results showed that aggregation of ACP particles is a process which from the earliest stages simultaneously takes place at wide length scales, from nanometers to micrometers, leading to a highly polydisperse precipitation system, with polydispersity and vol. % of larger aggregates increasing with concentration. Obtained results provide insight into developing a way of regulating ACP and consequently CaP formation by controlling aggregation on the scale of interest. Full article
(This article belongs to the Special Issue Biomimetic Growth of Calcium Phosphate Crystals)
Figures

Graphical abstract

Open AccessArticle Facile Low Temperature Hydrothermal Synthesis of BaTiO3 Nanoparticles Studied by In Situ X-ray Diffraction
Crystals 2018, 8(6), 253; https://doi.org/10.3390/cryst8060253
Received: 30 April 2018 / Revised: 5 June 2018 / Accepted: 15 June 2018 / Published: 17 June 2018
PDF Full-text (2387 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Ferroelectric materials are crucial for today’s technological society and nanostructured ferroelectric materials are important for the downscaling of devices. Controlled and reproducible synthesis of these materials are, therefore, of immense importance. Hydrothermal synthesis is a well-established synthesis route, with a large parameter space
[...] Read more.
Ferroelectric materials are crucial for today’s technological society and nanostructured ferroelectric materials are important for the downscaling of devices. Controlled and reproducible synthesis of these materials are, therefore, of immense importance. Hydrothermal synthesis is a well-established synthesis route, with a large parameter space for optimization, but a better understanding of nucleation and growth mechanisms is needed for full utilization and control. Here we use in situ X-ray diffraction to follow the nucleation and growth of BaTiO3 formed by hydrothermal synthesis using two different titanium precursors, an amorphous titania precipitate slurry and a Ti-citric acid complex solution. Sequential Rietveld refinement was used to extract the time dependency of lattice parameters, crystallite size, strain, and atomic displacement parameters. Phase pure BaTiO3 nanoparticles, 10–15 nm in size, were successfully synthesized at different temperatures (100, 125, and 150 °C) from both precursors after reaction times, ranging from a few seconds to several hours. The two precursors resulted in phase pure BaTiO3 with similar final crystallite size. Finally, two different growth mechanisms were revealed, where the effect of surfactants present during hydrothermal synthesis is discussed as one of the key parameters. Full article
(This article belongs to the Special Issue Synthesis, Properties and Applications of Metal Oxides Nanoparticles)
Figures

Figure 1

Open AccessReview Progress on Crystal Growth of Two-Dimensional Semiconductors for Optoelectronic Applications
Crystals 2018, 8(6), 252; https://doi.org/10.3390/cryst8060252
Received: 1 June 2018 / Revised: 13 June 2018 / Accepted: 13 June 2018 / Published: 16 June 2018
PDF Full-text (4148 KB) | HTML Full-text | XML Full-text
Abstract
Two-dimensional (2D) semiconductors are thought to belong to the most promising candidates for future nanoelectronic applications, due to their unique advantages and capability in continuing the downscaling of complementary metal–oxide–semiconductor (CMOS) devices while retaining decent mobility. Recently, optoelectronic devices based on novel synthetic
[...] Read more.
Two-dimensional (2D) semiconductors are thought to belong to the most promising candidates for future nanoelectronic applications, due to their unique advantages and capability in continuing the downscaling of complementary metal–oxide–semiconductor (CMOS) devices while retaining decent mobility. Recently, optoelectronic devices based on novel synthetic 2D semiconductors have been reported, exhibiting comparable performance to the traditional solid-state devices. This review briefly describes the development of the growth of 2D crystals for applications in optoelectronics, including photodetectors, light-emitting diodes (LEDs), and solar cells. Such atomically thin materials with promising optoelectronic properties are very attractive for future advanced transparent optoelectronics as well as flexible and wearable/portable electronic devices. Full article
Figures

Figure 1

Open AccessArticle The Role of Hyperconjugation on the Structure and C–H Stretching Frequencies of 3,3′-Ethane-1,2-diyl- bis-1,3,5-triazabicyclo[3.2.1]octane (ETABOC): An X-Ray Structure and Vibrational Study
Crystals 2018, 8(6), 251; https://doi.org/10.3390/cryst8060251
Received: 15 May 2018 / Accepted: 28 May 2018 / Published: 16 June 2018
PDF Full-text (2342 KB) | HTML Full-text | XML Full-text
Abstract
Structural and vibrational studies have been carried out for the most stable conformer of 3,3′-ethane-1,2-diyl-bis-1,3,5-triazabicyclo[3.2.1]octane (ETABOC) at the DFT/B3LYP/6-31G(dp) level using the Gaussian 03 software. In light of the computed vibrational parameters, the observed IR Bolhmann bands for the C2V, C
[...] Read more.
Structural and vibrational studies have been carried out for the most stable conformer of 3,3′-ethane-1,2-diyl-bis-1,3,5-triazabicyclo[3.2.1]octane (ETABOC) at the DFT/B3LYP/6-31G(dp) level using the Gaussian 03 software. In light of the computed vibrational parameters, the observed IR Bolhmann bands for the C2V, C2, and Ci symmetrical structures of ETABOC have been analyzed. Hyperconjugative interaction was done by Natural Bond Orbital Analysis. Interpretation of hyperconjugative interaction involving the lone pairs on the bridgehead nitrogen atoms with the neighboring C–N and C–C bonds defines the conformational preference of the title compound. The recorded X-ray diffraction bond parameters were compared with theoretical values calculated at B3LYP/6-31G(d,p) and HF/6-31G(d,p) level of theory showed that ETABOC adopts a chair conformation and possesses an inversion center. Full article
Figures

