Tailoring Single-Mode Random Lasing of Tin Halide Perovskites Integrated in a Vertical Cavity.

The development of random lasing (RL) with predictable and controlled properties is an important step to make these cheap optical sources stable and reliable. However, the design of tailored RL characteristics (emission energy, threshold, number of modes) is only obtained with complex photonic structures, while the simplest optical configurations able to tune the RL are still a challenge. This work demonstrates the tuning of the RL characteristics in spin-coated and inkjet-printed tin-based perovskites integrated into a vertical cavity with low quality factor. When the cavity mode is resonant with the photoluminescence (PL) peak energy, standard vertical lasing is observed. More importantly, single mode RL operation with the lowest threshold and a quality factor as high as 1 000 (twenty times the quality factor of the resonator) is obtained if the cavity mode lies above the PL peak energy due to higher gain. These results can have important technological implications toward the development of low-cost RL sources without chaotic behavior.

Large-Area, Flexible, Lead-Free Sn-Perovskite Solar Modules.

For the first time, large-area, flexible organic-inorganic tin perovskite solar modules are fabricated by means of an industry-compatible and scalable blade-coating technique. An 8-cell interconnected mini module with dimensions of 25 cm2 (active area = 8 × 1.5 cm2) reached 5.7% power conversion efficiency under 1000 W/m2 (AM 1.5G) and 9.4% under 2000 lx (white-LED).

Inkjet-printed h-BN memristors for hardware security.

Inkjet printing electronics is a growing market that reached 7.8 billion USD in 2020 and that is expected to grow to ∼23 billion USD by 2026, driven by applications like displays, photovoltaics, lighting, and radiofrequency identification. Incorporating two-dimensional (2D) materials into this technology could further enhance the properties of the existing devices and/or circuits, as well as enable the development of new concept applications. Along these lines, here we report an easy and cheap process to synthesize inks made of multilayer hexagonal boron nitride (h-BN)-an insulating 2D layered material-by the liquid-phase exfoliation method and use them to fabricate memristors. The devices exhibit multiple stochastic phenomena that are very attractive for use as entropy sources in electronic circuits for data encryption (physical unclonable functions [PUFs], true random number generators [TRNGs]), such as: (i) a very disperse initial resistance and dielectric breakdown voltage, (ii) volatile unipolar and non-volatile bipolar resistive switching (RS) with a high cycle-to-cycle variability of the state resistances, and (iii) random telegraph noise (RTN) current fluctuations. The clue for the observation of these stochastic phenomena resides on the unpredictable nature of the device structure derived from the inkjet printing process (i.e., thickness fluctuations, random flake orientations), which allows fabricating electronic devices with different electronic properties. The easy-to-make and cheap memristors here developed are ideal to encrypt the information produced by multiple types of objects and/or products, and the versatility of the inkjet printing method, which allows effortless deposition on any substrate, makes our devices especially attractive for flexible and wearable devices within the internet-of-things.

2D PEA2SnI4 Inkjet-Printed Halide Perovskite LEDs on Rigid and Flexible Substrates.

Lead-free PEA2SnI4-based perovskite LEDs are successfully inkjet-printed on rigid and flexible substrates. Red-emitting devices (λmax = 633 nm) exhibit, under ambient conditions, a maximum external quantum efficiency (EQEmax) of 1% with a related brightness of 30 cd/m2 at 10 mA/cm2.

Dielectric function of vanadium oxide thin films by thermal annealing.

The dielectric function of ${{\rm{VO}}_x}$ and ${{\rm{V}}_2}{{\rm{O}}_5}$ thin films is determined with the use of a spectroscopic Mueller matrix ellipsometer from 1.5 to 5.0 eV. The complex dielectric function of the films is calculated using the measured Mueller matrices filtered with the Cloude decomposition. ${{\rm{VO}}_x}$ shows high absorption in the UV region, a Tauc-Lorentz gap around 2.4 eV, and non-vanishing absorption in the visible. ${{\rm{V}}_2}{{\rm{O}}_5}$ shows a high absorption band centered at 2.87 eV, an indirect optical band gap at 1.95 eV, and a direct optical band gap at 2.33 eV. The ellipsometric characterization is supported by Raman, x-ray photoelectron, and photoluminescence spectroscopy.

Advanced Data Encryption ​using 2D Materials.

