Single Crystal Research Articles

Vacancy modulation dramatically enhance thermoelectric performance of InTe single crystal

InTe single crystals have demonstrated great promise in the field of thermoelectric materials, particularly when oriented along the [110] direction. This specific crystal orientation exhibits higher electronic conductivity and lower thermal conductivity compared to other orientations of InTe. Through first-principles calculations, we identified the anisotropic valence band and phonon dispersion as the underlying factors. Moreover, reducing the density of In+ vacancies in InTe was found to lower the band effective mass and modulate carrier scattering, enhancing the material quality factor (B). To explore these findings, we systematically grew InTe single crystals, achieving exceptional thermoelectric performance. A record-breaking power factor of 12.0 μW·cm–1·K–2 and a dimensionless figure of merit (zT) of 0.5 at room temperature were obtained. Notably, InTe crystals oriented along [110] with low In+ vacancy density exhibited the highest average zT of 0.63 among InTe-based thermoelectric materials within the 300–473K temperature range. Furthermore, we introduced an effective method of reducing In+ vacancies through Indium vapor annealing, resulting in the highest reported carrier mobility of 182 cm2·V–1·s–1 for InTe. Our study highlights the potential for improving InTe's thermoelectric performance near room temperature through vacancy modulation and crystal orientation.

Study on the effects of the oxidized copper foil on graphene nucleation and growth based on the restricted space

In this study, the oxidized copper foil and the original copper foil were used as substrates to fabricate graphene samples by low pressure chemical vapor deposition (LPCVD) in a restricted growth space. The results demonstrated that in the restricted growth chamber, the oxidized layer on the oxidized copper foil inhabited graphene nucleation in the early nucleation stage, but with the oxidized layer heavily decomposing, decomposed oxygen would accelerate graphene growth. Because the decomposition rate of the oxidized layer would increase with growth temperature increasing, the acceleration effect of oxygen atoms on graphene growth becomes more obvious at higher growth temperature. So millimeter-scale graphene single crystals could be easily fabricated at 1060 °C on the oxidized copper foils in the restricted growth chamber. With the help of density functional theory (DFT) calculations, the influence mechanism of oxygen atoms on graphene nucleation and growth on copper substrate was investigated. The results showed that the oxygen atoms could not only react with CH fragments to form CO fragments to consume the number of carbon monomers, but also accelerate the diffusion and clustering of CH fragments.

Tension-compression asymmetry in superelasticity of SrNi2P2 single crystals and the influence of low temperatures

ThCr2Si2-type intermetallic compounds are known to exhibit superelasticity associated with structural transitions through lattice collapse and expansion. These transitions occur via the formation and breaking of Si-type bonds, respectively, under uniaxial loading along the [0 0 1] direction. Unlike most ThCr2Si2-type intermetallic compounds, which have either an uncollapsed tetragonal structure or a collapsed tetragonal structure, SrNi2P2 possesses a third type of collapsed structured: a one-third orthorhombic structure, for which one expects the occurrence of unique structural transitions and superelastic behavior. In this study, uniaxial compression and tension tests were conducted on micron-sized SrNi2P2 single crystalline columns at room temperature, 200K, and 100K, to investigate the influence of loading direction and temperature on the superelasticity of SrNi2P2. Experimental data and density functional theory calculations revealed the presence of tension-compression asymmetry in the structural transitions and superelasticity, as well as an asymmetry in their temperature dependence, due to the opposite superelastic process associated with compression (forming P-P bonds) and tension (breaking P-P bonds). Additionally, following thermodynamics, the observations suggest that this asymmetric superelasticity could lead to an opposite elastocaloric effect between compression and tension, which could be beneficial potentially in obtaining large temperature changes compared to conventional superelastic solids that show the same elastocaloric effect regardless of loading direction. These results provide an important fundamental insight into the structural transitions, superelasticity processes, and potential elastocaloric effects in SrNi2P2.