Graphical abstract

Open AccessArticle Magnetic MOF for AO7 Removal and Targeted Delivery
Crystals 2018, 8(6), 250; https://doi.org/10.3390/cryst8060250
Received: 25 May 2018 / Revised: 6 June 2018 / Accepted: 13 June 2018 / Published: 15 June 2018
PDF Full-text (4200 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Owing to their high surface area and porosity, metal-organic frameworks (MOFs) have been gradually employed for a myriad of applications ranging from sensing, pollutant adsorption, and drug delivery to environmental remediation and catalysis. Magnetic nanoparticles-metal-organic frameworks (MMOFs) hybrid materials can facilitate facile removal
[...] Read more.
Owing to their high surface area and porosity, metal-organic frameworks (MOFs) have been gradually employed for a myriad of applications ranging from sensing, pollutant adsorption, and drug delivery to environmental remediation and catalysis. Magnetic nanoparticles-metal-organic frameworks (MMOFs) hybrid materials can facilitate facile removal of MOFs from solutions. In this report, we report the synthesis of Fe3O4@UiO-66 by encapsulation and simulated the drug loading and release by studying the adsorption and release of AO7. Thus, we loaded these MMOFs with AO7 and found that they were able to trigger and control its release by simply applying an external magnetic field. The magnetic field heats the magnets in the MOF, which causes the load to burst from the framework. Full article
Figures

Figure 1

Open AccessArticle Sonocrystallization—Case Studies of Salicylamide Particle Size Reduction and Isoniazid Derivative Synthesis and Crystallization
Crystals 2018, 8(6), 249; https://doi.org/10.3390/cryst8060249
Received: 23 May 2018 / Revised: 12 June 2018 / Accepted: 13 June 2018 / Published: 15 June 2018
PDF Full-text (2430 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Two case studies of salicylamide particle size reduction and isoniazid derivative synthesis and crystallization realized using sonocrystallization were investigated. The size, habit, structure, thermal behavior, and spectrometric properties of sonocrystallized crystals were analyzed through scanning electron microscopy (SEM), powder X-ray diffractometry (PXRD), differential
[...] Read more.
Two case studies of salicylamide particle size reduction and isoniazid derivative synthesis and crystallization realized using sonocrystallization were investigated. The size, habit, structure, thermal behavior, and spectrometric properties of sonocrystallized crystals were analyzed through scanning electron microscopy (SEM), powder X-ray diffractometry (PXRD), differential scanning calorimetry (DSC), and Fourier transform infrared (FTIR) spectroscopy. The effects of the operating parameters, such as sonication intensity, sonication duration, and solution concentration, on sonocrystallization were compared. The crystal size of salicylamide was reduced from 595 μm (the original size) and was efficiently manipulated to be between 40 and 80 μm. Moreover, compared with the crystal habits of unprocessed crystals and recrystallized crystals fabricated through conventional methods, the crystal habit of salicylamide could be modified to present a regular shape. The structure, thermal behavior, and spectrometric properties of sonocrystallized salicylamide were found to be in agreement with those of an unprocessed sample. For producing isoniazid derivative crystals, N′-(propan-2-ylidene)-isonicotinohydrazide was synthesized using isoniazid in acetone at 318 K. The resulting solution was then cooled by applying power ultrasound to isolate N′-(propan-2-ylidene)-isonicotinohydrazide crystals. The solid-state properties of the synthesized N′-(propan-2-ylidene)-isonicotinohydrazide was verified through PXRD, DSC, and FTIR spectroscopy. The feasibility of particle size manipulation was then demonstrated through sonocrystallization. Full article
(This article belongs to the Special Issue Advances in Ultrasound Stimulated Crystallization)
Figures

