Negative Thermal Expansion in ABC(MoO4)3 Compounds.

Negative thermal expansion (NTE) compounds provide a solution for the mismatch of coefficients of thermal expansion in highly integrated device design. However, the current NTE compounds are rare, and how to effectively design new NTE compounds is still challenging. Here, a new concept is proposed to design NTE compounds, that is, to increase the flexibility of framework structure by expanding the space in framework structure compounds. Taking the parent compound NaZr2(PO4)3 as a case, a new NTE system AIBIICIII(MoO4)3 (A = Li, Na, K, and Rb; B = Mg and Mn; C = Sc, In, and Lu) is designed. In these compounds, the large volume of MoO4 tetrahedron is used to replace the small volume of PO4 tetrahedron in NaZr2(PO4)3 to enhance structural space and NTE performance. Simultaneously, a joint study of temperature-dependent X-ray diffraction, Raman spectroscopy, and the first principles calculation reveals that the NTE in AIBIICIII(MoO4)3 series compounds arise from the coupled oscillation of polyhedral. Large-radius ions are conducive to enhancing the space and softening the framework structure to achieve the enhancement of NTE. The current strategy for designing NTE compounds is expected to be adopted in other compounds to obtain more NTE compounds.

The formation energy, phase transition, and negative thermal expansion of Fe2-xScxW3O12.

Tungstates with a molecular formula A2W3O12 exhibits a wider negative thermal expansion (NTE) temperature range than molybdates but are challenging to synthesize, especially when A = Fe or Cr with metastable structures. To enhance the structural stability of Fe2W3O12, Sc with lower electronegativity is adopted to substitute Fe according to Fe2-xScxW3O12, considering the thermodynamic stability of Sc2W3O12. It is shown that the solid solutions can be easily synthesized and the phase transition temperature (PTT) can be tuned to well below room temperature (RT). Theoretical calculations and experimental results show that the formation energy decreases and the W-O bond in Fe-O-W gradually strengthens as the substitution of Sc in Fe2-xScxW3O12 increases, indicating an increase in structural stability. NTE is enhanced after phase transition with an increase in the Sc content. The reduction in PTT and the enhancement in NTE properties of Fe2W3O12 could result in a decrease in the effective electronegativity of the Fe-site elements, resulting in a low formation energy and strengthened W-O bond in Fe-O-W, which corresponds to a more stable structure.

A linear scaling law for predicting phase transition temperature via averaged effective electronegativity derived from A2M3O12-based compounds.

The chemical flexibility of A2M3O12-based compounds enables the design of materials with versatile functionalities such as ferroelastic switching, ion conduction and negative thermal expansion (NTE) above the ferroelastic transition temperature (Tt), which is promising for a variety of applications. Quantitative prediction of Tt is essential but lacking. Herein we propose a concept of averaged effective electronegativity (AEE) and establish a linear relationship between the Tt and AEE for A2M3O12-based compounds. The linear scaling law is validated using first principles calculations of the effective charge on oxygen and its effectiveness is verified experimentally by designing high entropy compounds Scx1Zrx2Hfx3Fex4Moy1Vy2O12 and a NTE compound Zr2MoVPO12 with expected Tt. Generalization of the linear scaling law to other NTE oxides with displacive phase transition is also demonstrated. The findings can be used as a simple and effective approach to guide the design of novel compounds with desired properties and Tt.

Anomalous Thermal Expansion in Ta2WO8 Oxide Semiconductor over a Wide Temperature Range.

Expansion of material is one of the major impediments in the high precision instrument and engineering field. Low/zero thermal expansion compounds have drawn great attention because of their important scientific significance and enormous application value. However, the realization of low thermal expansion over a wide temperature range is still scarce. In this study, a low thermal expansion over a wide temperature range has been observed in the Ta2WO8 oxide semiconductor. It is a balance effect of the negative thermal expansion of the a axis and the positive thermal expansion of the b axis and the c axis to achieve low thermal expansion behavior. The results of the means of variable temperature X-ray diffraction and variable pressure Raman spectroscopy analysis indicated that the transverse vibration of bridging oxygen atoms is the driving force, which is corresponding to the low-frequency lattice modes with a negative Grüneisen parameter. The present study provides one wide band gap semiconductor Ta2WO8 with anomalous thermal expansion behavior.

Understanding Negative Thermal Expansion of Zn2GeO4 through Local Structure and Vibrational Dynamics.