Advanced data encryption requires the use of true random number generators (TRNGs) to produce unpredictable sequences of bits. TRNG circuits with high degree of randomness and low power consumption may be fabricated by using the random telegraph noise (RTN) current signals produced by polarized metal/insulator/metal (MIM) devices as entropy source. However, the RTN signals produced by MIM devices made of traditional insulators, i.e., transition metal oxides like HfO2 and Al2 O3 , are not stable enough due to the formation and lateral expansion of defect clusters, resulting in undesired current fluctuations and the disappearance of the RTN effect. Here, the fabrication of highly stable TRNG circuits with low power consumption, high degree of randomness (even for a long string of 224  - 1 bits), and high throughput of 1 Mbit s-1 by using MIM devices made of multilayer hexagonal boron nitride (h-BN) is shown. Their application is also demonstrated to produce one-time passwords, which is ideal for the internet-of-everything. The superior stability of the h-BN-based TRNG is related to the presence of few-atoms-wide defects embedded within the layered and crystalline structure of the h-BN stack, which produces a confinement effect that avoids their lateral expansion and results in stable operation.

Amorphous sub-nanometre Tb-doped SiO(x)N(y)/SiO2 superlattices for optoelectronics.

Amorphous sub-nanometre Tb-doped SiOxNy/SiO2 superlattices were fabricated by means of alternating deposition of 0.7 nm thick Tb-doped SiOxNy layers and of 0.9 nm thick SiO2 barrier layers in an electron-cyclotron-resonance plasma enhanced chemical vapour deposition system with in situ Tb-doping capability. High resolution transmission electron microscopy images showed a well-preserved superlattice morphology after annealing at a high temperature of 1000 °C. In addition, transparent indium tin oxide (ITO) electrodes were deposited by electron beam evaporation using a shadow mask approach to allow for the optoelectronic characterization of superlattices. Tb(3+) luminescent spectral features were obtained using three different excitation sources: UV laser excitation (photoluminescence (PL)), under a bias voltage (electroluminescence (EL)) and under a highly energetic electron beam (cathodoluminescence (CL)). All techniques displayed Tb(3+) inner transitions belonging to (5)D4 levels except for the CL spectrum, in which (5)D3 transition levels were also observed. Two competing mechanisms were proposed to explain the spectral differences observed between PL (or EL) and CL excitation: the population rate of the (5)D3 state and the non-radiative relaxation rate of the (5)D3-(5)D4 transition due to a resonant OH-mode. Moreover, the large number of interfaces (trapping sites) that electrons have to get through was identified as the main reason for observing a bulk-limited charge transport mechanism governed by Poole-Frenkel conduction in the J-V characteristic. Finally, a linear EL-J dependence was measured, with independent spectral shape and an EL onset voltage as low as 6.7 V. These amorphous sub-nanometre superlattices are meant to provide low-cost solutions in different areas including sensing, photovoltaics or photonics.

Retrieving the electronic properties of silicon nanocrystals embedded in a dielectric matrix by low-loss EELS.

In this work we apply low-loss electron energy loss spectroscopy (EELS) to probe the structural and electronic properties of single silicon nanocrystals (NCs) embedded in three different dielectric matrices (SiO2, SiC and Si(3)N(4)). A monochromated and aberration corrected transmission electron microscope has been operated at 80 kV to avoid sample damage and to reduce the impact of radiative losses. We present a novel approach to disentangle the electronic features corresponding to pure Si-NCs from the surrounding dielectric material contribution through an appropriate computational treatment of hyperspectral datasets. First, the different material phases have been identified by measuring the plasmon energy. Due to the overlapping of Si-NCs and dielectric matrix information, the variable shape and position of mixed plasmonic features increases the difficulty of non-linear fitting methods to identify and separate the components in the EELS signal. We have managed to solve this problem for silicon oxide and nitride systems by applying multivariate analysis methods that can factorize the hyperspectral datacubes in selected regions. By doing so, the EELS spectra are re-expressed as a function of abundance of Si-NC-like and dielectric-like factors. EELS contributions from the embedded nanoparticles as well as their dielectric surroundings are thus studied in a new light, and compared with the dielectric material and crystalline silicon from the substrate. Electronic properties such as band gaps and plasmon shifts can be obtained by a straightforward examination. Finally, we have calculated the complex dielectric functions and the related electron effective mass and density of valence electrons.

Structural and compositional properties of Er-doped silicon nanoclusters/oxides for multilayered photonic devices studied by STEM-EELS.