Graphical abstract

Open AccessArticle Investigation of HfO2 Thin Films on Si by X-ray Photoelectron Spectroscopy, Rutherford Backscattering, Grazing Incidence X-ray Diffraction and Variable Angle Spectroscopic Ellipsometry
Crystals 2018, 8(6), 248; https://doi.org/10.3390/cryst8060248
Received: 23 April 2018 / Revised: 31 May 2018 / Accepted: 5 June 2018 / Published: 12 June 2018
Cited by 1 | PDF Full-text (3396 KB) | HTML Full-text | XML Full-text
Abstract
Hafnium oxide (HfO2) thin films have been made by atomic vapor deposition (AVD) onto Si substrates under different growth temperature and oxygen flow. The effect of different growth conditions on the structure and optical characteristics of deposited HfO2 film has
[...] Read more.
Hafnium oxide (HfO2) thin films have been made by atomic vapor deposition (AVD) onto Si substrates under different growth temperature and oxygen flow. The effect of different growth conditions on the structure and optical characteristics of deposited HfO2 film has been studied using X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectrometry (RBS), grazing incidence X-ray diffraction (GIXRD) and variable angle spectroscopic ellipsometry (VASE). The XPS measurements and analyses revealed the insufficient chemical reaction at the lower oxygen flow rate and the film quality improved at higher oxygen flow rate. Via GIXRD, it was found that the HfO2 films on Si were amorphous in nature, as deposited at lower deposition temperature, while being polycrystalline at higher deposition temperature. The structural phase changes from interface to surface were demonstrated. The values of optical constants and bandgaps and their variations with the growth conditions were determined accurately from VASE and XPS. All analyses indicate that appropriate substrate temperature and oxygen flow are essential to achieve high quality of the AVD-grown HfO2 films. Full article
(This article belongs to the Special Issue Functional Oxide Based Thin-Film Materials)
Figures

Figure 1

Open AccessArticle Influence of Doping Tb on the Mechanical Properties and Martensitic Transformation of Ni-Mn-Sn Magnetic Shape Memory Alloys
Crystals 2018, 8(6), 247; https://doi.org/10.3390/cryst8060247
Received: 17 May 2018 / Revised: 4 June 2018 / Accepted: 5 June 2018 / Published: 11 June 2018
PDF Full-text (2808 KB) | HTML Full-text | XML Full-text
Abstract
Brittleness and low working temperature are two key factors that restrict the application of Ni-Mn-Sn alloys. Element doping is an effective means to improve performance of materials. In present paper, martensitic transformation (MT) and mechanical properties of Ni48Mn39Sn13−
[...] Read more.
Brittleness and low working temperature are two key factors that restrict the application of Ni-Mn-Sn alloys. Element doping is an effective means to improve performance of materials. In present paper, martensitic transformation (MT) and mechanical properties of Ni48Mn39Sn13−xTbx (x = 0, 0.5, 1, 2, and 5 at.%) alloys are investigated. It is found that the Tb addition refines significantly the grains and causes the formation of a Tb-rich phase. All the samples undergo the martensitic transformation from parent phase to martensite. And the martensitic transformation characteristic temperatures increase remarkably from −60.7 °C for x = 0 to 364.1 °C for x = 5. The appropriate amount of Tb addition in Ni48Mn39Sn13−xTbx (x = 0, 0.5, 1, 2, and 5 at.%) alloys significantly enhances the compressive strength and improves the ductility, which can be ascribed to the grain refinement. The compressive stress of 571.8 MPa and strain 22.0% are obtained in the Ni48Mn39Sn11Tb2 alloy. Then the mechanical properties decrease with the further increased Tb content. Simultaneous improving of martensitic transformation temperature and mechanical properties in Ni-Mn-Sn magnetic alloy are achieved by Tb doping. Full article
Figures

Figure 1

Open AccessArticle The Inverse-Square Interaction Phase Diagram: Unitarity in the Bosonic Ground State
Crystals 2018, 8(6), 246; https://doi.org/10.3390/cryst8060246
Received: 22 April 2018 / Revised: 4 June 2018 / Accepted: 4 June 2018 / Published: 8 June 2018
PDF Full-text (7015 KB) | HTML Full-text | XML Full-text
Abstract
Ground-state properties of bosons interacting via inverse square potential (three dimensional Calogero-Sutherland model) are analyzed. A number of quantities scale with the density and can be naturally expressed in units of the Fermi energy and Fermi momentum multiplied by a dimensionless constant (Bertsch
[...] Read more.
Ground-state properties of bosons interacting via inverse square potential (three dimensional Calogero-Sutherland model) are analyzed. A number of quantities scale with the density and can be naturally expressed in units of the Fermi energy and Fermi momentum multiplied by a dimensionless constant (Bertsch parameter). Two analytical approaches are developed: the Bogoliubov theory for weak and the harmonic approximation (HA) for strong interactions. Diffusion Monte Carlo method is used to obtain the ground-state properties in a non-perturbative manner. We report the dependence of the Bertsch parameter on the interaction strength and construct a Padé approximant which fits the numerical data and reproduces correctly the asymptotic limits of weak and strong interactions. We find good agreement with beyond-mean field theory for the energy and the condensate fraction. The pair distribution function and the static structure factor are reported for a number of characteristic interactions. We demonstrate that the system experiences a gas-solid phase transition as a function of the dimensionless interaction strength. A peculiarity of the system is that by changing the density it is not possible to induce the phase transition. We show that the low-lying excitation spectrum contains plasmons in both phases, in agreement with the Bogoliubov and HA theories. Finally, we argue that this model can be interpreted as a realization of the unitary limit of a Bose system with the advantage that the system stays in the genuine ground state contrarily to the metastable state realized in experiments with short-range Bose gases. Full article
(This article belongs to the Special Issue Quantum Crystals)
Figures

