Ultrafast Photoinduced Phase Change in SnSe.

Time-resolved multiterahertz (THz) spectroscopy is used to observe an ultrafast, nonthermal electronic phase change in SnSe driven by interband photoexcitation with 1.55 eV pump photons. The transient THz photoconductivity spectrum is found to be Lorentzian-like, indicating charge localization and phase segregation. The rise of photoconductivity is bimodal in nature, with both a fast and slow component due to excitation into multiple bands and subsequent intervalley scattering. The THz conductivity magnitude, dynamics, and spectra show a drastic change in character at a critical excitation fluence of approximately 6 mJ/cm^{2} due to a photoinduced phase segregation and a macroscopic collapse of the band gap.

Modulation of Vacancy Defects and Texture for High Performance n-Type Bi2 Te3 via High Energy Refinement.

The carrier concentration in n-type layered Bi2 Te3 -based thermoelectric (TE) material is significantly impacted by the donor-like effect, which would be further intensified by the nonbasal slip during grain refinement of crushing, milling, and deformation, inducing a big challenge to improve its TE performance and mechanical property simultaneously. In this work, high-energy refinement and hot-pressing are used to stabilize the carrier concentration due to the facilitated recovery of cation and anion vacancies. Based on this, combined with SbI3 doping and hot deformation, the optimized carrier concentration and high texture degree are simultaneously realized. As a result, a peak figure of merit (zT) of 1.14 at 323 K for Bi2 Te2.7 Se0.3  + 0.05 wt.% SbI3 sample with the high bending strength of 100 Mpa is obtained. Furthermore, a 31-couple thermoelectric cooling device consisted of n-type Bi2 Te2.7 Se0.3  + 0.05 wt.% SbI3 and commercial p-type Bi0.5 Sb1.5 Te3 legs is fabricated, which generates the large maximum temperature difference (ΔTmax ) of 85 K at a hot-side temperature of 343 K. Thus, the discovery of recovery effect in high energy refinement and hot-pressing has significant implications for improving TE performance and mechanical strength of n-type Bi2 Te3 , thereby promoting its applications in harsh conditions.

Dynamic crystallography reveals spontaneous anisotropy in cubic GeTe.

Cubic energy materials such as thermoelectrics or hybrid perovskite materials are often understood to be highly disordered1,2. In GeTe and related IV-VI compounds, this is thought to provide the low thermal conductivities needed for thermoelectric applications1. Since conventional crystallography cannot distinguish between static disorder and atomic motions, we develop the energy-resolved variable-shutter pair distribution function technique. This collects structural snapshots with varying exposure times, on timescales relevant for atomic motions. In disagreement with previous interpretations3-5, we find the time-averaged structure of GeTe to be crystalline at all temperatures, but with anisotropic anharmonic dynamics at higher temperatures that resemble static disorder at fast shutter speeds, with correlated ferroelectric fluctuations along the <100>c direction. We show that this anisotropy naturally emerges from a Ginzburg-Landau model that couples polarization fluctuations through long-range elastic interactions6. By accessing time-dependent atomic correlations in energy materials, we resolve the long-standing disagreement between local and average structure probes1,7-9 and show that spontaneous anisotropy is ubiquitous in cubic IV-VI materials.

Triple-Wavelength Lasing with a Stabilized ß-LaBSiO5:Nd3+ Crystal.

Multi-wavelength lasers, especially the triple-wavelength laser around 1060 nm, could be produced by the 4F3/2 → 4I11/2 transition of Nd3+ and present numerous challenges and opportunities in the field of optoelectronics. The Nd3+-doped high-temperature phase of LaBSiO5 (ß-LBSO) is an ideal crystal to produce triple-wavelength lasers; however, the crystal growth is challenging because of the phase transition from ß-LBSO to low-temperature phase (α-LBSO) at 162 °C. This phase transition is successfully suppressed when the doping content of Nd3+ is larger than 6.3 at. %, and the Nd3+-doped ß-LBSO is stable at room temperature. The local disorder of BO4 tetrahedra due to Nd3+ doping is essential to the stabilization of ß-LBSO. For the first time, the ß-LBSO:8%Nd3+ crystal with a dimension of 1.8 × 1.8 × 1.8 cm3 is obtained through the top-seeded solution method. The crystal shows strong optical absorption in the range of 785-815 nm, matching well with the commercial laser diode pumping source. The optical emission of 4F3/2 → 4I11/2 splits into four peaks with the highest optical emission cross section of 2.14 × 10-20 cm2 at 1068 nm. The continuous-wave triple-wavelength generation of coherent light at 1047, 1071, and 1092 nm is achieved with the highest output power of 235 mW and efficiency of 12.1%.