Zn2GeO4 is a multifunctional material whose intrinsic thermal expansion properties below ambient temperature have not been explored until now. Herein, the thermal expansion of Zn2GeO4 is investigated by synchrotron X-ray diffraction, with the finding that Zn2GeO4 exhibits very low negative (αv = -2.02 × 10-6 K-1, 100-300 K) and positive (αv = +2.54 × 10-6 K-1, 300-475 K) thermal expansion below and above room temperature, respectively. A combined study of neutron powder diffraction and extended X-ray absorption fine structure spectroscopy shows that the negative thermal expansion (NTE) of Zn2GeO4 originates from the transverse vibrations of O atoms in the four- and six-membered rings with ZnO4-GeO4 tetrahedra. In addition, the results of temperature- and pressure-dependent Raman spectra identify the low-frequency phonon modes (50-150 cm-1) with negative Grüneisen parameters softening upon pressuring and stiffening upon heating during the lattice contraction, thus contributing to the NTE. This study not only reports the interesting thermal expansion behavior of Zn2GeO4 but also provides further insights into the NTE mechanism of novel structures.

Zero Thermal Expansion in Ta2Mo2O11 by Compensation Effects.

Although zero thermal expansion (ZTE) materials have broad application prospects for high precision engineering, they are rare. Here, a new ZTE material, Ta2Mo2O11 (αl = 0.37 × 10-6 K-1, 200-600 K), is reported. A joint study of high-resolution synchrotron X-ray diffraction, temperature- and pressure-dependent Raman spectroscopy, and first-principles calculations was performed to investigate the structure and dynamics of Ta2Mo2O11 with the aim of understanding its ZTE mechanism. Ta2Mo2O11 displays a layered structure, stacking along the [001] direction. Analysis of the phonon modes indicates that positive and negative contributions to thermal expansion are balanced, and a shrinkage occurs along the layers, while the interlayer distance expands with increasing temperature, thus giving rise to the ZTE behavior of Ta2Mo2O11. The present study provides a promising ZTE material and new insights into the mechanisms of thermal expansion.

Hydrate formation and its effects on the thermal expansion properties of HfMgW3O12.

HfMgW3O12 is a representative material with negative thermal expansion in the ABM3O12 (A = Zr, Hf; B = Mg, Mn, Zn, M = W, Mo) family. Herein we report a novel feature of hydration in HfMgW3O12 and its effect on the thermal expansion and its structures which have not been determined previously. It is found that hydrate formation in HfMgW3O12 occurs under ambient or moisture conditions and restrain the low energy librational and translational and even high energy bending and stretching motions of the polyhedra. The coefficient of thermal expansion could be tailored from negative to zero and positive depending on the hydration levels. The unhydrated HfMgW3O12 adopts an orthorhombic structure with space group Pna21 (33) without phase transition at least from 80 K to 573 K, but pressure-induced structure transition and amorphization are found to occur at about 0.19 Gpa and above 3.93 GPa, respectively.

Structure and Negative Thermal Expansion in Zr0.3Sc1.7Mo2.7V0.3O12.

A2M3O12-based materials have received considerable attention owing to their wide range of negative thermal expansion (NTE) and chemical flexibility toward novel materials design. However, the structure and NTE mechanism remain challenging. Here, Zr4+ and V5+ are used as a unit to compensatorily replace Sc3+ and Mo6+ in Sc2Mo3O12 to tune its thermal expansion. Its crystal structure, phase transition, NTE property, and corresponding mechanisms are studied by high-resolution synchrotron X-ray diffraction, powder X-ray diffraction, ultralow-frequency Raman spectroscopy, and density functional theory calculations. The results show that Zr0.3Sc1.7Mo2.7V0.3O12 adopts an orthorhombic (Pbcn) structure at room temperature, with V atoms occupying the position of Mo1 atoms and Zr atoms occupying the position of Sc atoms, and transforms to monoclinic (P21/a) structure at ∼133 K (45 K lower than that of Sc2Mo3O12). It exhibits excellent NTE in a broader range. Most of the phonon modes below 350 cm-1 have negative Grüneisen parameters, of which the lowest and next-lowest frequency (38.5 and 45.8 cm-1) optical phonon modes arising from the translational vibrations of the Sc/Zr and Mo/V atoms in the plane of the nonlinear linkage Sc/Zr-O-Mo/V have the largest and next-largest negative Grüneisen parameters and positive total anharmonicity, and contribute most to the NTE.