Figure 1

Open AccessArticle The Behavior of the Deformation Vibration of NH3 in Semi-Organic Crystals under High Pressure Studied by Raman Spectroscopy
Crystals 2018, 8(6), 245; https://doi.org/10.3390/cryst8060245
Received: 4 May 2018 / Revised: 28 May 2018 / Accepted: 5 June 2018 / Published: 7 June 2018
PDF Full-text (1621 KB) | HTML Full-text | XML Full-text
Abstract
Single-crystal samples of the semi-organic compounds mono-l-alaninium nitrate and monoglycine nitrate have been studied by Raman spectroscopy in a diamond-anvil cell up to 5.5 GPa, in order to observe the behavior of the deformation mode of NH3 units. It was
[...] Read more.
Single-crystal samples of the semi-organic compounds mono-l-alaninium nitrate and monoglycine nitrate have been studied by Raman spectroscopy in a diamond-anvil cell up to 5.5 GPa, in order to observe the behavior of the deformation mode of NH3 units. It was observed for these semi-organic crystals that increasing pressure produces a decrease in the wavenumber of the band associated with the deformation vibration, differently from most of the modes. Comparatively, mono-l-alaninium has a higher dν/dP than monoglycine nitrate, for the band associated with the deformation vibration. The anomalous behavior is explained in terms of the effect of high pressure in the short and linear intermolecular hydrogen bonds. Full article
(This article belongs to the Section Interactions in Crystal Structures)
Figures

Figure 1

Open AccessArticle Relationship between Dislocation Density and Oxygen Concentration in Silicon Crystals during Directional Solidification
Crystals 2018, 8(6), 244; https://doi.org/10.3390/cryst8060244
Received: 26 April 2018 / Revised: 1 June 2018 / Accepted: 5 June 2018 / Published: 7 June 2018
PDF Full-text (1661 KB) | HTML Full-text | XML Full-text
Abstract
This paper reports the relationship between oxygen concentration and dislocation multiplication in silicon crystals during directional solidification using numerical analysis. Based on the Alexander–Haasen–Sumino model, this analysis involved oxygen diffusion from the bulk to dislocation cores during crystal growth and annealing processes in
[...] Read more.
This paper reports the relationship between oxygen concentration and dislocation multiplication in silicon crystals during directional solidification using numerical analysis. Based on the Alexander–Haasen–Sumino model, this analysis involved oxygen diffusion from the bulk to dislocation cores during crystal growth and annealing processes in a furnace. The results showed that the dislocation density mainly increased during cooling process, rather than crystal growth, when the effect of oxygen diffusion to dislocation cores was ignored. On the contrary, the dislocation density increased during both crystal growth and cooling processes when the effect of interstitial oxygen diffusion was considered. At a dislocation density larger than 1.0 × 105 cm−2, the interstitial oxygen concentration in bulk decreased due to the diffusion process, if interstitial oxygen atoms were between dislocations, whereas the concentration at dislocation cores increases. Full article
(This article belongs to the Special Issue Growth and Evaluation of Multicrystalline Silicon)
Figures

Figure 1

Open AccessArticle Large-Scale Assembly and Mask-Free Fabrication of Graphene Transistors via Optically Induced Electrodeposition
Crystals 2018, 8(6), 239; https://doi.org/10.3390/cryst8060239
Received: 19 May 2018 / Revised: 31 May 2018 / Accepted: 5 June 2018 / Published: 7 June 2018
PDF Full-text (3844 KB) | HTML Full-text | XML Full-text
Abstract
Graphene, known as an alternative for silicon, has significant potential in microelectronic applications. The assembly of graphene on well-defined metal electrodes is a critical step in the fabrication of microelectronic devices. Herein, we present a convenient, rapid, and large-scale assembly method for deposition
[...] Read more.
Graphene, known as an alternative for silicon, has significant potential in microelectronic applications. The assembly of graphene on well-defined metal electrodes is a critical step in the fabrication of microelectronic devices. Herein, we present a convenient, rapid, and large-scale assembly method for deposition of Ag electrodes, namely optically induced electrodeposition (OIED). This technique enables us to achieve custom-designed and mask-free fabrication of graphene transistors. The entire assembly process can be completed within a few tens of seconds. Our results show that graphene-based transistors fabricated with Ag electrodes function as a p-type semiconductor. Transfer curves of different samples reveal similar trends of slightly p-type characteristics, which shows that this method is reliable and repeatable. Full article
(This article belongs to the Special Issue Graphene Mechanics)
Figures