Valence Disproportionation of GeS in the PbS Matrix Forms Pb5Ge5S12 Inclusions with Conduction Band Alignment Leading to High n-Type Thermoelectric Performance.

Converting waste heat into useful electricity using solid-state thermoelectrics has a potential for enormous global energy savings. Lead chalcogenides are among the most prominent thermoelectric materials, whose performance decreases with an increase in chalcogen amounts (e.g., PbTe > PbSe > PbS). Herein, we demonstrate the simultaneous optimization of the electrical and thermal transport properties of PbS-based compounds by alloying with GeS. The addition of GeS triggers a complex cascade of beneficial events as follows: Ge2+ substitution in Pb2+ and discordant off-center behavior; formation of Pb5Ge5S12 as stable second-phase inclusions through valence disproportionation of Ge2+ to Ge0 and Ge4+. PbS and Pb5Ge5S12 exhibit good conduction band energy alignment that preserves the high electron mobility; the formation of Pb5Ge5S12 increases the electron carrier concentration by introducing S vacancies. Sb doping as the electron donor produces a large power factor and low lattice thermal conductivity (κlat) of ∼0.61 W m-1 K-1. The highest performance was obtained for the 14% GeS-alloyed samples, which exhibited an increased room-temperature electron mobility of ∼121 cm2 V-1 s-1 for 3 × 1019 cm-3 carrier density and a ZT of 1.32 at 923 K. This is ∼55% greater than the corresponding Sb-doped PbS sample and is one of the highest reported for the n-type PbS system. Moreover, the average ZT (ZTavg) of ∼0.76 from 400 to 923 K is the highest for PbS-based systems.

Thermoelectric Performance of the 2D Bi2Si2Te6 Semiconductor.

Bi2Si2Te6, a 2D compound, is a direct band gap semiconductor with an optical band gap of ∼0.25 eV, and is a promising thermoelectric material. Single-phase Bi2Si2Te6 is prepared by a scalable ball-milling and annealing process, and the highly densified polycrystalline samples are prepared by spark plasma sintering. Bi2Si2Te6 shows a p-type semiconductor transport behavior and exhibits an intrinsically low lattice thermal conductivity of ∼0.48 W m-1 K-1 (cross-plane) at 573 K. The first-principles density functional theory calculations indicate that such low lattice thermal conductivity is derived from the interactions between acoustic phonons and low-lying optical phonons, local vibrations of Bi, the low Debye temperature, and strong anharmonicity result from the unique 2D crystal structure and metavalent bonding of Bi2Si2Te6. The Bi2Si2Te6 exhibits an optimal figure of merit ZT of ∼0.51 at 623 K, which can be further enhanced by the substitution of Bi with Pb. Pb doping leads to a large increase in power factor S2σ, from ∼3.9 µW cm-1 K-2 of Bi2Si2Te6 to ∼8.0 µW cm-1 K-2 of Bi1.98Pb0.02Si2Te6 at 773 K, owing to the increase in carrier concentration. Moreover, Pb doping induces a further reduction in the lattice thermal conductivity to ∼0.38 W m-1 K-1 (cross-plane) at 623 K in Bi1.98Pb0.02Si2Te6, due to strengthened point defect (PbBi') scattering. The simultaneous optimization of the power factor and lattice thermal conductivity achieves a peak ZT of ∼0.90 at 723 K and a high average ZT of ∼0.66 at 400-773 K in Bi1.98Pb0.02Si2Te6.

