Fixed Volume Effect on Polar Properties and Phase Diagrams of Ferroelectric Semi-ellipsoidal Nanoparticles

For advanced applications in modern industry it is very important to reduce the volume of ferroelectric nanoparticles without serious deterioration of their polar properties. In many practically important cases fixed volume (rather than fixed size) corresponds to realistic technological conditions of nanoparticles fabrication. The letter is focused on the theoretical study of the behavior of ferroelectric polarization, paramagnetoelectric coefficient and phase diagrams of semi-ellipsoidal nanoparticles with fixed volume V. Our approach combines the Landau-Ginzburg-Devonshire phenomenology, classical electrostatics and elasticity theory. Our results show that the size effects of the phase diagrams and polarization of semi-ellipsoidal BiFeO3 nanoparticles nontrivially depends on V. These findings provide a path to optimize the polar properties of nanoparticles by controlling their phase diagrams at a fixed volume.Comment: 15 pages, 5 figures, we added the section IV. Paramagnetoelectric (PME) coefficient at fixed volume in this version and changed title and abstract accordingl

Structural and Optical Properties of Silicon Nanowire Arrays Fabricated by Metal Assisted Chemical Etching With Ammonium Fluoride

Here we report on the metal assisted chemical etching method of silicon nanowires (SiNWs) manufacturing, where the commonly used hydrofluoric acid (HF) has been successfully replaced with ammonium fluoride (NH4F). The mechanism of the etching process and the effect of the pH values of H2O2: NH4F solutions on the structural and optical properties of nanowires were studied in detail. By an impedance and Mott-Schottky measurements it was shown that silver-assisted chemical etching of silicon can be attributed to a facilitated charge carriers transport through Si/SiOx/Ag interface. It was shown that the shape of nanowires changes from pyramidal to vertical with pH decreasing. Also it was established that the length of SiNW arrays non-linearly depends on the pH for the etching time of 10 min. A strong decrease of the total reflectance to 5–10% was shown for all the studied samples at the wavelength <800 nm, in comparison with crystalline silicon substrate (c-Si). At the same time, the intensities of the interband photoluminescence and the Raman scattering of SiNWs are increased strongly in compare to c-Si value, and also they were depended on both the length and the shape of SiNW: the biggest values were for the long pyramidal nanowires. That can be explained by a strong light scattering and partial light localization in SiNWs. Hereby, arrays of SiNWs, obtained by using weakly toxic ammonium fluoride, have great potential for usage in photovoltaics, photonics, and sensorics

Diffusion doping route to plasmonic Si/SiOx nanoparticles

International audienceSemiconductor nanoparticles (SNPs) are a valuable building block for functional materials. Capabilities for engineering of electronic structure of SNPs can be further improved with development of techniques of doping by diffusion, as post-synthetic introduction of impurities does not affect the nucleation and growth of SNPs. Diffusion of dopants from an external source also potentially allows for temporal control of radial distribution of impurities. In this paper we report on the doping of Si/SiOx SNPs by annealing particles in gaseous phosphorus. The technique can provide efficient incorporation of impurities, controllable with precursor vapor pressure. HRTEM and X-ray diffraction studies confirmed that obtained particles retain their nanocrystallinity. Elemental analysis revealed doping levels up to 10%. Electrical activity of the impurity was confirmed through thermopower measurements and observation of localized surface plasmon resonance in IR spectra. The plasmonic behavior of etched particles and EDX elemental mapping suggest uniform distribution of phosphorus in the crystalline silicon cores. Impurity activation efficiencies up to 34% were achieved, which indicate high electrical activity of thermodynamically soluble phosphorus in oxide-terminated nanosilicon

The strain-induced transitions of the piezoelectric, pyroelectric and electrocaloric properties of the CuInP2_2S6_6 films