Figure 1

Open AccessArticle Systematics of the Third Row Transition Metal Melting: The HCP Metals Rhenium and Osmium
Crystals 2018, 8(6), 243; https://doi.org/10.3390/cryst8060243
Received: 6 April 2018 / Revised: 23 May 2018 / Accepted: 25 May 2018 / Published: 6 June 2018
PDF Full-text (18959 KB) | HTML Full-text | XML Full-text
Abstract
The melting curves of rhenium and osmium to megabar pressures are obtained from an extensive suite of ab initio quantum molecular dynamics (QMD) simulations using the Z method. In addition, for Re, we combine QMD simulations with total free energy calculations to obtain
[...] Read more.
The melting curves of rhenium and osmium to megabar pressures are obtained from an extensive suite of ab initio quantum molecular dynamics (QMD) simulations using the Z method. In addition, for Re, we combine QMD simulations with total free energy calculations to obtain its phase diagram. Our results indicate that Re, which generally assumes a hexagonal close-packed (hcp) structure, melts from a face-centered cubic (fcc) structure in the pressure range 20–240 GPa. We conclude that the recent DAC data on Re to 50 GPa in fact encompass both the true melting curve and the low-slope hcp-fcc phase boundary above a triple point at (20 GPa, 4240 K). A linear fit to the Re diamond anvil cell (DAC) data then results in a slope that is 2.3 times smaller than that of the actual melting curve. The phase diagram of Re is topologically equivalent to that of Pt calculated by us earlier on. Regularities in the melting curves of Re, Os, and five other 3rd-row transition metals (Ta, W, Ir, Pt, Au) form the 3rd-row transition metal melting systematics. We demonstrate how this systematics can be used to estimate the currently unknown melting curve of the eighth 3rd-row transition metal Hf. Full article
(This article belongs to the Special Issue High-Pressure Studies of Crystalline Materials)
Figures

Figure 1

Open AccessReview Analysing the Prospects of Perovskite Solar Cells within the Purview of Recent Scientific Advancements
Crystals 2018, 8(6), 242; https://doi.org/10.3390/cryst8060242
Received: 6 April 2018 / Revised: 12 May 2018 / Accepted: 16 May 2018 / Published: 6 June 2018
PDF Full-text (22091 KB) | HTML Full-text | XML Full-text
Abstract
For any given technology to be successful, its ability to compete with the other existing technologies is the key. Over the last five years, perovskite solar cells have entered the research spectrum with tremendous market prospects. These cells provide easy and low cost
[...] Read more.
For any given technology to be successful, its ability to compete with the other existing technologies is the key. Over the last five years, perovskite solar cells have entered the research spectrum with tremendous market prospects. These cells provide easy and low cost processability and are an efficient alternative to the existing solar cell technologies in the market. In this review article, we first go over the innovation and the scientific findings that have been going on in the field of perovskite solar cells (PSCs) and then present a short case study of perovskite solar cells based on their energy payback time. Our review aims to be comprehensive, considering the cost, the efficiency, and the stability of the PSCs. Later, we suggest areas for improvement in the field, and how the future might be shaped. Full article
Figures

Figure 1

Open AccessReview Influence of Dislocations in Transition Metal Oxides on Selected Physical and Chemical Properties
Crystals 2018, 8(6), 241; https://doi.org/10.3390/cryst8060241
Received: 6 March 2018 / Revised: 23 May 2018 / Accepted: 27 May 2018 / Published: 4 June 2018
PDF Full-text (25036 KB) | HTML Full-text | XML Full-text
Abstract
Studies on dislocations in prototypic binary and ternary oxides (here TiO2 and SrTiO3) using modern TEM and scanning probe microscopy (SPM) techniques, combined with classical etch pits methods, are reviewed. Our review focuses on the important role of dislocations in
[...] Read more.
Studies on dislocations in prototypic binary and ternary oxides (here TiO2 and SrTiO3) using modern TEM and scanning probe microscopy (SPM) techniques, combined with classical etch pits methods, are reviewed. Our review focuses on the important role of dislocations in the insulator-to-metal transition and for redox processes, which can be preferentially induced along dislocations using chemical and electrical gradients. It is surprising that, independently of the growth techniques, the density of dislocations in the surface layers of both prototypical oxides is high (109/cm2 for epipolished surfaces and up to 1012/cm2 for the rough surface). The TEM and locally-conducting atomic force microscopy (LCAFM) measurements show that the dislocations create a network with the character of a hierarchical tree. The distribution of the dislocations in the plane of the surface is, in principle, inhomogeneous, namely a strong tendency for the bundling and creation of arrays or bands in the crystallographic <100> and <110> directions can be observed. The analysis of the core of dislocations using scanning transmission electron microscopy (STEM) techniques (such as EDX with atomic resolution, electron-energy loss spectroscopy (EELS)) shows unequivocally that the core of dislocations possesses a different crystallographic structure, electronic structure and chemical composition relative to the matrix. Because the Burgers vector of dislocations is per se invariant, the network of dislocations (with additional d1 electrons) causes an electrical short-circuit of the matrix. This behavior is confirmed by LCAFM measurements for the stoichiometric crystals, moreover a similar dominant role of dislocations in channeling of the current after thermal reduction of the crystals or during resistive switching can be observed. In our opinion, the easy transformation of the chemical composition of the surface layers of both model oxides should be associated with the high concentration of extended defects in this region. Another important insight for the analysis of the physical properties in real oxide crystals (matrix + dislocations) comes from the studies of the nucleation of dislocations via in situ STEM indentation, namely that the dislocations can be simply nucleated under mechanical stimulus and can be easily moved at room temperature. Full article
(This article belongs to the Special Issue Crystal Dislocations: Their Impact on Physical Properties of Crystals)
Figures