Direct visualization of polaron formation in the thermoelectric SnSe.

SnSe is a layered material that currently holds the record for bulk thermoelectric efficiency. The primary determinant of this high efficiency is thought to be the anomalously low thermal conductivity resulting from strong anharmonic coupling within the phonon system. Here we show that the nature of the carrier system in SnSe is also determined by strong coupling to phonons by directly visualizing polaron formation in the material. We employ ultrafast electron diffraction and diffuse scattering to track the response of phonons in both momentum and time to the photodoping of free carriers across the bandgap, observing the bimodal and anisotropic lattice distortions that drive carrier localization. Relatively large (18.7 Å), quasi-one-dimensional (1D) polarons are formed on the 300-fs timescale with smaller (4.2 Å) 3D polarons taking an order of magnitude longer (4 ps) to form. This difference appears to be a consequence of the profoundly anisotropic electron-phonon coupling in SnSe, with strong Fröhlich coupling only to zone-center polar optical phonons. These results demonstrate a high density of polarons in SnSe at optimal doping levels. Strong electron-phonon coupling is critical to the thermoelectric performance of this benchmark material and, potentially, high performance thermoelectrics more generally.

Polycrystalline SnSe with a thermoelectric figure of merit greater than the single crystal.

Thermoelectric materials generate electric energy from waste heat, with conversion efficiency governed by the dimensionless figure of merit, ZT. Single-crystal tin selenide (SnSe) was discovered to exhibit a high ZT of roughly 2.2-2.6 at 913 K, but more practical and deployable polycrystal versions of the same compound suffer from much poorer overall ZT, thereby thwarting prospects for cost-effective lead-free thermoelectrics. The poor polycrystal bulk performance is attributed to traces of tin oxides covering the surface of SnSe powders, which increases thermal conductivity, reduces electrical conductivity and thereby reduces ZT. Here, we report that hole-doped SnSe polycrystalline samples with reagents carefully purified and tin oxides removed exhibit an ZT of roughly 3.1 at 783 K. Its lattice thermal conductivity is ultralow at roughly 0.07 W m-1 K-1 at 783 K, lower than the single crystals. The path to ultrahigh thermoelectric performance in polycrystalline samples is the proper removal of the deleterious thermally conductive oxides from the surface of SnSe grains. These results could open an era of high-performance practical thermoelectrics from this high-performance material.

Defect engineering in thermoelectric materials: what have we learned?

Thermoelectric energy conversion is an all solid-state technology that relies on exceptional semiconductor materials that are generally optimized through sophisticated strategies involving the engineering of defects in their structure. In this review, we summarize the recent advances of defect engineering to improve the thermoelectric (TE) performance and mechanical properties of inorganic materials. First, we introduce the various types of defects categorized by dimensionality, i.e. point defects (vacancies, interstitials, and antisites), dislocations, planar defects (twin boundaries, stacking faults and grain boundaries), and volume defects (precipitation and voids). Next, we discuss the advanced methods for characterizing defects in TE materials. Subsequently, we elaborate on the influences of defect engineering on the electrical and thermal transport properties as well as mechanical performance of TE materials. In the end, we discuss the outlook for the future development of defect engineering to further advance the TE field.

Demonstration of Energy-Resolved γ-Ray Detection at Room Temperature by the CsPbCl3 Perovskite Semiconductor.

