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Complex correlated states emerging from many-body interactions between quasiparticles (electrons, excitons and phonons) are at the core of condensed matter physics and material science. In low-dimensional materials, quantum confinement affects the electronic, and subsequently, optical properties for these correlated states. Here, by combining photoluminescence, optical reflection measurements and ab initio theoretical calculations, we demonstrate an unconventional excitonic state and its bound phonon sideband in layered silicon diphosphide (SiP2), where the bound electron–hole pair is composed of electrons confined within one-dimensional phosphorus–phosphorus chains and holes extended in two-dimensional SiP2 layers. The excitonic state and emergent phonon sideband show linear dichroism and large energy redshifts with increasing temperature. Our ab initio many-body calculations confirm that the observed phonon sideband results from the correlated interaction between excitons and optical phonons. With these results, we propose layered SiP2 as a platform for the study of excitonic physics and many-particle effects.

The excitonic insulator is an electronically driven phase of matter that emerges upon the spontaneous formation and Bose condensation of excitons. Detecting this exotic order in candidate materials is a subject of paramount importance, as the size of the excitonic gap in the band structure establishes the potential of this collective state for superfluid energy transport. However, the identification of this phase in real solids is hindered by the coexistence of a structural order parameter with the same symmetry as the excitonic order. Only a few materials are currently believed to host a dominant excitonic phase, Ta 2 NiSe 5 being the most promising. Here, we test this scenario by using an ultrashort laser pulse to quench the broken-symmetry phase of this transition metal chalcogenide. Tracking the dynamics of the material’s electronic and crystal structure after light excitation reveals spectroscopic fingerprints that are compatible only with a primary order parameter of phononic nature. We rationalize our findings through state-of-the-art calculations, confirming that the structural order accounts for most of the gap opening. Our results suggest that the spontaneous symmetry breaking in Ta 2 NiSe 5 is mostly of structural character, hampering the possibility to realize quasi-dissipationless energy transport.

Two-dimensional (2D) magnets have been the recent research focus due to their potential to meet requirements of continuous miniaturization of spintronic devices. However, very few intrinsic 2D ferromagnetic materials, in particular room-temperature magnets, have been demonstrated because of spin fluctuations and disturbed superexchange caused by the dimensional reduction. Herein, a synchronous ultrasonic exfoliation and doping method is proposed to fabricate ferromagnetic 2D black phosphorus (BP) through the adsorption of phthalocyanine cobalt (CoPc). The electron transfer from BP to CoPc is confirmed by X-ray photoelectron spectroscopy, which is believed to be responsible for the ferromagnetic ground state in as-doped BP (Co-BP) with a saturation magnetization of 0.18 emu g−1. The density functional theory calculations well-support the charge transfer and the origin of ferromagnetism in Co-BP. In addition, the electron transfer results in the restricted activity of lone pair electrons, which might improve the antioxidant capacity of BP. Our study shed light on room-temperature ferromagnetism in 2D materials.

Topological materials have received much attention because of their intriguing nontrivial physical properties. Their robust topological surface states (TSSs) afford a stable electron bath that facilitates surface reactions, which has been successfully used to promote reactions on transition metals (TMs). As emergent heterogeneous catalysts, TSS-TMs have introduced new catalytic effects. However, the direct application of TSSs to catalysis has thus far remained elusive. In the present study, we show that Bi2Se3, one of the most representative topological insulators, functions as an excellent catalyst for the oxidative carbonylation of amines with CO and O2 to synthesize urea derivatives, showing superior activity compared with conventional TM-containing heterogeneous and homogeneous catalysts. For example, when Bi2Se3 nanoparticles were used as catalysts, the carbonylation of butylamine was completed in 4 h at 20 °C with a yield of 99%, whereas noble-metal-based catalysts do not function at such a low temperature. In addition, the turnover frequency (TOF) of Bi2Se3 (41 h−1) is five times greater than that for BiSe, which has a crystal structure similar to that of Bi2Se3 but with substantially weakened TSSs. Density functional theory calculations further reveal that the TSSs facilitate the activation of O2 through a triplet-to-singlet spin-conversion reaction, which is the key step for the generation of urea derivatives from amines. These findings indicate a new application area of topological insulators in heterogeneous catalysis.

