First principles based multiparadigm modeling of electronic structures and dynamics

Electronic structures and dynamics are the key to linking the material composition and structure to functionality and performance.

An essential issue in developing semiconductor devices for photovoltaics is to design materials with optimal band gaps and relative positioning of band levels. Approximate DFT methods have been justified to predict band gaps from KS/GKS eigenvalues, but the accuracy is decisively dependent on the choice of XC functionals. We show here for CuInSe₂ and CuGaSe₂, the parent compounds of the promising CIGS solar cells, conventional LDA and GGA obtain gaps of 0.0-0.01 and 0.02-0.24 eV (versus experimental values of 1.04 and 1.67 eV), while the historically first global hybrid functional, B3PW91, is surprisingly the best, with band gaps of 1.07 and 1.58 eV. Furthermore, we show that for 27 related binary and ternary semiconductors, B3PW91 predicts gaps with a MAD of only 0.09 eV, which is substantially better than all modern hybrid functionals, including B3LYP (MAD of 0.19 eV) and screened hybrid functional HSE06 (MAD of 0.18 eV).

The laboratory performance of CIGS solar cells (> 20% efficiency) makes them promising candidate photovoltaic devices. However, there remains little understanding of how defects at the CIGS/CdS interface affect the band offsets and interfacial energies, and hence the performance of manufactured devices. To determine these relationships, we use the B3PW91 hybrid functional of DFT with the AEP method that we validate to provide very accurate descriptions of both band gaps and band offsets. This confirms the weak dependence of band offsets on surface orientation observed experimentally. We predict that the CBO of perfect CuInSe₂/CdS interface is large, 0.79 eV, which would dramatically degrade performance. Moreover we show that band gap widening induced by Ga adjusts only the VBO, and we find that Cd impurities do not significantly affect the CBO. Thus we show that Cu vacancies at the interface play the key role in enabling the tunability of CBO. We predict that Na further improves the CBO through electrostatically elevating the valence levels to decrease the CBO, explaining the observed essential role of Na for high performance. Moreover we find that K leads to a dramatic decrease in the CBO to 0.05 eV, much better than Na. We suggest that the efficiency of CIGS devices might be improved substantially by tuning the ratio of Na to K, with the improved phase stability of Na balancing phase instability from K. All these defects reduce interfacial stability slightly, but not significantly.

A number of exotic structures have been formed through high pressure chemistry, but applications have been hindered by difficulties in recovering the high pressure phase to ambient conditions (i.e., one atmosphere and room temperature). Here we use dispersion-corrected DFT (PBE-ulg flavor) to predict that above 60 GPa the most stable form of N₂O (the laughing gas in its molecular form) is a 1D polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03-0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions both polymers relax below 14 GPa to the same stable non-planar trans-polymer, accompanied by possible electronic structure transitions. The predicted phonon spectrum and dissociation kinetics validate the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a new type of conducting polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions.

Modeling non-adiabatic electron dynamics has been a long-standing challenge for computational chemistry and materials science, and the eFF method presents a cost-efficient alternative. However, due to the deficiency of FSG representation, eFF is limited to low-Z elements with electrons of predominant s-character. To overcome this, we introduce a formal set of ECP extensions that enable accurate description of p-block elements. The extensions consist of a model representing the core electrons with the nucleus as a single pseudo particle represented by FSG, interacting with valence electrons through ECPs. We demonstrate and validate the ECP extensions for complex bonding structures, geometries, and energetics of systems with p-block character (C, O, Al, Si) and apply them to study materials under extreme mechanical loading conditions.

Despite its success, the eFF framework has some limitations, originated from both the design of Pauli potentials and the FSG representation. To overcome these, we develop a new framework of two-level hierarchy that is a more rigorous and accurate successor to the eFF method. The fundamental level, GHA-QM, is based on a new set of Pauli potentials that renders exact QM level of accuracy for any FSG represented electron systems. To achieve this, we start with using exactly derived energy expressions for the same spin electron pair, and fitting a simple functional form, inspired by DFT, against open singlet electron pair curves (H₂ systems). Symmetric and asymmetric scaling factors are then introduced at this level to recover the QM total energies of multiple electron pair systems from the sum of local interactions. To complement the imperfect FSG representation, the AMPERE extension is implemented, and aims at embedding the interactions associated with both the cusp condition and explicit nodal structures. The whole GHA-QM+AMPERE framework is tested on H element, and the preliminary results are promising.

Natural cone formation for fast ignition of laser fusion

We propose to utilize the leading pulse of a petawatt class laser to create a conic plasma channel in the dense plasmas. This plasma channel could serve as a natural cone to guide the main pulse to the cone tip, as behaves similarly to the physical Au cone. We estimate that the leading pulse of a petawatt laser could create a natural cone with cone tip only about 100 mu m away from the edge of compressed core plasma. The natural cone formation should be compatible for a good uniform compression and efficient fast heating of the imploded fuel.

Algorithm of far-field centre estimation based on phase-only matched filter

Estimation of the far-field centre is carried out in beam auto-alignment. In this paper, the features of the far-field of a square beam are presented. Based on these features, a phase-only matched filter is designed, and the algorithm of centre estimation is developed. Using the simulated images with different kinds of noise and the 40 test images that are taken in sequence, the accuracy of this algorithm is estimated. Results show that the error is no more than one pixel for simulated noise images with a 99% probability, and the stability is restricted within one pixel for test images. Using the improved algorithm, the consumed time is reduced to 0.049 s.