Figure 1

Open AccessReview Dislocations and Plastic Deformation in MgO Crystals: A Review
Crystals 2018, 8(6), 240; https://doi.org/10.3390/cryst8060240
Received: 29 March 2018 / Revised: 4 May 2018 / Accepted: 10 May 2018 / Published: 31 May 2018
PDF Full-text (6835 KB) | HTML Full-text | XML Full-text
Abstract
This review paper focuses on dislocations and plastic deformation in magnesium oxide crystals. MgO is an archetype ionic ceramic with refractory properties which is of interest in several fields of applications such as ceramic materials fabrication, nano-scale engineering and Earth sciences. In its
[...] Read more.
This review paper focuses on dislocations and plastic deformation in magnesium oxide crystals. MgO is an archetype ionic ceramic with refractory properties which is of interest in several fields of applications such as ceramic materials fabrication, nano-scale engineering and Earth sciences. In its bulk single crystal shape, MgO can deform up to few percent plastic strain due to dislocation plasticity processes that strongly depend on external parameters such as pressure, temperature, strain rate, or crystal size. This review describes how a combined approach of macro-mechanical tests, multi-scale modeling, nano-mechanical tests, and high pressure experiments and simulations have progressively helped to improve our understanding of MgO mechanical behavior and elementary dislocation-based processes under stress. Full article
(This article belongs to the Special Issue Crystal Dislocations: Their Impact on Physical Properties of Crystals)
Figures

Figure 1

Open AccessArticle Experimental Value of the Specific Surface Energy of the Cleavage {10.4} Calcite Rhombohedron in the Presence of Its Saturated Aqueous Solution
Crystals 2018, 8(6), 238; https://doi.org/10.3390/cryst8060238
Received: 26 April 2018 / Revised: 20 May 2018 / Accepted: 28 May 2018 / Published: 30 May 2018
PDF Full-text (2040 KB) | HTML Full-text | XML Full-text
Abstract
In this study, we describe a method to obtain experimental values of the surface energy of calcite. A zenithal imaging device was used to acquire pictures of droplets of CaCO3 saturated aqueous solution on the surface of a calcite crystal sample. Pictures
[...] Read more.
In this study, we describe a method to obtain experimental values of the surface energy of calcite. A zenithal imaging device was used to acquire pictures of droplets of CaCO3 saturated aqueous solution on the surface of a calcite crystal sample. Pictures were used to measure the contact angle between the droplets and the {10.4} calcite surfaces. The method is discussed along with its geometrical ground, as well as the theoretical foundation of the contact angle calculation. A comparison is made with the literature data; a good agreement is found between our experimental values and those obtained from the more recent ab initio calculations. Full article
(This article belongs to the Special Issue Carbonates)
Figures

Figure 1

Open AccessArticle Simultaneous Enhancement of Electrical Conductivity and Seebeck Coefficient of [6,6]-Phenyl-C71 Butyric Acid Methyl Ester (PC70BM) by Adding Co-Solvents
Crystals 2018, 8(6), 237; https://doi.org/10.3390/cryst8060237
Received: 8 April 2018 / Revised: 20 May 2018 / Accepted: 22 May 2018 / Published: 26 May 2018
PDF Full-text (3944 KB) | HTML Full-text | XML Full-text
Abstract
Chemical modification by co-solvents added to [6,6]-Phenyl-C71 butyric acid methyl ester, commonly known as an n-type semiconducting fullerene derivative PC70BM, is reported to change the electrical and thermoelectric properties of this system. Power factor of the casted PC70BM samples
[...] Read more.
Chemical modification by co-solvents added to [6,6]-Phenyl-C71 butyric acid methyl ester, commonly known as an n-type semiconducting fullerene derivative PC70BM, is reported to change the electrical and thermoelectric properties of this system. Power factor of the casted PC70BM samples achieves values higher than that determined for a variety of organic compounds, including conducting polymers, such as PEDOT:PSS in the pristine form. After chemical functionalization by different solvents, namely N,N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-Methyl-2-pyrrolidone (NMP), acetonitrile (AC), and 1,2-Dichloroethane (DCE), the four-probe in-plane electrical conductivity and Seebeck coefficient measurements indicate a simultaneous increase of the electrical conductivity and the Seebeck coefficient. The observed effect is more pronounced for solvents with a high boiling point, such as N,N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-Methyl-2-pyrrolidone (NMP), than in acetonitrile (AC) and 1,2-Dichloroethane (DCE). We identified the origin of these changes using Hall mobility measurements, which demonstrate enhancement of the PC70BM charge carrier mobility upon addition of the corresponding solvents due to the improved packaging of the fullerene compound and chemical interaction with entrapped solvent molecules within the layers. Full article
(This article belongs to the Special Issue Materials Processing and Crystal Growth for Thermoelectrics)
Figures