Ammonia (NH3) is pivotal to the fertilizer industry and one of the most commonly produced chemicals1. The direct use of atmospheric nitrogen (N2) had been challenging, owing to its large bond energy (945 kilojoules per mole)2,3, until the development of the Haber–Bosch process. Subsequently, many strategies have been explored to reduce the activation barrier of the N≡N bond and make the process more efficient. These include using alkali and alkaline earth metal oxides as promoters to boost the performance of traditional iron- and ruthenium-based catalysts4–6 via electron transfer from the promoters to the antibonding bonds of N2 through transition metals7,8. An electride support further lowers the activation barrier because its low work function and high electron density enhance electron transfer to transition metals9,10. This strategy has facilitated ammonia synthesis from N2 dissociation11 and enabled catalytic operation under mild conditions; however, it requires the use of ruthenium, which is expensive. Alternatively, it has been shown that nitrides containing surface nitrogen vacancies can activate N2 (refs. 12–15). Here we report that nickel-loaded lanthanum nitride (LaN) enables stable and highly efficient ammonia synthesis, owing to a dual-site mechanism that avoids commonly encountered scaling relations. Kinetic and isotope-labelling experiments, as well as density functional theory calculations, confirm that nitrogen vacancies are generated on LaN with low formation energy, and efficiently bind and activate N2. In addition, the nickel metal loaded onto the nitride dissociates H2. The use of distinct sites for activating the two reactants, and the synergy between them, results in the nickel-loaded LaN catalyst exhibiting an activity that far exceeds that of more conventional cobalt- and nickel-based catalysts, and that is comparable to that of ruthenium-based catalysts. Our results illustrate the potential of using vacancy sites in reaction cycles, and introduce a design concept for catalysts for ammonia synthesis, using naturally abundant elements. Ammonia is synthesized using a dual-site approach, whereby nitrogen vacancies on LaN activate N2, which then reacts with hydrogen atoms produced over the Ni metal to give ammonia.

Angle-resolved XPS combined with argon ion etching was used to characterize the surface functional groups and the chemical structure of Ti3C2Tx MXene. Survey scanning obtained on the sample surface showed that the sample mainly contains C, O, Ti and F elements, and a little Al element. Analyzing the angle-resolved narrow scanning of these elements indicated that a layer of C and O atoms was adsorbed on the top surface of the sample, and there were many O or F related Ti bonds except Ti–C bond. XPS results obtained after argon ion etching indicated staggered distribution between C–Ti–C bond and O–Ti–C, F–Ti bond. It is confirmed that Ti atoms and C atoms were at the center layer of Ti3C2Tx MXene, while O atoms and F atoms were located at both the upper and lower surface of Ti3C2 layer acting as surface functional groups. The surface functional groups on the Ti3C2 layer were determined to include O2−, OH−, F− and O−–F−, among which F atoms could also desorb from Ti3C2Tx MXene easily. The schematic atomic structure of Ti3C2Tx MXene was derived from the analysis of XPS results, being consistent with theoretical chemical structure and other experimental reports. The results showed that angle-resolved XPS combing with argon ion etching is a good way to analysis 2D thin layer materials.

The ecological devastation observed in the 21st century requires everyone’s participation, including corporates. Many companies have, therefore, incorporated these ecological concerns into their sustainability decisions. We reviewed studies on the nexus of ecological and entrepreneurial sustainability in the context of corporates (large enterprises). The review focuses on clarifying concepts and building a conceptual framework to enhance a better and comprehensive understanding of the ecological side of corporate entrepreneurship sustainability. Through a systematic review of 53 selected papers, we provide inputs for integrating the ecological aspects into company policies and philosophy, in order to build a green business that balances business opportunities with environmental commitments. The study initiates new research agendas by creating a new construct—sustainable corporate ecological entrepreneurship (SCEE).