The low-dimensional ferroelectrics, ferrielectrics and antiferroelectrics are of urgent scientific interest due to their unusual polar, piezoelectric, electrocaloric and pyroelectric properties. The strain engineering and strain control of the ferroelectric properties of layered 2D Van der Waals materials, such as CuInP$_2$(S,Se)$_6$ monolayers, thin films and nanoflakes, are of fundamental interest and especially promising for their advanced applications in nanoscale nonvolatile memories, energy conversion and storage, nano-coolers and sensors. Here, we study the polar, piezoelectric, electrocaloric and pyroelectric properties of thin strained films of a ferrielectric CuInP$_2$S$_6$ covered by semiconducting electrodes and reveal an unusually strong effect of a mismatch strain on these properties. In particular, the sign of the mismatch strain and its magnitude determine the complicated behavior of piezoelectric, electrocaloric and pyroelectric responses. The strain effect on these properties is opposite, i.e., "anomalous", in comparison with many other ferroelectric films, for which the out-of-plane remanent polarization, piezoelectric, electrocaloric and pyroelectric responses increase strongly for tensile strains and decrease or vanish for compressive strains.Comment: 16 pages, 5 figures, to be presented at the VI Lithuanian-Polish Meeting on Physics of Ferroelectric

Bending-induced isostructural transitions in ultrathin layers of van der Waals ferrielectrics

Using Landau-Ginzburg-Devonshire (LGD) phenomenological approach we analyze the bending-induced re-distribution of electric polarization and field, elastic stresses and strains inside ultrathin layers of van der Waals ferrielectrics. We consider a CuInP2S6 (CIPS) thin layer with fixed edges and suspended central part, the bending of which is induced by external forces. The unique aspect of CIPS is the existence of two ferrielectric states, FI1 and FI2, corresponding to big and small polarization values, which arise due to the specific four-well potential of the eighth-order LGD functional. When the CIPS layer is flat, the single-domain FI1 state is stable in the central part of the layer, and the FI2 states are stable near the fixed edges. With an increase of the layer bending below the critical value, the sizes of the FI2 states near the fixed edges decreases, and the size of the FI1 region increases. When the bending exceeds the critical value, the edge FI2 states disappear being substituted by the FI1 state, but they appear abruptly near the inflection regions and expand as the bending increases. The bending-induced isostructural FI1-FI2 transition is specific for the bended van der Waals ferrielectrics described by the eighth (or higher) order LGD functional with consideration of linear and nonlinear electrostriction couplings. The isostructural transition, which is revealed in the vicinity of room temperature, can significantly reduce the coercive voltage of ferroelectric polarization reversal in CIPS nanoflakes, allowing for the curvature-engineering control of various flexible nanodevices.Comment: 26 pages, 7 figures and Appendices A-

Is there warming in the pipeline? A multi-model analysis of the Zero Emissions Commitment from CO₂

The Zero Emissions Commitment (ZEC) is the change in global mean temperature expected to occur following the cessation of net CO2 emissions and as such is a critical parameter for calculating the remaining carbon budget. The Zero Emissions Commitment Model Intercomparison Project (ZECMIP) was established to gain a better understanding of the potential magnitude and sign of ZEC, in addition to the processes that underlie this metric. A total of 18 Earth system models of both full and intermediate complexity participated in ZECMIP. All models conducted an experiment where atmospheric CO2 concentration increases exponentially until 1000 PgC has been emitted. Thereafter emissions are set to zero and models are configured to allow free evolution of atmospheric CO2 concentration. Many models conducted additional second-priority simulations with different cumulative emission totals and an alternative idealized emissions pathway with a gradual transition to zero emissions. The inter-model range of ZEC 50 years after emissions cease for the 1000 PgC experiment is −0.36 to 0.29 ∘C, with a model ensemble mean of −0.07 ∘C, median of −0.05 ∘C, and standard deviation of 0.19 ∘C. Models exhibit a wide variety of behaviours after emissions cease, with some models continuing to warm for decades to millennia and others cooling substantially. Analysis shows that both the carbon uptake by the ocean and the terrestrial biosphere are important for counteracting the warming effect from the reduction in ocean heat uptake in the decades after emissions cease. This warming effect is difficult to constrain due to high uncertainty in the efficacy of ocean heat uptake. Overall, the most likely value of ZEC on multi-decadal timescales is close to zero, consistent with previous model experiments and simple theory

The impact of a line probe assay based diagnostic algorithm on time to treatment initiation and treatment outcomes for multidrug resistant TB patients in Arkhangelsk region, Russia