Graphical abstract

Open AccessArticle Coordination Behavior of Bis-Imidazole and Various Carboxylate Ligands towards Zn(II) and Cd(II) Ions: Synthesis, Structure, and Photoluminescence Study
Crystals 2018, 8(6), 236; https://doi.org/10.3390/cryst8060236
Received: 3 May 2018 / Revised: 24 May 2018 / Accepted: 24 May 2018 / Published: 25 May 2018
PDF Full-text (3245 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Four coordination polymers (CPs) based on bis-imidazole ligands (1,2-bimb and 1,2-bmimb), namely, {[Zn(1,2-bimb)(2,5-dtpa)] H2O}n (1), {[Cd2(1,2-bimb)2(5-hipa)2] 2H2O} (2), {Zn2(1,2-bimb)(L)(CH3COO) DMF·2H2O}n (
[...] Read more.
Four coordination polymers (CPs) based on bis-imidazole ligands (1,2-bimb and 1,2-bmimb), namely, {[Zn(1,2-bimb)(2,5-dtpa)] H2O}n (1), {[Cd2(1,2-bimb)2(5-hipa)2] 2H2O} (2), {Zn2(1,2-bimb)(L)(CH3COO) DMF·2H2O}n (3) and {Cd(1,2-bmimb)(3-npa)}n (4), have been synthesized by solvothermal reactions (1,2-bimb = 1,2-bis((1H-imidazol-1-yl)methyl)benzene, 1,2-bmimb = 1,2-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene, 2,5-H2dtpa = 2,5-diaminoterephthalic acid, 5-H2hipa = 5-hydroxyisophthalic acid, H3L= 3,3′,3′′-(2,4,6-trioxo-1,3,5-triazinane-1,3,5-triyl)tripropanoic acid, 3-H2npa = 3-nitrophthalic acid) and structurally verified by single-crystal X-ray diffraction analyses and further characterized by powder X-ray diffraction (PXRD), elemental analyses and infrared spectroscopy (IR). Complex 1 and 2 show a dinuclear 2D layered structure. Complex 4 exhibits a two-dimensional network consisting of [Cd(3-npa)]n and [Cd(1,2-bmimb)]n chains. Both 1,2 and 4 display a 4-connected sql topology sheet, which can be further expanded into a 3D supramolecular network through π···π interaction between layers. Complex 3 features a 3D (3,6)-connected {42·6}·{44·610·8}-3,6T24 topology structure consisting of 2D bilayers. Structural comparison reveals that it is not only the substituents at different positions of ancillary ligands and the primary bis(imidazole) linkers that play crucial roles in the control of the final structures. Besides, the photoluminescence properties of 14 have been investigated in the solid state at room temperature. Full article
Figures

Graphical abstract

Open AccessCommunication Ba4[Mn3N6], a Quasi-One-Dimensional Mixed-Valent Nitridomanganate (II, IV)
Crystals 2018, 8(6), 235; https://doi.org/10.3390/cryst8060235
Received: 25 April 2018 / Revised: 17 May 2018 / Accepted: 18 May 2018 / Published: 25 May 2018
PDF Full-text (4176 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The mixed-valent nitridomanganate Ba4[Mn3N6] was prepared using a gas–solid high temperature route. The crystal structure was determined employing high resolution synchrotron powder diffraction data: space group Pbcn, a = 9.9930(1) Å, b = 6.17126(8) Å, c
[...] Read more.
The mixed-valent nitridomanganate Ba4[Mn3N6] was prepared using a gas–solid high temperature route. The crystal structure was determined employing high resolution synchrotron powder diffraction data: space group Pbcn, a = 9.9930(1) Å, b = 6.17126(8) Å, c = 14.4692(2) Å, V = 892.31(2) Å3, Z = 4. The manganese atoms in the structure of Ba4[Mn3N6] are four-fold coordinated by nitrogen forming infinite corrugated chains of edge-sharing [MnN4] tetrahedra. The chains demonstrate a complete charge order of Mn species. Magnetization measurements and first principle calculations indicate quasi-one dimensional magnetic behavior. In addition, chemical bonding analysis revealed pronounced Mn–Mn interactions along the chains. Full article
(This article belongs to the Special Issue Compounds with Polar Metallic Bonding)
Figures