2D Organic-Inorganic Lead Perovskite: Advancing X-Ray Detection Capability

Two-dimensional (2D) perovskite single crystals have risen to be prominent in the domain of optoelectronic materials due to their exceptional characteristics including notably low ion migration and defect density. A distinguishing feature is the strategic inclusion of larger organic amine spacer, alternately inserted between inorganic lead halide octahedral layers. This spacer effectively mitigates ion migration, even under higher bias voltages, which is particularly advantageous for X-ray detection. However, the simultaneous realization of multiple functions within this realm remains a formidable challenge. In this work, we have synthesized a high-quality organic spacer-incorporated single layered 2D perovskite single crystal of [CYP]PbBr4 (CYP = 1-cyclohexylpiperazine). Our findings reveal the impressive potential of [CYP]PbBr4 in the domain of X-ray detection, as evidenced by the ultrahigh X-ray sensitivity, long-term stability, and astonishingly low detection limit of 1.72 nGyairs-1. Notably, [CYP]PbBr4 also emits bright broadband yellow light with quantum yield of 30.3%, and the fabricated white LED achieves a high Color Rendering Index of 94.1, which surpasses that of commercially available white LED based on YAG: Ce3+ (< 80).

KMg4Bi3: A Narrow Band Gap Semiconductor with a Channel Structure.

The creation of new families of intermetallic or Zintl-phase compounds with high-spin orbit elements has attracted a considerable amount of interest due to the presence of unique electronic, magnetic, and topological phenomena in these materials. Here, we establish the synthesis and structural and electronic characterization of KMg4Bi3 single crystals having a new structure type. KMg4Bi3 crystallizes in space group Cmcm having unit cell parameters a = 4.7654(11) Å, b = 15.694(4) Å, and c = 13.4200(30) Å and features an edge-sharing MgBi4 tetrahedral framework that forms cage-like one-dimensional channels around K+ ions. Diffuse reflectance absorption measurements indicate that this material has a narrow band gap of 0.27 eV, which is in close agreement with the electronic structure calculations that predict it to be a trivial insulator. Electronic transport measurements from 80 to 380 K indicate this material behaves like a narrow band gap semiconductor doped to ∼1018 holes/cm-3, with thermopowers of ∼100 μV/K and appreciable magnetoresistance. Electronic structure calculations indicate this material is close to a topological phase transition and becomes a topological insulator when the lattice is uniformly expanded by 3.5%. Overall, this unique structure type expands the landscape of potential quantum materials.

Enabling resonant ultrasound spectroscopy in high magnetic fields.

Resonant ultrasound spectroscopy (RUS) is a powerful method to determine elastic constants with high accuracy and precision from a single measurement of the mechanical resonances of a sample. Conventionally, the quantitative extraction of elastic moduli with RUS assumes free boundary conditions which can often lead to the adoption of unstable sample positioning between ultrasonic transducers that is incompatible with extreme environments like high magnetic fields. We show that, under specific conditions, introducing a small amount of adhesive between a RUS sample and ultrasonic transducers introduces a perturbation to the free resonance condition which can be accounted for by a simple model. This means elastic constants can be determined to within the uncertainty of conventional RUS, but with significant improvements including sample stability and control of sample orientation. We demonstrate the efficacy of this approach with measurements on a range of materials including room temperature measurements on polycrystalline metals, temperature-dependent measurements of the structural phase transition in strontium titanate single crystals, and magnetic field-dependent measurements of magnetic phase transitions in gadolinium polycrystals up to 14 T.

Structural, optical, thermal, and dielectric studies of urea-doped potassium hydrogen phthalate single crystals: effect of Ocimum Tenuiflorum extract

Structural, optical, thermal, and dielectric studies of urea-doped potassium hydrogen phthalate single crystals: effect of Ocimum Tenuiflorum extract

Si-doped (AlGa)2O3 growth on a-, m- and r-plane α-Al2O3 substrates by molecular beam epitaxy

We reported the growth of (AlGa)2O3 layers on (11 2¯ 0), (10 1¯ 0), and (10 1¯ 2) α-Al2O3 substrates using MBE, and the electrical characterization of Si-doped (AlGa)2O3 layers. The Ga2O3 layers grown on (10 1¯ 0) and (10 1¯ 2) α-Al2O3 were α-phase single crystals, while the Ga2O3 layer grown on (11 2¯ 0) α-Al2O3 consisted of (11 2¯ 0) α-Ga2O3 and ( 2¯ 01) β-Ga2O3. The Al composition of the (11 2¯ 0) and (10 1¯ 0) (AlGa)2O3 layers was controlled by varying the Al flux. The Si-doped (10 1¯ 0) α-(Al x Ga1-x )2O3 layers with x = 0–0.41 were electrically conducting.