BACKGROUND: In the Arkhangelsk region of Northern Russia, multidrug-resistant (MDR) tuberculosis (TB) rates in new cases are amongst the highest in the world. In 2014, MDR-TB rates reached 31.7% among new cases and 56.9% among retreatment cases. The development of new diagnostic tools allows for faster detection of both TB and MDR-TB and should lead to reduced transmission by earlier initiation of anti-TB therapy. STUDY AIM: The PROVE-IT (Policy Relevant Outcomes from Validating Evidence on Impact) Russia study aimed to assess the impact of the implementation of line probe assay (LPA) as part of an LPA-based diagnostic algorithm for patients with presumptive MDR-TB focusing on time to treatment initiation with time from first-care seeking visit to the initiation of MDR-TB treatment rather than diagnostic accuracy as the primary outcome, and to assess treatment outcomes. We hypothesized that the implementation of LPA would result in faster time to treatment initiation and better treatment outcomes. METHODS: A culture-based diagnostic algorithm used prior to LPA implementation was compared to an LPA-based algorithm that replaced BacTAlert and Löwenstein Jensen (LJ) for drug sensitivity testing. A total of 295 MDR-TB patients were included in the study, 163 diagnosed with the culture-based algorithm, 132 with the LPA-based algorithm. RESULTS: Among smear positive patients, the implementation of the LPA-based algorithm was associated with a median decrease in time to MDR-TB treatment initiation of 50 and 66 days compared to the culture-based algorithm (BacTAlert and LJ respectively, p<0.001). In smear negative patients, the LPA-based algorithm was associated with a median decrease in time to MDR-TB treatment initiation of 78 days when compared to the culture-based algorithm (LJ, p<0.001). However, several weeks were still needed for treatment initiation in LPA-based algorithm, 24 days in smear positive, and 62 days in smear negative patients. Overall treatment outcomes were better in LPA-based algorithm compared to culture-based algorithm (p = 0.003). Treatment success rates at 20 months of treatment were higher in patients diagnosed with the LPA-based algorithm (65.2%) as compared to those diagnosed with the culture-based algorithm (44.8%). Mortality was also lower in the LPA-based algorithm group (7.6%) compared to the culture-based algorithm group (15.9%). There was no statistically significant difference in smear and culture conversion rates between the two algorithms. CONCLUSION: The results of the study suggest that the introduction of LPA leads to faster time to MDR diagnosis and earlier treatment initiation as well as better treatment outcomes for patients with MDR-TB. These findings also highlight the need for further improvements within the health system to reduce both patient and diagnostic delays to truly optimize the impact of new, rapid diagnostics

Long-term climate change commitment and reversibility: an EMIC intercomparison

This paper summarizes the results of an intercomparison project with Earth System Models of Intermediate Complexity (EMICs) undertaken in support of the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (AR5). The focus is on long-term climate projections designed to: (i) quantify the climate change commitment of different radiative forcing trajectories, and (ii) explore the extent to which climate change is reversible on human timescales. All commitment simulations follow the four Representative Concentration Pathways (RCPs) and their extensions to 2300. Most EMICs simulate substantial surface air temperature and thermosteric sea level rise commitment following stabilization of the atmospheric composition at year-2300 levels. The meridional overturning circulation (MOC) is weakened temporarily and recovers to near pre-industrial values in most models for RCPs 2.6–6.0. The MOC weakening is more persistent for RCP 8.5. Elimination of anthropogenic CO2 emissions after 2300 results in slowly decreasing atmospheric CO2 concentrations. At year 3000 atmospheric CO2 is still at more than half its year-2300 level in all EMICs for RCPs 4.5–8.5. Surface air temperature remains constant or decreases slightly and thermosteric sea level rise continues for centuries after elimination of CO2 emissions in all EMICs. Restoration of atmospheric CO2 from RCP to pre-industrial levels over 100–1000 years requires large artificial removal of CO2 from the atmosphere and does not result in the simultaneous return to pre-industrial climate conditions, as surface air temperature and sea level response exhibit a substantial time lag relative to atmospheric CO2