The detection of γ-rays at room temperature with high-energy resolution using semiconductors is one of the most challenging applications. The presence of even the smallest amount of defects is sufficient to kill the signal generated from γ-rays which makes the availability of semiconductors detectors a rarity. Lead halide perovskite semiconductors exhibit unusually high defect tolerance leading to outstanding and unique optoelectronic properties and are poised to strongly impact applications in photoelectric conversion/detection. Here we demonstrate for the first time that large size single crystals of the all-inorganic perovskite CsPbCl3 semiconductor can function as a high-performance detector for γ-ray nuclear radiation at room temperature. CsPbCl3 is a wide-gap semiconductor with a bandgap of 3.03 eV and possesses a high effective atomic number of 69.8. We identified the two distinct phase transitions in CsPbCl3, from cubic (Pm-3m) to tetragonal (P4/mbm) at 325 K and finally to orthorhombic (Pbnm) at 316 K. Despite crystal twinning induced by phase transitions, CsPbCl3 crystals in detector grade can be obtained with high electrical resistivity of ∼1.7 × 109 Ω·cm. The crystals were grown from the melt with volume over several cubic centimeters and have a low thermal conductivity of 0.6 W m-1 K-1. The mobilities for electron and hole carriers were determined to ∼30 cm2/(V s). Using photoemission yield spectroscopy in air (PYSA), we determined the valence band maximum at 5.66 ± 0.05 eV. Under γ-ray exposure, our Schottky-type planar CsPbCl3 detector achieved an excellent energy resolution (∼16% at 122 keV) accompanied by a high figure-of-merit hole mobility-lifetime product (3.2 × 10-4 cm2/V) and a long hole lifetime (16 µs). The results demonstrate considerable defect tolerance of CsPbCl3 and suggest its strong potential for γ-radiation and X-ray detection at room temperature and above.

Strong Valence Band Convergence to Enhance Thermoelectric Performance in PbSe with Two Chemically Independent Controls.

We present an effective approach to favorably modify the electronic structure of PbSe using Ag doping coupled with SrSe or BaSe alloying. The Ag 4d states make a contribution to in the top of the heavy hole valence band and raise its energy. The Sr and Ba atoms diminish the contribution of Pb 6s2 states and decrease the energy of the light hole valence band. This electronic structure modification increases the density-of-states effective mass, and strongly enhances the thermoelectric performance. Moreover, the Ag-rich nanoscale precipitates, discordant Ag atoms, and Pb/Sr, Pb/Ba point defects in the PbSe matrix work together to reduce the lattice thermal conductivity, resulting a record high average ZTavg of around 0.86 over 400-923 K.

High Figure of Merit in Gallium-Doped Nanostructured n-Type PbTe-xGeTe with Midgap States.

PbTe-based thermoelectric materials are some of the most promising for converting heat into electricity, but their n-type versions still lag in performance the p-type ones. Here, we introduce midgap states and nanoscale precipitates using Ga-doping and GeTe-alloying to considerably improve the performance of n-type PbTe. The GeTe alloying significantly enlarges the energy band gap of PbTe and subsequent Ga doping introduces special midgap states that lead to an increased density of states (DOS) effective mass and enhanced Seebeck coefficients. Moreover, the nucleated Ga2Te3 nanoscale precipitates and off-center discordant Ge atoms in the PbTe matrix cause intense phonon scattering, strongly reducing the thermal conductivity (∼0.65 W m-1 K-1 at 623 K). As a result, a high room-temperature thermoelectric figure of merit ZT ∼ 0.59 and a peak ZTmax of ∼1.47 at 673 K were obtained for the Pb0.98Ga0.02Te-5%GeTe. The ZTavg value that is most relevant for devices is ∼1.27 from 400 to 773 K, the highest recorded value for n-type PbTe.

Enhancement of Thermoelectric Performance for n-Type PbS through Synergy of Gap State and Fermi Level Pinning.

We report that Ga-doped and Ga-In-codoped n-type PbS samples show excellent thermoelectric performance in the intermediate temperature range. First-principles electronic structure calculations reveal that Ga doping can cause Fermi level pinning in PbS by introducing a gap state between the conduction and valence bands. Furthermore, Ga-In codoping introduces an extra conduction band. These added electronic features lead to high electron mobilities up to µH ∼ 630 cm2 V-1 s-1 for n of 1.67 × 1019 cm-3 and significantly enhanced Seebeck coefficients in PbS. Consequently, we obtained a maximum power factor of ∼32 µW cm-1 K-2 at 300 K for Pb0.9875Ga0.0125S, which is the highest reported for PbS-based systems giving a room-temperature figure of merit, ZT, of ∼0.35 and ∼0.82 at 923 K. For the codoped Pb0.9865Ga0.0125In0.001S, the maximum ZT rises to ∼1.0 at 923 K and achieves a record-high average ZT (ZTavg) of ∼0.74 in the temperature range of 400-923 K.