Variation of (001) surface structures of strontium titanate single crystals caused by flash event under direct/alternative current electric fields

Variation of (001) surface structures of strontium titanate single crystals caused by flash event under direct/alternative current electric fields

High-light-yield and fast-response β-Ga2O3–Al2O3 thick-film scintillators epitaxially grown via chemical vapor deposition

β-gallia (β-Ga2O3) has been investigated for adoption in power semiconductor wafers; however, it is a promising scintillating material for X-ray detection screens. Thus, the research on methods for growing β-gallia crystals has attracted considerable attention. Herein, 15-μm thick Ga2O3–Al2O3 solid solution films with β-gallia structure were synthesized using metal–organic chemical vapor deposition (CVD) at deposition rate of 15 μm h−1. A high scintillation light yield of 5400 photons per 5.5 MeV and a fast decay response of 5.1 ns of the produced films were observed, which were comparable or superior to those of the β-Ga2O3 single crystals and transparent ceramics. CVD method proved advantageous for the rapid synthesis of micrometer-thick Ga2O3-based scintillation screens.

Lanthanide complexes of monosubstituted Calix[4]arene-ligands: Synthesis, structures, and magnetic properties of [Ln2(L)2(MeOH)4] (Ln = La, Gd, Tb, Tm) (H3L = mono-O-propargyl-calix[4]arene)

The ability of the propargylated calix[4]arene ligand H3L (= 25-(2-propynyloxy)-26,27,28-trihydroxy-calix[4]arene) to bind lanthanide ions has been studied. The triply deprotonated ligand was found to support dinuclear neutral complexes of composition [Ln2L2(MeOH)4] (Ln= La (1), Gd (2), Tb (3), Tm (4)). Spectroscopic data for 1-4 as well as X-ray crystallographic analysis of single crystals of 1∙(MeOH)2 and 2∙(MeOH)2 reveal that two [LnL] entities dimerize via two phenolato groups to generate a centrosymmetric (MeOH)2O3Ln(μ-O)2LnO3(OHMe)2 core structure. The Ln3+ ions reside in a distorted mono-capped octahedral coordination environment. Squid magnetic measurements for the Gd3+ and Tb3+ complexes agree with the formulation as dinuclear compounds, and reveal the presence of very weak antiferromagnetic exchange interactions (J < 0.1 cm−1). The ability of the La3+ complex to react with azides in a click reaction is also demonstrated.

Interplay of intermolecular and intramolecular vibrations mediates ultrafast singlet fission

Singlet fission (SF) is an exciton multiplication process that splits a singlet exciton in organic semiconductors into two triplet excitons and thus, can overcome the Shockley–Queisser limit to improve the solar energy conversion efficiency in photovoltaics. In this paper, we construct a unified model for the ultrafast primary step of the SF process. To achieve this, we investigate the dynamics of vibrational modes and their interactions with the relevant electronic excited states in prototypical SF materials, pentacene (exothermic SF) and tetracene (endothermic SF) single crystals. Additionally, the functional role of the charge transfer (CT) state is also examined. Using the refined parameters obtained from the reported experimental results, we deduce that the intermolecular vibrations mediate the SF in pentacene with the assistance from strong vibronic couplings to intramolecular modes, which drives the SF process to occur within 100 fs. In this timescale, the CT state has a limiting role towards the SF process in pentacene. However, the CT state plays an important role in a relatively slower SF process in tetracene. Our results disentangle the role of underlying vibrational coherences and clarify the importance of the CT state in tetracene crystal. Hence, with our unified model, we can study the coherent dynamics of the SF process, which can principally be extended to other SF materials as well.

