Transient charge-driven 3D conformal printing via pulsed-plasma impingement.

Seamless integration of microstructures and circuits on three-dimensional (3D) complex surfaces is of significance and is catalyzing the emergence of many innovative 3D curvy electronic devices. However, patterning fine features on arbitrary 3D targets remains challenging. Here, we propose a facile charge-driven electrohydrodynamic 3D microprinting technique that allows micron- and even submicron-scale patterning of functional inks on a couple of 3D-shaped dielectrics via an atmospheric-pressure cold plasma jet. Relying on the transient charging of exposed sites arising from the weakly ionized gas jet, the specified charge is programmably deposited onto the surface as a virtual electrode with spatial and time spans of ~mm in diameter and ~µs in duration to generate a localized electric field accordantly. Therefore, inks with a wide range of viscosities can be directly drawn out from micro-orifices and deposited on both two-dimensional (2D) planar and 3D curved surfaces with a curvature radius down to ~1 mm and even on the inner wall of narrow cavities via localized electrostatic attraction, exhibiting a printing resolution of ~450 nm. In addition, several conformal electronic devices were successfully printed on 3D dielectric objects. Self-aligned 3D microprinting, with stacking layers up to 1400, is also achieved due to the electrified surfaces. This microplasma-induced printing technique exhibits great advantages such as ultrahigh resolution, excellent compatibility of inks and substrates, antigravity droplet dispersion, and omnidirectional printing on 3D freeform surfaces. It could provide a promising solution for intimately fabricating electronic devices on arbitrary 3D surfaces.

Plasma parameters correction method based on plasma image-spectrum fusion for matrix effect elimination in LIBS.

Matrix effect is one of the obstacles that hinders the rapid development of laser-induced breakdown spectroscopy (LIBS), and it is currently a hot, challenging, and focal point in research. To eliminate the matrix effect, this study proposed a plasma parameters correction method based on plasma image-spectrum fusion (PPC-PISF). This method corrects the total number density, plasma temperature, and electron number density variations caused by matrix effect using effective features in plasma images and spectra. To verify the feasibility of this method, experiments were conducted on pressed and metal samples, and the results were compared with those corrected by image-assisted LIBS (IA-LIBS). For the pressed samples, after correction by PPC-PISF, the R2 of the calibration curves all improved to above 0.993, the average root-mean-square error (RMSE) decreased by 41.05%, and the average relative error (ARE) decreased by 59.35% evenly in comparison to IA-LIBS. For the metal samples, after correction by PPC-PISF, the R2 of the calibration curves all increased to above 0.997. Additionally, the RMSE decreased by 29.63% evenly, the average ARE decreased by 38.74% compared to IA-LIBS. The experimental results indicate that this method is an effective method for eliminating the matrix effect, promoting the further development of LIBS in industrial detection.

A plasma image-spectrum fusion correction strategy for improving spectral stability based on radiation model in laser induced breakdown spectroscopy.

Spectral fluctuation is one of the main obstacles affecting the further development of LIBS, and it is also the current research hotspot and difficulty. To meet the requirements of industrial monitoring, a novel method named plasma image-spectrum fusion laser induced breakdown spectroscopy (PISF-LIBS) was proposed to correct the spectral fluctuation and improve the quantitative accuracy. In this method, by systematically analyzing the spectral radiation model, six main factors affecting the spectral stability were obtained. Further, the standard spectrum in the ideal plasma state which is not affected by these six factors was calculated, and the deviation from the actual spectrum was obtained. According to the above analysis, the calculated deviation was mainly affected by these six factors and can be estimated through them. Therefore, this study creatively proposed to use the effective information in the plasma images and spectra to indirectly characterize the deviation, so as to realize the correction of spectral fluctuation. To verify the wide applicability of PISF-LIBS in experimental conditions, the LIBS spectra of aluminum alloy obtained under four different experimental conditions were used. After PISF-LIBS correction, the R2 increased to more than 0.974, and the RMSE, MAPE and RSD of the prediction set decreased by 44.789%, 47.854% and 51.687% on average. To further verify the wide applicability of PISF-LIBS in experimental samples, alloy steel samples and pressed samples were also used. For alloy steel samples, after PISF-LIBS correction, the R2 increased to more than 0.996, and the RMSE, MAPE and RSD of the prediction set decreased by 48.337%, 52.856% and 25.819% evenly. For pressed samples, the R2 increased over 0.992, and the RMSE, MAPE and RSD of the prediction set decreased by 61.493%, 61.080% and 39.945% averagely. The experimental results prove the effectiveness and wide applicability of PISF-LIBS in spectral fluctuation correction.