Summary Although perovskite has been widely explored in optoelectronic devices, it has been rarely explored as a Schottky junction. Here, we demonstrate a light- and mechanical-energy co-harvesting generator based on a dynamic metal/perovskite Schottky junction. In dark conditions, by moving Al over perovskite film (conductivity: 70.0 S/cm), output voltage and current density of −0.70 V and −41.1 A/m2, respectively, are achieved. As defects eliminate the photo-generated carriers in the static metal/perovskite junction under light illumination, the photoresponse is negligible. Strikingly, the output current of dynamic metal/perovskite junction under light illumination is enhanced by 3-fold compared with the dynamic junction in the dark condition. This nonlinear photo-enhanced effect is proposed as a result of strong interaction between the photo-generated and bound back carriers in the dynamic Schottky junction as well as the high light-absorption coefficient of perovskite. A flexible Al/perovskite generator has been demonstrated as a wearable energy-harvesting device.

Intermetallic silicide compounds, LaScSi and Y$_5$Si$_3$, known for being hydrogen (H) storage materials, are drawing attention as candidates for electrides in which anions are substituted by unbound electrons. It is inferred from a muon spin rotation experiment that the local field at the muon site (which is the same site as that for H) in these compounds exhibits a large negative shift under an external magnetic field, which is mostly independent of temperature. Such anomalous diamagnetism signals a unique property of electride electrons associated with transition metals. Moreover, the diamagnetic shift decreases with increasing H content, suggesting that the electride electrons existing coherently in the hollow interstitial positions are adsorbed by H to form hydride ions (H$^-$), 6 pages, 5 figures

Photo-induced phase transitions have been intensively studied owing to the ability to control a material of interest in the ultrafast manner, which can induce exotic phases unable to be attained at equilibrium. However, the key mechanisms are still under debate, and it has currently been a central issue how the couplings between the electron, lattice, and spin degrees of freedom are evolving during photo-induced phase transitions. Here, we develop a new analysis method, frequency-domain angle-resolved photoemission spectroscopy, to gain precise insight into electron-phonon couplings during photo-induced insulator-to-metal transitions for Ta$_2$NiSe$_5$. We demonstrate that multiple coherent phonons generated by displacive excitations show band-selective coupling to the electrons. Furthermore, we find that the lattice modulation corresponding to the 2 THz phonon mode, where Ta lattice is sheared along the a-axis, is the most relevant for the photo-induced semimetallic state.

The excitonic insulator Ta$_2$NiSe$_5$ experiences a first-order structural transition under pressure from rippled to flat layer-structure at Ps = 3 GPa, which drives the system from an almost zero-gap semiconductor to a semimetal. The pressure-induced semimetal, with lowering temperature, experiences a transition to another semimetal with a partial-gap of 0.1-0.2 eV, accompanied with a monoclinic distortion analogous to that occurs at the excitonic transition below Ps. We argue that the partial-gap originates primarily from a symmetry-allowed hybridization of Ta-conduction and Ni-valence bands due to the lattice distortion, indicative of the importance of electron-lattice coupling. The transition is suppressed with increasing pressure to Pc = 8 GPa. Superconductivity with a maximum Tsc = 1.2 K emerges around Pc, likely mediated by strongly electron-coupled soft phonons. The electron-lattice coupling is as important ingredient as the excitonic instability in Ta2NiSe5., Comment: 6 pages, 4 figures