Structural, vibrational and thermal expansion properties of Sc2W4O15.

A novel oxide material with the formula of Sc2W4O15 and orthorhombic symmetry is synthesized by solid state reactions and its structure, composition, vibrational properties and thermal expansion are investigated and identified by temperature-dependent X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), X-ray photoelectron spectrometry (XPS) and dilatometry. It is shown that the oxide material with an orthorhombic symmetry shows a similar structure to that of Sc2W3O12, but with W partially occupying the position of Sc, leading to not only the corner-sharing ScO6-WO4 connections but also the corner-sharing WO6-WO4 connections. Raman spectroscopic studies show that compared to Sc2W3O12, the FWHMs of most Raman modes in Sc2W4O15 increase due to the occupation of W6+ in the Sc3+ position. Besides, the W-O bonds in Sc2W4O15 are slightly harder than those in Sc2W3O12. An intrinsic thermal contraction in a wide range of temperatures (93-572 K) is demonstrated, which is attributed to the librational and translational vibrations of the corner-sharing polyhedra as well as the transverse vibrations of the bridging O atoms in the Sc-O-W and W-O-W linkages.

Near-Zero Thermal Expansion and Phase Transitions in HfMg1-x Zn x Mo3O12.

The effects of Zn2+ incorporation on the phase formation, thermal expansion, phase transition, and vibrational properties of HfMg1-x Zn x Mo3O12 are investigated by XRD, dilatometry, and Raman spectroscopy. The results show that (i) single phase formation is only possible for x ≤ 0.5, otherwise, additional phases of HfMo2O8 and ZnMoO4 appear; (ii) The phase transition temperature from monoclinic to orthorhombic structure of the single phase HfMg1-x Zn x Mo3O12 can be well-tailored, which increases with the content of Zn2+; (iii) The incorporation of Zn2+ leads to an pronounced reduction in the positive expansion of the b-axis and an enhanced negative thermal expansion (NTE) in the c-axes, leading to a near-zero thermal expansion (ZTE) property with lower anisotropy over a wide temperature range; (iv) Replacement of Mg2+ by Zn2+ weakens the Mo-O bonds as revealed by obvious red shifts of all the Mo-O stretching modes with increasing the content of Zn2+ and improves the sintering performance of the samples which is observed by SEM. The mechanisms of the negative and near-ZTE are discussed.

A paper triboelectric nanogenerator for self-powered electronic systems.

Paper, as one of the most important inventions of mankind, is still widely used in our daily life. In this study, the paper is explored as a platform for power sources based on the universally known triboelectric friction. A novel paper triboelectric nanogenerator (P-TENG) was successfully developed, which could harvest mechanical energy from ambient sources and generate considerable electrical energy. The maximum power density of the P-TENG reached 53 W m-2. In addition, the P-TENG possesses a natural advantage of being able to be integrated within a book, and thus can effectively convert mechanical energy from the action of turning book pages into electricity. When turning a book page, the output voltage and current of the P-TENG were obtained to be about 400 V and 0.17 mA, respectively. This generated electricity could directly light up 80 commercial white light-emitting diodes (LEDs) connected in series without any energy storage process. The white LEDs powered by the P-TENG can provide sufficient illumination for reading printed text in darkness. This research provides a promising solution for developing paper-based self-powered electronic systems.

Negative thermal expansion and broad band photoluminescence in a novel material of ZrScMo2VO12.

In this paper, we present a novel material with the formula of ZrScMo2VO12 for the first time. It was demonstrated that this material exhibits not only excellent negative thermal expansion (NTE) property over a wide temperature range (at least from 150 to 823 K), but also very intense photoluminescence covering the entire visible region. Structure analysis shows that ZrScMo2VO12 has an orthorhombic structure with the space group Pbcn (No. 60) at room temperature. A phase transition from monoclinic to orthorhombic structure between 70 and 90 K is also revealed. The intense white light emission is tentatively attributed to the n- and p-type like co-doping effect which creates not only the donor- and acceptor-like states in the band gap, but also donor-acceptor pairs and even bound exciton complexes. The excellent NTE property integrated with the intense white-light emission implies a potential application of this material in light emitting diode and other photoelectric devices.

A monolayer of hierarchical silver hemi-mesoparticles with tunable surface topographies for highly sensitive surface-enhanced Raman spectroscopy.