High resolution scanning transmission electron microscopy with an aberration corrected and monochromated instrument has been used for the assessment of the silicon-based active layer stack for novel optoelectronic devices. This layer contains a multilayer structure consisting of alternate thin layers of pure silica (SiO2) and silicon-rich silicon oxide (SRO, SiOx). Upon high temperature annealing the SRO sublayer segregates into a Si nanocluster (Si-nc) precipitated phase and a SiO2 matrix. Additionally, erbium (Er) ions have been implanted and used as luminescent centres in order to obtain narrow emission at 1.54 µm. Our study exploits the combination of high angle annular dark field (HAADF) imaging with a sub-nanometer electron probe and electron energy loss spectroscopy (EELS) with an energy resolution below 0.2 eV. The structural and chemical information is obtained from the studied multilayer structure. In addition, the instrumental techniques for calibration, deconvolution, fitting and analysis of the EELS spectra are explained in detail. The spatial distribution of the Si-nanoclusters (Si-ncs) and the SiO2 barriers is accurately delimited in the multilayer. Additionally, the quality of the studied multilayer in terms of composition, roughness and defects is analysed and discussed. Er clusterization has not been observed; even so, blue-shifted plasmon and interband transition energies for silica are measured, in the presence of Er ions and sizable nanometer-size effects.

Structural factors impacting carrier transport and electroluminescence from Si nanocluster-sensitized Er ions.

We present an analysis of factors influencing carrier transport and electroluminescence (EL) at 1.5 µm from erbium-doped silicon-rich silica (SiOx) layers. The effects of both the active layer thickness and the Si-excess content on the electrical excitation of erbium are studied. We demonstrate that when the thickness is decreased from a few hundred to tens of nanometers the conductivity is greatly enhanced. Carrier transport is well described in all cases by a Poole-Frenkel mechanism, while the thickness-dependent current density suggests an evolution of both density and distribution of trapping states induced by Si nanoinclusions. We ascribe this observation to stress-induced effects prevailing in thin films, which inhibit the agglomeration of Si atoms, resulting in a high density of sub-nm Si inclusions that induce traps much shallower than those generated by Si nanoclusters (Si-ncs) formed in thicker films. There is no direct correlation between high conductivity and optimized EL intensity at 1.5 µm. Our results suggest that the main excitation mechanism governing the EL signal is impact excitation, which gradually becomes more efficient as film thickness increases, thanks to the increased segregation of Si-ncs, which in turn allows more efficient injection of hot electrons into the oxide matrix. Optimization of the EL signal is thus found to be a compromise between conductivity and both number and degree of segregation of Si-ncs, all of which are governed by a combination of excess Si content and sample thickness. This material study has strong implications for many electrically-driven devices using Si-ncs or Si-excess mediated EL.

Thickness-dependent optimization of Er3+ light emission from silicon-rich silicon oxide thin films.

This study investigates the influence of the film thickness on the silicon-excess-mediated sensitization of Erbium ions in Si-rich silica. The Er3+ photoluminescence at 1.5 µm, normalized to the film thickness, was found five times larger for films 1 µm-thick than that from 50-nm-thick films intended for electrically driven devices. The origin of this difference is shared by changes in the local density of optical states and depth-dependent interferences, and by limited formation of Si-based sensitizers in "thin" films, probably because of the prevailing high stress. More Si excess has significantly increased the emission from "thin" films, up to ten times. This paves the way to the realization of highly efficient electrically excited devices.

High Q light-emitting Si-rich Si3N4 microdisks.

We report on the optical properties of active silicon (Si)-rich Si3N4 microdisk cavities in the visible range. We have studied the correlation between the quality (Q) factor of the cavities and the active material deposition parameters. Microphotoluminescence measurements revealed subangstrom whispering galley modes resonances and a maximum Q of 104 around 760 nm. These values improve significantly the best results reported so far for Si-based light-emitting circular resonators in the visible range. In contrast to what is reported for Si-rich SiO2-based microcavities, we demonstrate the absence of a spectral widening at high pump fluxes associated to carrier absorption mechanisms, which allows high emitted power without degrading the Q of the cavity. These results open the route toward the monolithic integration of those structures into more complex circuits including Si photodetectors.

Ultrafast all-optical switching in a silicon-nanocrystal-based silicon slot waveguide at telecom wavelengths.

We demonstrate experimentally all-optical switching on a silicon chip at telecom wavelengths. The switching device comprises a compact ring resonator formed by horizontal silicon slot waveguides filled with highly nonlinear silicon nanocrystals in silica. When pumping at power levels about 100 mW using 10 ps pulses, more than 50% modulation depth is observed at the switch output. The switch performs about 1 order of magnitude faster than previous approaches on silicon and is fully fabricated using complementary metal oxide semiconductor technologies.