Ruthenium (Ru) loaded catalysts are of significant interest for ammonia synthesis under mild reaction conditions. The B5 sites have been reported as the active sites for ammonia formation, i.e., Ru with other coordinations were inactive, which has limited the utilization efficiency of Ru metal. The implantation of Ru into intermetallic compounds is considered to be a promising approach to tune the catalytic activity and utilization efficiency of Ru. Here we report an acid-durable electride, LnRuSi (Ln = La, Ce, Pr and Nd), as a B5-site-free Ru catalyst. The active Ru plane with a negative charge is selectively exposed by chemical etching using disodium dihydrogen ethylenediaminetetraacetate (EDTA-2Na) acid, which leads to 2–4-fold enhancement in the ammonia formation rate compared with that of the original catalyst. The turnover frequency (TOF) of LnRuSi is estimated to be approximately 0.06 s−1, which is 600 times higher than that of pure Ru powder. Density functional theory (DFT) calculations revealed that the dissociation of N2 occurs easily on the exposed Ru plane of LaRuSi. This systematic study provides firm evidence that layered Ru with a negative charge in LnRuSi is a new type of active site that differs significantly from B5 sites.

Discovering an active and durable catalyst for oxygen reduction reaction is crucial to the commercialization of fuel cells, but remains grand challenging. Here we report, for the first time, the trace doping of early transition metal (ETM) Re into ultrathin PtNiGa nanowires (Re-PtNiGa NWs) to construct a novel catalyst integrating the superior activity, long-time durability, and high utilization efficiency of Pt atoms. Impressively, the Re-PtNiGa tetrametallic NWs present a 19.6-fold enhancement in mass activity (3.49 A mg−1Pt) compared to commercial Pt/C catalyst and only a 10.6% loss in mass activity after 20,000 cycles of durability test. Moreover, the real fuel cell assembled by Re-PtNiGa NWs on the cathode strongly supports its great potential in fuel cells. The density functional theory calculations reveal that introduction of ETM Re into PtNiGa NWs could weaken binding strength of oxygenated species and elevate dissolution potential, well rationalizing the great enhancements in activity and durability.

The ceramic coatings on the surface of aluminum alloy substrates with micro-grooves have been successfully fabricated in the silicate solution via micro-arc oxidation (MAO) approach. Microstructure characterization showed that the larger main discharge channels were located in the center of micro-groove, the smaller secondary discharge channels were located on both sides of main discharge channel; and a few irregular micro-pores existed in the vicinity of all discharge channels, which were mainly cause by the rapid cooling and solidification of discharge channels hindering the removal of gases produced via reaction. Moreover, the growing direction of coating in the initial stage was mainly outward-growth and resulted in the formation of inverted triangle coating structure, which was due to the sharp-angled effect. But in the final growing stage, the inward-growth behavior played a key role owing to the spark transfer. According to above results and discussion, the formation of smooth, uniform and homogeneous ceramic coating on the surface of whole trapezoidal micro-groove substrate contained four stages: anodic oxidation growth, sharp corner rapid growth, coating homogenization and groove self-filling.

Ammonia (NH

In this paper, Na-doped ZnO thin films were grown by MOCVD using cyclopentadienylsodium (CpNa) as the sodium source. The effects of substrate temperature and sodium source temperature on the properties of Na-doped ZnO thin films were studied. SIMS measurement verified that higher substrate temperature would result in higher Na doping content in ZnO:Na thin films. SEM and Hall measurements revealed that both surface morphology and electrical properties of ZnO:Na thin films showed nonlinear variation with substrate temperature and sodium source temperature. When the substrate temperature or the sodium source temperature was increased, the surface morphology of ZnO:Na thin films turned to sheet structures tilted in all directions first and then back to perpendicular hexagonal structure dominant morphology, and the hole concentration increased first and then decreased. This nonlinear variation trend was ascribed to be related to the variation of doping content and impurity position in ZnO:Na thin films, especially the Na impurity position.

We have measured anisotropic electrical resistivity of quasi-one-dimensional Ta2NiSe5 single crystals under pressure. While the in-plane anisotropy is almost pressure independent, the inter-plane one greatly decreases at P c ∼ 3 GPa accompanied by a pressure-induced semiconductor-semimetal transition. Nevertheless, a similar anomaly in the temperature dependence of in-plane anisotropy has been observed in each phase. This anomaly in the low-pressure phase below P c is regarded as an excitonic transition, and thus both of these anomalies are suppressed with increasing pressure. These results suggest that the suppression of the excitonic binding energy with pressure is caused by the increase of free carrier densities and the inter-plane conductivity.