Graphical abstract

Open AccessArticle An Examination of the Electron Densities in a Series of Tripodal Cobalt Complexes Bridged by Magnesium, Calcium, Strontium, and Barium
Crystals 2018, 8(6), 234; https://doi.org/10.3390/cryst8060234
Received: 10 May 2018 / Revised: 18 May 2018 / Accepted: 19 May 2018 / Published: 25 May 2018
PDF Full-text (18325 KB) | HTML Full-text | XML Full-text
Abstract
X-ray crystallographic and theoretical charge-density data for a series of compounds—[(Co(Ts3tren))M(Co(Ts3tren))], (M = Mg, Ca, Sr and Ba)—were examined. The crystal structures were isostructural, and the alkaline-earth-metal ions had the same six-coordinate environment oxygen donor atoms which was octahedral
[...] Read more.
X-ray crystallographic and theoretical charge-density data for a series of compounds—[(Co(Ts3tren))M(Co(Ts3tren))], (M = Mg, Ca, Sr and Ba)—were examined. The crystal structures were isostructural, and the alkaline-earth-metal ions had the same six-coordinate environment oxygen donor atoms which was octahedral despite the large variation in their ionic radii. The isomorphism of these molecules was surprising, and a theoretical examination of their electronic structures, with various metal ions along the series, provided detailed insight into their stabilities. The theoretical and experimental data were consistent and agreed well. The local properties of the Co(II) ion and its donor atoms were relatively independent of the alkaline earth metals. Full article
(This article belongs to the Special Issue Experimental and Theoretical Electron Density Analysis of Crystals)
Figures

Figure 1

Open AccessArticle Raman Scattering as a Probe of the Magnetic State of BEDT-TTF Based Mott Insulators
Crystals 2018, 8(6), 233; https://doi.org/10.3390/cryst8060233
Received: 14 March 2018 / Revised: 30 April 2018 / Accepted: 16 May 2018 / Published: 23 May 2018
Cited by 1 | PDF Full-text (501 KB) | HTML Full-text | XML Full-text
Abstract
Quasi-two-dimensional Mott insulators based on BEDT-TTF molecules have recently demonstrated a variety of exotic states, which originate from electron–electron correlations and geometrical frustration of the lattice. Among those states are a triangular S = 1/2 spin liquid and quantum dipole liquid. In this
[...] Read more.
Quasi-two-dimensional Mott insulators based on BEDT-TTF molecules have recently demonstrated a variety of exotic states, which originate from electron–electron correlations and geometrical frustration of the lattice. Among those states are a triangular S = 1/2 spin liquid and quantum dipole liquid. In this article, we show the power of Raman scattering technique to characterize magnetic and electronic excitations of these states. Our results demonstrate a distinction between a spectrum of magnetic excitations in a simple Mott insulator with antiferromagnetic interactions, and a spectrum of an insulator with an additional on-site charge degree of freedom. Full article
Figures

Figure 1

Open AccessReview Emerging Characterizing Techniques in the Fine Structure Observation of Metal Halide Perovskite Crystal
Crystals 2018, 8(6), 232; https://doi.org/10.3390/cryst8060232
Received: 30 March 2018 / Revised: 10 May 2018 / Accepted: 16 May 2018 / Published: 23 May 2018
PDF Full-text (4748 KB) | HTML Full-text | XML Full-text
Abstract
Driven by its appealing application in the energy harvesting industry, metal halide perovskite solar cells are attracting increasing attention from various fields, such as chemistry, materials, physics, and energy-related industries. While the energy conversion efficiency of the perovskite solar cell is being investigated
[...] Read more.
Driven by its appealing application in the energy harvesting industry, metal halide perovskite solar cells are attracting increasing attention from various fields, such as chemistry, materials, physics, and energy-related industries. While the energy conversion efficiency of the perovskite solar cell is being investigated often by various research groups, the relationship between the surface structure and the property is still ambiguous and, therefore, becomes an urgent topic due to its wide application in the real environment. Recently, the fine structure characterization of perovskite crystals has been analysed by varying techniques, such as XRD, synchrotron-based grazing incidence XRD, XAFS, and STM, in addition to others. In this review article, we will summarize recent progresses in the monitoring of fine nanostructures of the surface and crystal structures of perovskite films, mainly by XAFS, XRD, and STM, focusing on the discussion of the relationship between the properties and the stability of perovskite solar cells. Furthermore, a prospective is given for the development of experimental approaches towards fine structure characterization. Full article
Figures

Figure 1

Back to Top