We proposed a facile green synthesis system to synthesize large-scale Ag hemi-mesoparticles monolayer on Cu foil. Ag hemi-mesoparticles have different surface morphologies on their surfaces, including ridge-like, meatball-like, and fluffy-like shapes. In the reaction, silver nitrate was reduced by copper at room temperature in dimethyl sulfoxide via the galvanic displacement reaction. The different surface morphologies of the Ag hemi-mesoparticles were adjusted by changing the reaction time, and the hemi-mesoparticle surface formed fluffy-spherical nanoprotrusions at longer reaction time. At the same time, we explored the growth mechanism of silver hemi-mesoparticles with different surface morphologies. With 4-mercaptobenzoic acid as Raman probe molecules, the fluffy-like silver hemi-mesoparticles monolayer with the best activity of surface enhanced Raman scattering (SERS), the enhancement factor is up to 7.33 × 10(7) and the detection limit can reach 10(-10)M. SERS measurements demonstrate that these Ag hemi-mesoparticles can serve as sensitive SERS substrates. At the same time, using finite element method, the distribution of the localized electromagnetic field near the particle surface was simulated to verify the enhanced mechanism. This study helps us to understand the relationship between morphology Ag hemi-mesoparicles and the properties of SERS.

Realization of high sensitive SERS substrates with one-pot fabrication of Ag-Fe3O4 nanocomposites.

Ag-Fe3O4 nanocomposites were synthesized by the redox reaction between Ag2O and Fe(OH)2 in the absence of additional reductant at moderate temperature and atmospheric condition. The as-synthesized Ag-Fe3O4 nanocomposites are assembled into an orderly arrayed SERS substrate holding clean and reproducible properties with an applied external magnetic field. 4-mercaptobenzoic acid (4-MBA) is chosen as the probe molecule to test the enhancement factors (EF), uniformity and reproducibility of the SERS substrate. Experimental results indicate that the EF of 4-MBA on our proposed SERS substrate is up to 5.2×10(6) and the detection limit is down to ∼10(-10) M. The SERS spectra of 4-MBA molecules ranging from 200 cm(-1) to 2000 cm(-1) were randomly collected from a number of positions on the substrate and six Ag-Fe3O4 nanocomposites substrates are measured with the same procedure. It is shown that the SERS substrate have the good uniformity and reproducibility with low standard deviation, indicating our proposed Ag-Fe3O4 nanocomposites with external magnetic field control abilities have potential applications in the fields of magnetic separation and SERS techniques.

Interaction of crystal water with the building block in Y2Mo3O12 and the effect of Ce3+ doping.

Ce(3+) ions are introduced into the lattice of Y2Mo3O12 with a sol-gel method with the aim to reduce its hygroscopicity and pursue the interaction of crystal water molecules with the building block. It is found that Ce(3+) ions occupy the positions of Y(3+) in the lattice and have the function of expelling crystal water molecules in the microchannels so that the number of crystal water molecules decreases significantly as the Ce(3+) content increases and a complete depletion of the crystal water is achieved when the content of Ce(3+) is higher than 8 mol%. Based on the binding energy changes of Mo 3d and Y 3d with and without Ce(3+) in the lattice, the configuration of the crystal water in the building block is deduced, namely, a crystal water serves as a spring with its O(2-) pointing to the Y(3+) in an octahedron and with its H(+) approaching the next nearest O(2-) in the Y-O-Mo bridge. With such a configuration, the effects of the crystal water on the thermal expansion properties of Y2Mo3O12 and the like are explained. It is also shown that the number of crystal water molecules per molecular formula can be quantified by the full width at half maximum of the Raman bands or relative intensity with linear relationships, suggesting that Raman spectroscopy can be a potential tool in quantifying crystal water molecules at room temperature in this or related materials.

[Stabilising porous silicon luminescence by a novel titanium-doped stain etching approach].

Porous silicon (PS) with good luminescent stability and homogeneity was fabricated by using a novel titanium-doped stain etching approach. The blue shift and degrading of the photoluminescence (PL) were not observed when stored and annealed in ambient air. The good luminescent stability is attributed to the surface passivation of the PS by both oxygen and titanium during fabrication. The PL position is independent of the etching time. The results indicate that the photon excitation process meets the quantum confinement mechanism since the PL intensity reaches its maximum when the particle size-dependent band gap is in resonance with the exciting photon energy. The photon emission process is, however, not a direct band-band transition, rather through a surface state within the band gap, instead.