The excitonic insulator (EI) is an intriguing phase of condensed excitons undergoing a Bose-Einstein-Condensation (BEC)-type transition. A prominent candidate has been identified in Ta2NiSe5. Ultrafast spectroscopy allows tracing the coherent response of the EI condensate directly in the time domain. Probing the collective electronic response we can identify fingerprints for the Higgs-amplitude equivalent mode of the condensate. In addition we find a peculiar coupling of the EI phase to a low frequency phonon mode. We will discuss the transient response on multiple energies scales ranging from the exciton dynamics to the coherent THz response of the gap. Publisher PDF

The excitonic insulator is an intriguing correlated electron phase formed of condensed excitons. A promising candidate is the small band gap semiconductor Ta2NiSe5. Here we investigate the quasiparticle and coherent phonon dynamics in Ta2NiSe5 in a time resolved pump probe experiment. Using the models originally developed by Kabanov et al. for superconductors, we show that the material's intrinsic gap can be described as almost temperature independent for temperatures up to about 250 K to 275 K. This behavior supports the existence of the excitonic insulator state in Ta2NiSe5. The onset of an additional temperature dependent component to the gap above these temperatures suggests that the material is located in the BEC-BCS crossover regime. Furthermore, we show that this state is very stable against strong photoexcitation, which reveals that the free charge carriers are unable to effectively screen the attractive Coulomb interaction between electrons and holes, likely due to the quasi one-dimensional structure of Ta2NiSe5., 27 pages, 8 figures

This work was partly supported by JSPS KAKENHI Grants No. 24224010, No. 15H05852, and No. 17H01140.

The excitonic insulator is a long conjectured correlated electron phase of narrow-gap semiconductors and semimetals, driven by weakly screened electron–hole interactions. Having been proposed more than 50 years ago, conclusive experimental evidence for its existence remains elusive. Ta2NiSe5 is a narrow-gap semiconductor with a small one-electron bandgap EG of TC=326 K, a putative excitonic insulator is stabilized. Here we report an optical excitation gap Eop ∼0.16 eV below TC comparable to the estimated exciton binding energy EB. Specific heat measurements show the entropy associated with the transition being consistent with a primarily electronic origin. To further explore this physics, we map the TC–EG phase diagram tuning EG via chemical and physical pressure. The dome-like behaviour around EG∼0 combined with our transport, thermodynamic and optical results are fully consistent with an excitonic insulator phase in Ta2NiSe5.

The physicochemical properties of ZnO are always determined by its chemical composition and physical form. Here we showed a new type of Mg-alloyed ZnO nanostructures by using templating method. Depending on the molar ratio of ordinary metal salts in the reagents, the Mg contents in Zn 1− x Mg x O alloyed nanostructures could be controlled precisely with the tunable optoelectronic properties and reached to a maximum value as high as 48%. We found that the Mg contents in the Zn 1− x Mg x O alloyed nanostructures were evolutive in annealing process and it illustrated that the concentrations of Mg in Zn 1− x Mg x O had a fixed maximum value after annealing at a corresponding temperature. Moreover, we found the precipitation of MgO in Zn 1− x Mg x O nanostructures was in specific crystal planes. We demonstrated that this new findings of their crystal growth characteristics can be helpful to understand the alloyed ZnO nanostructures deeply.

${\mathrm{Ta}}_{2}{\mathrm{NiS}}_{5}$ is supposed to be a simple semiconductor in which excitonic instability of ${\mathrm{Ta}}_{2}{\mathrm{NiSe}}_{5}$ is suppressed due to its large band gap. However, the Ni $2p$ core-level photoemission of ${\mathrm{Ta}}_{2}{\mathrm{NiS}}_{5}$ exhibits a satellite indicating Ni $3d$ orbitals are mixed into its conduction band as expected in an excitonic insulator. The valence band does not show dispersion flattening and spectral sharpening which are fingerprints of an excitonic insulator. Instead, Ni $3p\ensuremath{-}3d$ resonant photoemission indicates Mottness of the Ni $3d$ electron in ${\mathrm{Ta}}_{2}{\mathrm{NiS}}_{5}$ with negative charge-transfer energy. The present results show that ${\mathrm{Ta}}_{2}{\mathrm{NiS}}_{5}$ can be viewed as a valence bond insulator with a band gap exceeding the exciton binding energy.