Investigating the electrical and optical characteristics of lead-free all-inorganic Cs3Sb2Br9 single crystals

In recent years, halide perovskites have emerged as promising materials for electronic devices. While lead-based perovskites have been extensively studied, exploration of lead-free variants has been limited. Here, we highlight the innovation of observing negative photoconductivity (NPC) induced by light, followed by self-recovery, in lead-free Cs3Sb2Br9 perovskite single crystals. Our study reveals the self-trapping of holes at the Vk center, corresponding to the Br2− dimer, within the midband states of this vacancy-ordered perovskite. This leads to the entrapment of photogenerated charge carriers by charged defect states denoted as Vk, creating an internal electrical field that counteracts the externally imposed field, resulting in NPC. We demonstrate the innovation through the construction of a prototype photodetector with notable sensitivity, featuring high responsivity (6.77 mA/W), detectivity (2.83 × 1012 Jones), and a dark-to-light current ratio of approximately 10. This recognition of retroactive photocurrent in optically active perovskite materials holds promise for advancing highly sensitive detectors.

Monolithic deformable mirror based on lithium niobate single crystal for high-resolution X-ray adaptive microscopy

X-ray microscopy is very promising not only for nondestructive and high-spatial-resolution observation of the internal structure of a sample but also for elemental distribution and chemical state analysis. However, the spatial resolution of microscopes remains unsatisfactory owing to the fabrication error in the objective lens. To realize an ultra-high-resolution, we propose and develop a monolithic deformable mirror based on a lithium niobite single crystal and a novel adaptive imaging system based on it. An X-ray interferometer confirmed that shape modification is possible with an accuracy of 0.67 nm in peak to valley under high stability (0.17 nm over 7 h) and hysteresis-free deformation control. Introducing this adaptive mirror into an X-ray microscope based on advanced Kirkpatrick-Baez mirror optics and correcting the wavefront aberration demonstrated that the X-ray image quality could be significantly improved.

The competition between charge density wave and superconductivity in the kagome metal CsV3(Sb1-xPbx)5 single crystals

Kagome metal AV3Sb5 (A = K, Rb, Cs) has garnered considerable attention for its abundant exotic quantum phenomena and the special competitive relationship between charge density wave (CDW) and superconductivity (SC). In this work we explore the unconventional coupling between charge density wave and superconductivity by means of the substitutional doping of Pb atoms with Sb atoms. Microscopic characterization and performance tests provide valuable phase diagram information for CsV3(Sb1-xPbx)5. Upon Pb doping, a pronounced competition between the charge density wave transition temperature TCDW and the superconducting temperature Tc was observed. Analysis of changes in Debye temperature ΘD and lattice constant, it is shown that Pb doping affects atomic bonding and may strengthen the coupling between adjacent kagome layers to some extent. Furthermore, the small angular shift of the diffraction peak and increased full width at half maximum (FWHM) indicate that the doping causes crystal defects and distorts the crystal structure, which will change the charge density in the local area and may affect the superconductivity. This result further reveals a close correlation between the superconductivity of the system and the electronic structure of the kagome plane in the CsV3Sb5 system. Overall, our results suggest that the observed competition arises from the complex interplay of multiple factors.

Phase Diagrams of Anthracene Derivatives in Pyridinium Ionic Liquids.

Crystal engineering for single crystallization of π-conjugated molecules has attracted much attention because of their electronic, photonic, and mechanical properties. However, reproducibility is a problem in conventional printing techniques because control of solvent evaporation is difficult. We investigated the phase diagrams of two anthracene derivatives in synthesized ionic liquids for non-volatile crystal engineering to determine the critical points for nucleation and crystal growth. Anthracene and 9,10-dibromoanthracene were used as representative π-conjugated molecules that form crystal structures with different packing types. Ionic liquids with an alkylpyridinium cation and bis(fluorosulfonyl)amide were good solvents for the anthracene derivatives from ca. 0 °C to 200 °C. The solubilities (critical points for crystal growth) of the anthracene derivatives in the ionic liquids reached the 100 mM level, which is similar to those in organic solvents. Ionic liquids with phenyl and octyl groups tended to show high-temperature dependence (a high dissolution entropy) with 9,10-dibromoanthracene. The precipitation temperature (critical point for crystal nucleation) at each 9,10-dibromoanthracene concentration was lower than the dissolution temperature. The differences between the dissolution and precipitation temperatures (supersaturated region) in the ionic liquids were greater than those in an organic solvent.