All-Scale Hierarchically Structured p-Type PbSe Alloys with High Thermoelectric Performance Enabled by Improved Band Degeneracy.

We show an example of hierarchically designing electronic bands of PbSe toward excellent thermoelectric performance. We find that alloying 15 mol % PbTe into PbSe causes a negligible change in the light and heavy valence band energy offsets (Δ EV) of PbSe around room temperature; however, with rising temperature it makes Δ EV decrease at a significantly higher rate than in PbSe. In other words, the temperature-induced valence band convergence of PbSe is accelerated by alloying with PbTe. On this basis, applying 3 mol % Cd substitution on the Pb sites of PbSe0.85Te0.15 decreases Δ EV and enhances the Seebeck coefficient at all temperatures. Excess Cd precipitates out as CdSe1- yTe y, whose valence band aligns with that of the p-type Na-doped PbSe0.85Te0.15 matrix. This enables facile charge transport across the matrix/precipitate interfaces and retains the high carrier mobilities. Meanwhile, compared to PbSe the lattice thermal conductivity of PbSe0.85Te0.15 is significantly decreased to its amorphous limit of 0.5 W m-1 K-1. Consequently, a highest peak ZT of 1.7 at 900 K and a record high average ZT of ∼1 (400-900 K) for a PbSe-based system are achieved in the composition Pb0.95Na0.02Cd0.03Se0.85Te0.15, which are ∼70% and ∼50% higher than those of Pb0.98Na0.02Se control sample, respectively.

Hierarchical GeP5/Carbon Nanocomposite with Dual-Carbon Conductive Network as Promising Anode Material for Sodium-Ion Batteries.

Due to the Earth's scarcity of lithium, replacing lithium with earth-abundant and low-cost sodium for sodium-ion batteries (SIBs) has recently become a promising substitute for lithium-ion batteries. However, the shortage of appropriate anode materials limits the development of SIBs. Here, a dual-carbon conductive network enhanced GeP5 (GeP5/acetylene black/partially reduced graphene oxide sheets (GeP5/AB/p-rGO)) composite is successfully prepared by a facile ball milling method. The dual-carbon network not only provides more transport pathways for electrons but also relaxes the huge volume change of the electrode material during the charge/discharge process. Compared with only AB- or GO-modified GeP5 (GeP5/AB or GeP5/GO) composite, the GeP5/AB/p-rGO composite shows a superior sodium storage performance with an excellent rate and cycle performance. It delivers a high reversible capacity of 597.5 and 175 mAh/g at the current density of 0.1 and 5.0 A/g, respectively. Furthermore, at the current density of 0.5 A/g, the GeP5/AB/p-rGO composite shows the reversible capacity of 400 mAh/g after 50 cycles with a little capacity attenuation. All above results prove that the GeP5/AB/p-rGO composite has a good prospect of application as an anode material for SIBs.

Scalable Synthesis of Honeycomblike V2O5/Carbon Nanotube Networks as Enhanced Cathodes for Lithium-Ion Batteries.

A green and scalable route to form a honeycomblike macroporous network by homogeneously weaving V2O5 nanowires and carbon nanotubes (CNTs) was developed. The intertwinement between V2O5 nanowires and CNTs not only integrates nanopores into the macroporous system but also elevates the collection and transfer of charges through the conductive network. The unique combination of V2O5 nanowires and CNTs renders the composite monolith with synergic properties for substantially enhancing electrochemical kinetics of lithiation/delithiation when used as a lithium-ion battery (LIB) cathode. This work presents a useful approach for a large-scale production of cellular monoliths as high-performance LIB cathodes.

Homologous Series of 2D Chalcogenides Cs-Ag-Bi-Q (Q = S, Se) with Ion-Exchange Properties.