Optical transmission larger than 1 (T > 1) through ZnS-SiO2/AgOx/ZnS-SiO2 sandwiched thin films

Optical transmission through flat media should be smaller than 1. However, we have observed optical transmission up to T=1.18. The samples were ZnS-SiO2/AgOx/ZnS-SiO2 sandwiched thin films on glass substrate. The supertransmission could only be observed in the near field. We attribute the supertransmission to the lateral propagation relayed by the laser activated and decomposed Ag nanoparticles. (c) 2006 American Institute of Physics.

Super-resolution with a nonlinear thin film: Beam reshaping via internal multi-interference

In laser applications, the size of the focus spot can be reduced beyond the diffraction limit with a thin film of strong nonlinear optical Kerr effect. We present a concise theoretical simulation of the device. The origin of the super-resolution is found to be mainly from the reshaping effect due to the strongly nonlinear refraction mediated multi-interference inside the thin film. In addition, both diffraction and self-focusing effects have been explored and found negligible for highly refractive and ultrathin films in comparison with the reshaping effect. Finally, the theoretic model has been verified in experiments with single Ge2Sb2Te5 film and SiN/Si/SiN/Ge2Sb2Te2 multilayer structures. (c) 2006 American Institute of Physics.

On the dynamic readout of sub-diffraction-limit pit arrays with a silver thin film

Fast moving arrays of periodic sub-diffraction-limit pits were dynamically read out via a silver thin film. The mechanism of the dynamic readout is analysed and discussed in detail, both experimentally and theoretically. The analysis and experiment show that, in the course of readout, surface plasmons can be excited at the silver/air interface by the focused laser beam and amplified by the silver thin film. The surface plasmons are transmitted into the substrate/silver interface with a large enhancement. The surface waves at the substrate/silver interface are scattered by the sinusoidal pits of sub-diffraction-limit size. The scattered waves are collected by a converging lens and guided into the detector for the readout.

Negative refraction via domain wall resonances in a homogeneous mixture of ferro- and nonmagnetic substances

We deliver the general conditions on the synthetic proportions for a homogeneous mixture of ferro- and nonmagnetic substances to become left-handed. As an alternative for left-handed metamaterials, we consider mixing ferromagnetic materials with nonmagnetic microscopic particles. In the mixture, the ferromagnetic material provides the needed permeability via domain wall resonances at high frequencies, whereas the nonmagnetic material gives the required permittivity. Using the effective medium theory, we have found that when the concentration of the nonmagnetic particles falls into a certain range, the refractive index of the mixture is negative, n < 0, which includes the double negative ( epsilon < 0 and mu < 0) and other cases ( e. g. epsilon < 0 and mu > 0). We finally give the requirements on the microscopic material properties for the ferromagnetic materials to reach the domain wall resonances at high frequencies.

Design of super-resolution filters with a Gaussian beam in optical data storage systems

Super-resolution filters based on a Gaussian beam are proposed to reduce the focusing spot in optical data storage systems. Both of amplitude filters and pure-phase filters are designed respectively to gain the desired intensity distributions. Their performances are analysed and compared with those based on plane wave in detail. The energy utilizations are presented. The simulation results show that our designed super-resolution filters are favourable for use in optical data storage systems in terms of performance and energy utilization.

A feasible approach to optical-electrical hybrid data storage using phase change material

We present our experimental results supporting optical-electrical hybrid data storage by optical recording and electrical reading using Ge2Sb2Te5as recording medium. The sheet resistance of laser- irradiated Ge2Sb2Te5. lms exhibits an abrupt change of four orders of magnitude ( from 10 7 to 10 3./ sq) with increasing laser power, current- voltage curves of the amorphous area and the laser- crystallized dots, measured by a conductive atomic force microscope ( C- AFM), show that their resistivities are 2.725 and 3.375 x 10- 3., respectively, the surface current distribution in the. lms also shows high and low resistance states. All these results suggest that the laser- recorded bit can be read electrically by measuring the change of electrical resistivity, thus making optical electrical hybrid data storage possible.

A Z-scan model for optical nonlinear nanometric films

The Z-scan technique is useful for measuring the nonlinear refractive index of thin films. In conventional Z-scan theories, two effects are often ignored, namely the losses due to the internal multi-interference and the nonlinear absorption inside the sample. Therefore, the theories are restricted to relatively thick films. For films thinner than about 100 nm, the two effects become significant, and thus cannot be ignored. In the present work, we present a Z-scan theory that takes both effects into account. The proposed model calculation is suitable for optical nonlinear films of nanometric thickness. With numerical simulations, we demonstrate dramatic deviations from the conventional Z-scan calculations.

Super-resolution scanning laser microscopy with a third-order optical nonlinear thin film

In a configuration of optical far-field scanning microscopy, super-resolution achieved by inserting a third-order optical nonlinear thin film is demonstrated and analyzed in terms of the frequency response function. Without the thin film the microscopy is diffraction limited; thus, subwavelength features cannot be resolved. With the nonlinear thin film inserted, the resolution is dramatically improved and thus the microscopy resolves features significantly smaller than the smallest spacing allowed by the diffraction limit. A theoretical model is established and the device is analyzed for the frequency response function. The results show that the frequency response function exceeds the cutoff spatial frequency of the microscopy defined by the laser wavelength and the numerical aperture of the convergent lens. The main contribution to the improvement of the cutoff spatial frequency is from the phase change induced by the complex transmission of the nonlinear thin film. Experimental results are presented and are shown to be consistent with the results of theoretical simulations.