Na2MgP2S6: A new solid electrolyte for sodium ion batteries

Transparent needles-like single crystals of Na2MgP2S6 were obtained by self-flux synthesis route from Na2S, Mg, and P2S5. The crystal structure of the new compound was determined from single-crystal X-ray diffraction data [wR(F2) = 0.066, 1088 reflections, 58 variables]. The chemical composition was confirmed by energy dispersive X-ray spectroscopy (EDX), and the ionic conductivity was measured using electrochemical impedance spectroscopy (EIS). Na2MgP2S6 crystallizes in the orthorhombic system, space group Pbcn (N° 60), a = 7.3629 (3) Å, b = 21.5547 (8) Å, c = 6.2155 (3) Å, V = 986.43 (7) Å3 and Z = 4. The sulfur atoms form a distorted hexagonal close packing within which the sodium, magnesium, and P-P dimer units are octahedrally coordinated and form a honeycomb-like structure. Two of the three sodium atomic positions are partially occupied. Na2MgP2S6 exhibits an ionic conductivity of 8.8×10−7 S cm−1 (Ea = 0.48 eV) at 29.6 °C.

The temperature dependent optical and scintillation characterisation of Bridgman grown CsPbX[formula omitted] (X = Br, Cl) single crystals

Lead halide perovskites are reportedly a very promising group of materials for scintillation due to their fast sub-nanosecond exciton luminescence, small band-gaps, and high theoretical light yield. Unfortunately, they only show emission at cryogenic temperatures. In this work single crystals of CsPbBr3 and CsPbCl3 are studied at cryogenic temperatures. Upon comparing the 10 K emission spectra measured under X-ray and UV–vis excitation, a new near-infrared emission was found for both CsPbBr3 and CsPbCl3 only present under X-ray excitation. The integral light yields of CsPbBr3 and CsPbCl3 at 10 K are estimated to be 34,000 and 2,200 photons/MeV under 40 keV X-ray excitation, respectively. The main components of the light yield of CsPbBr3 at 10 K are the near band-gap free exciton emission that suffers from self-absorption and the broad near-infrared emission that falls outside the typical detection range of a photo-multiplier tube. Due to the combination of the two aforementioned effects it was not possible to measure a γ-ray pulse height spectrum for CsPbBr3 at 10 K. Despite all the suitable properties, like the fast decay, a small band-gap, and the positive prospects of 3D perovskite based scintillators, we conclude that these materials perform poorly as scintillation crystals.

Atomic behavior of nickel-based single crystal superalloy during heat treatment process based on molecular dynamics

The heat treatment process plays a pivotal role in enhancing the characteristics of nickel-based single crystal (NBSC) superalloys. Nevertheless, there exists a paucity of comprehensive investigations concerning the microstructural evolution of NBSC superalloys during heat treatment. This study employs a molecular dynamics simulation method to control the temperature of the NBSC superalloy precisely, aiming to unveil intricate details regarding microstructural evolution, temperature distribution patterns, mechanical properties, and other pertinent aspects during the cooling phase. Additionally, a comparative analysis of internal defect evolution under varying cooling rates is undertaken. The findings highlight the consistently heightened activity of atoms in the γ phase compared to those in the γ′ phase. Notably, the stability disparity between these phases gradually diminishes as the temperature decreases during the cooling process. At elevated temperatures, the prevalence of amorphous phases and dislocations in the γ phase channel diminishes concomitantly with the temperature reduction. Strain distribution in the alloy primarily concentrates in the γ phase channel and the central cross position of the γ′ phase. The temperature reduction correlates with a decline in the alloy model’s strain. In the initial phase of strain reduction, stress fluctuation trends in the X, Y, and Z directions exhibit an initial increase followed by a gradual decrease. Furthermore, the atomic number of HCP defects and dislocation density exhibit distinct patterns of change contingent upon the cooling rates employed.

Surface morphology of naphtacene single crystals grown by physical vapor transport technique

Abstract The surface morphology of naphtacene single crystals grown by the physical vapor transport technique was investigated by atomic force microscopy and white-beam X-ray topography. Locally, two types of line pattern were observed on the basal (001) plane along the [110] and [010] directions, and analyzed from crystallographic viewpoints. Such line patterns are considered in relation to crystallographic periodicities, dislocation lines, and slip-plane phenomena.