Time-resolved spectral-image laser-induced breakdown spectroscopy for precise qualitative and quantitative analysis of milk powder quality by fully excavating the matrix information.

A novel and effective method named time-resolved spectral-image laser-induced breakdown spectroscopy (TRSI-LIBS) was proposed to achieve precise qualitative and quantitative analysis of milk powder quality. To verify the feasibility of TRSI-LIBS, qualitative and quantitative analysis of milk powder quality was carried out. For qualitative analysis of foreign protein adulteration, the accuracy of models based on TRSI-LIBS was higher than those based on LIBS, with an accuracy improvement of about 5% to 10%. For the quantitative analysis of foreign protein adulteration and element content, the quantitative analysis models based on TSRI-LIBS also had better effect. For instance, limit of detection (LOD),determination coefficient of prediction (R2p), root-mean-square error of prediction (RMSEP) and average relative error of prediction (AREP) of quantitative model of calcium (Ca) content based on TRSI-LIBS improved from 1.47 mg/g, 0.95, 0.35 mg/g and 23.29% to 0.81 mg/g, 0.98, 0.20 mg/g and 12.60%.

Accuracy improvement of single-sample calibration laser-induced breakdown spectroscopy with self-absorption correction.

The single sample calibration laser-induced breakdown spectroscopy (SSC-LIBS) is quite suitable for the fields where the standard sample is hard to obtain, including space exploration, geology, archaeology, and jewelry identification. But in practice, the self-absorption effect of plasma destroys the linear relationship of spectral intensity and element concentration based on the Lomakin-Scherbe formula which is the guarantee of the high accuracy of the SSC-LIBS. Thus, the self-absorption effect limits the quantitative accuracy of SSC-LIBS greatly. In this work, an improved SSC-LIBS with self-absorption correction (SSC-LIBS with SAC) is proposed for the promotion of quantitative accuracy of SSC-LIBS. The SSC-LIBS with SAC can correct the intensity ratio of spectral lines in the calculation of SSC-LIBS through relative self-absorption coefficient K without complicated preparatory information. The alloy samples and pressed ore samples were used to verify the effect of the SSC-LIBS with SAC. Compared with SSC-LIBS, for alloy samples, the average RMSEP and average ARE of SSC-LIBS with SAC decreased from 0.83 wt.% and 13.75% to 0.40 wt.% and 4.06%, respectively. For the pressed ore samples, the average RMSEP and average ARE of SSC-LIBS with SAC decreased from 4.77 wt.% and 90.48% to 2.34 wt.% and 14.60%. The experimental result indicates that SSC-LIBS with SAC has a great improvement of quantitative accuracy and better universality compared with traditional SSC-LIBS, which is a mighty promotion of the wide application of SSC-LIBS.

Tunable valley splitting and an anomalous valley Hall effect in hole-doped WS2 by proximity coupling with a ferromagnetic MnO2 monolayer.

Two-dimensional (2D) valleytronic systems can provide information storage and processing advantages that complement or surpass those of conventional charge and spin-based semiconductor technologies. For efficient use of the valley degree of freedom, the major challenge currently is to lift the valley degeneracy to achieve valley splitting for further valleytronic operations. In this work, we demonstrate that valley splitting and efficient hole-doping in monolayer WS2 can be achieved by the proximity coupling effect of 2D ferromagnetic MnO2 using density functional theory and Berry curvature calculations. A valley splitting of 43 meV is induced in the valence band of WS2. The efficient hole-doping moves the Fermi level just located between the valence band maxima of the K and K' valleys, which is suitable for the valley-polarized transport. The magnitude of valley splitting relies on the strength of interfacial orbital hybridization and can be tuned continually by applying interfacial compression or an electric field. Owing to the sizable Berry curvature and time-reversal symmetry breaking of WS2, a spin- and valley-polarized anomalous Hall current can be generated. Then, we proposed a valleytronic device that can be used as a filter for both the spin and valley based on this WS2/MnO2 van der Waals heterostructure.