Optimizing the activity of layered molybdenum disulfide (MoS2) toward hydrogen evolution reaction (HER) process is generally achieved by improving the electrical transport, intrinsic activity, and/or the number of active sites. However, simultaneously coupling these factors to achieve remarkable MoS2-based electrocatalysts has been seldom reported. Herein, we report a facile approach to the defect-rich one-dimensional MoS2 hierarchical architecture (1D-DRHA MoS2), which synergistically integrate the advantageous structural features of rich defects and one-dimensional hierarchal morphology. Toward HER process, the 1D-DRHA MoS2 electrocatalyst exhibited an overpotential of 119 mV at 10 mA cm−2, a Tafel slope of 50.7 mV dec-1, accompanied by an excellent stability. Notably, the activity is competitive to the state-of-the-art MoS2-based electrocatalysts for HER. The combination of experimental evidences and density functional theory calculations demonstrated the incorporation of rich defects and one-dimensional hierarchical structure improved electric conductivity, intrinsic activity, and active sites, which together accounted for the boosted HER performance.

To define the role of the NOTCH signaling pathway in the development of chemoresistance and the associated epithelial-mesenchymal transition (EMT), we investigated the effect of Notch3 on adriamycin (ADM)-resistant human breast cancer cells (MCF-7/ADM cells). We found that Notch3 was downregulated and involved in the chemoresistance of MCF-7/ADM cells, while forced expression of Notch3 reversed the chemoresistance. Furthermore, fos-related antigen 1 (Fra1) was negatively regulated by Notch3 and was highly expressed in MCF-7/ADM cells. Increased Fra1 activated the EMT process. Finally, Notch3 expression was confirmed in clinically chemoresistant samples of breast cancers from patients receiving anthracycline-based chemotherapy. Low expression of Notch3 was an unfavorable predictor of distant relapse-free survival in ER positive breast cancers. Taken together, our findings demonstrate that the Notch3-Fra1 signaling pathway mediates chemoresistance via the EMT.

The excitonic insulator is an intriguing electronic phase of quasi-condensed excitons. A prominent candidate is the small bandgap semiconductor Ta2NiSe5, in which excitons are believed to undergo a BEC-like transition. But experimental evidence for the existence of a coherent condensate in this material is still missing. A direct fingerprint of such a state would be the observation of its collective modes, which are equivalent to the Higgs- and Goldstone-modes in superconductors. Here we report evidence for the existence of a coherent amplitude response in the excitonic insulator phase of Ta2NiSe5. Using non-linear excitations with short laser pulses we identify a phonon-coupled state of the condensate that can be understood as a coupling of its electronic Higgs-mode to a low frequency phonon. The Higgs-mode contribution substantiates the picture of an electronically driven phase transition and characterizes the transient order parameter of the excitonic insulator as a function of temperature and excitation density., Comment: 32 pages, 12 figures, 1 table

The Na-doped p-type ZnO thin films were prepared by DC reactive magnetron sputtering. Two types of substrates were used for separate testing purposes: silicon wafers for crystallinity measurements and glass slides for electrical and optical transmittance measurements. The lowest room-temperature resistivity under the optimal condition was 59.9 Ω cm, with a Hall mobility of 0.406 cm2 V−1s−1 and a carrier concentration of 2.57 × 1017 cm−3. The Na-doped ZnO thin films possessed a good crystallinity with c-axis orientation and a high transmittance (∼85%) in the visible region. The effects of the substrate temperature on the crystallinity and the electrical properties were discussed.