Four new layered chalcogenides Cs1.2Ag0.6Bi3.4S6, Cs1.2Ag0.6Bi3.4Se6, Cs0.6Ag0.8Bi2.2S4, and Cs2Ag2.5Bi8.5Se15 are described. Cs1.2Ag0.6Bi3.4S6 and Cs1.2Ag0.6Bi3.4Se6 are isostructural and have a hexagonal P63/mmc space group; their structures consist of [Ag/Bi]2Q3 (Q = S, Se) quintuple layers intercalated with disordered Cs cations. Cs0.6Ag0.8Bi2.2S4 also adopts a structure with the hexagonal P63/mmc space group and its structure has an [Ag/Bi]3S4 layer intercalated with a Cs layer. Cs1.2Ag0.6Bi3.4S6 and Cs0.6Ag0.8Bi2.2S4 can be ascribed to a new homologous family Ax[MmS1+m] (m = 1, 2, 3···). Cs2Ag2.5Bi7.5Se15 is orthorhombic with Pnnm space group, and it is a new member of the A2[M5+nSe9+n] homology with n = 6. The Cs ions in Cs1.2Ag0.6Bi3.4S6 and Cs0.6Ag0.8Bi2.2S4 can be exchanged with other cations, such as Ag+, Cd2+, Co2+, Pb2+, and Zn2+ forming new phases with tunable band gaps between 0.66 and 1.20 eV. Cs1.2Ag0.6Bi3.4S6 and Cs0.6Ag0.8Bi2.2S4 possess extremely low thermal conductivity (<0.6 W·m-1·K-1).

A 3D Chemically Modified Graphene Hydrogel for Fast, Highly Sensitive, and Selective Gas Sensor.

Reduced graphene oxide (RGO) has proved to be a promising candidate in high-performance gas sensing in ambient conditions. However, trace detection of different kinds of gases with simultaneously high sensitivity and selectivity is challenging. Here, a chemiresistor-type sensor based on 3D sulfonated RGO hydrogel (S-RGOH) is reported, which can detect a variety of important gases with high sensitivity, boosted selectivity, fast response, and good reversibility. The NaHSO3 functionalized RGOH displays remarkable 118.6 and 58.9 times higher responses to NO2 and NH3, respectively, compared with its unmodified RGOH counterpart. In addition, the S-RGOH sensor is highly responsive to volatile organic compounds. More importantly, the characteristic patterns on the linearly fitted response-temperature curves are employed to distinguish various gases for the first time. The temperature of the sensor is elevated rapidly by an imbedded microheater with little power consumption. The 3D S-RGOH is characterized and the sensing mechanisms are proposed. This work gains new insights into boosting the sensitivity of detecting various gases by combining chemical modification and 3D structural engineering of RGO, and improving the selectivity of gas sensing by employing temperature dependent response characteristics of RGO for different gases.

Co9 S8 /MoS2 Yolk-Shell Spheres for Advanced Li/Na Storage.

Uniform sized Co9 S8 /MoS2 yolk-shell spheres with an average diameter of about 500 nm have been synthesized by a facile route. When evaluated as anodes for lithium-ion and sodium-ion batteries, these Co9 S8 /MoS2 yolk-shell spheres show high specific capacities, excellent rate capabilities, and good cycling stability.

Controllable Preparation of Square Nickel Chalcogenide (NiS and NiSe2) Nanoplates for Superior Li/Na Ion Storage Properties.

A facile and bottom-up approach has been presented to prepare 2D Ni-MOFs based on cyanide-bridged hybrid coordination polymers. After thermally induced sulfurization and selenization processes, Ni-MOFs were successfully converted into NiS and NiSe2 nanoplates with carbon coating due to the decomposition of its organic parts. When evaluated as anodes of Li-ion batteries (LIBs) and Na-ion batteries (NIBs), NiS and NiSe2 nanoplates show high specific capacities, excellent rate capabilities, and stable cycling stability. The NiS plates show good Li storage properties, while NiSe2 plates show good Na storage properties as anode materials. The study of the diffusivity of Li(+) in NiS and Na(+) in NiSe2 shows consistent results with their Li/Na storage properties. The 2D MOFs-derived NiS and NiSe2 nanoplates reported in this work explore a new approach for the large-scale synthesis of 2D metal sulfides or selenides with potential applications for advanced energy storage.