Selective Growth of GaP Crystals on CMOS-Compatible Si Nanotip Wafers by Gas Source Molecular Beam Epitaxy.

Gallium phosphide (GaP) is a III-V semiconductor with remarkable optoelectronic properties, and it has almost the same lattice constant as silicon (Si). However, to date, the monolithic and large-scale integration of GaP devices with silicon remains challenging. In this study, we present a nanoheteroepitaxy approach using gas-source molecular-beam epitaxy for selective growth of GaP islands on Si nanotips, which were fabricated using complementary metal-oxide semiconductor (CMOS) technology on a 200 mm n-type Si(001) wafer. Our results show that GaP islands with sizes on the order of hundreds of nanometers can be successfully grown on CMOS-compatible wafers. These islands exhibit a zinc-blende phase and possess optoelectronic properties similar to those of a high-quality epitaxial GaP layer. This result marks a notable advancement in the seamless integration of GaP-based devices with high scalability into Si nanotechnology and integrated optoelectronics.

Mixed Organic Cations Promote Ambient Light-Induced Formation of Metallic Lead in Lead Halide Perovskite Crystals.

One major concern toward the performance and stability of halide perovskite-based optoelectronic devices is the formation of metallic lead that promotes nonradiative recombination of charge carriers. The origin of metallic lead formation is being disputed whether it occurs during the perovskite synthesis or only after light, electron, or X-ray beam irradiation or thermal annealing. Here, we show that the quantity of metallic lead detected in perovskite crystals depends on the concentration and composition of the precursor solution. Through a controlled crystallization process, we grew black-colored mixed dimethylammonium (DMA)/methylammonium (MA) lead tribromide crystals. The black color is suggested to be due to the presence of small lead clusters. Despite the unexpected black coloring, the crystals show higher crystallinity and less defect density with respect to the standard yellow-colored DMA/MAPbBr3 crystals, as indicated by X-ray rocking curve and dark current measurements, respectively. While the formation of metallic lead could still be induced by external factors, the precursor solution composition and concentration can facilitate the formation of metallic lead during the crystallization process. Our results indicate that additional research is required to fully understand the perovskite precursor solution chemistry.

Strongly enhanced sensitivities of CMOS compatible plasmonic titanium nitride nanohole arrays for refractive index sensing under oblique incidence.

Titanium nitride (TiN) is a complementary metal-oxide-semiconductor (CMOS) compatible material with large potential for the fabrication of plasmonic structures suited for device integration. However, the comparatively large optical losses can be detrimental for application. This work reports a CMOS compatible TiN nanohole array (NHA) on top of a multilayer stack for potential use in integrated refractive index sensing with high sensitivities at wavelengths between 800 and 1500 nm. The stack, consisting of the TiN NHA on a silicon dioxide (SiO2) layer with Si as substrate (TiN NHA/SiO2/Si), is prepared using an industrial CMOS compatible process. The TiN NHA/SiO2/Si shows Fano resonances in reflectance spectra under oblique excitation, which are well reproduced by simulation using both finite difference time domain (FDTD) and rigorous coupled-wave analysis (RCWA) methods. The sensitivities derived from spectroscopic characterizations increase with the increasing incident angle and match well with the simulated sensitivities. Our systematic simulation-based investigation of the sensitivity of the TiN NHA/SiO2/Si stack under varied conditions reveals that very large sensitivities up to 2305 nm per refractive index unit (nm RIU-1) are predicted when the refractive index of superstrate is similar to that of the SiO2 layer. We analyze in detail how the interplay between plasmonic and photonic resonances such as surface plasmon polaritons (SPPs), localized surface plasmon resonances (LSPRs), Rayleigh Anomalies (RAs), and photonic microcavity modes (Fabry-Pérot resonances) contributes to this result. This work not only reveals the tunability of TiN nanostructures for plasmonic applications but also paves the way to explore efficient devices for sensing in broad conditions.

Quantitative protein sensing with germanium THz-antennas manufactured using CMOS processes.

The development of a CMOS manufactured THz sensing platform could enable the integration of state-of-the-art sensing principles with the mixed signal electronics ecosystem in small footprint, low-cost devices. To this aim, in this work we demonstrate a label-free protein sensing platform using highly doped germanium plasmonic antennas realized on Si and SOI substrates and operating in the THz range of the electromagnetic spectrum. The antenna response to different concentrations of BSA shows in both cases a linear response with saturation above 20 mg/mL. Ge antennas on SOI substrates feature a two-fold sensitivity as compared to conventional Si substrates, reaching a value of 6 GHz/(mg/mL), which is four-fold what reported using metal-based metamaterials. We believe that this result could pave the way to a low-cost lab-on-a-chip biosensing platform.

Tailoring Photoluminescence by Strain-Engineering in Layered Perovskite Flakes.

Strain is an effective strategy to modulate the optoelectronic properties of 2D materials, but it has been almost unexplored in layered hybrid organic-inorganic metal halide perovskites (HOIPs) due to their complex band structure and mechanical properties. Here, we investigate the temperature-dependent microphotoluminescence (PL) of 2D (C6H5CH2CH2NH3)2Cs3Pb4Br13 HOIP subject to biaxial strain induced by a SiO2 ring platform on which flakes are placed by viscoelastic stamping. At 80 K, we found that a strain of <1% can change the PL emission from a single peak (unstrained) to three well-resolved peaks. Supported by micro-Raman spectroscopy, we show that the thermomechanically generated strain modulates the bandgap due to changes in the octahedral tilting and lattice expansion. Mechanical simulations demonstrate the coexistence of tensile and compressive strain along the flake. The observed PL peaks add an interesting feature to the rich phenomenology of photoluminescence in 2D HOIPs, which can be exploited in tailored sensing and optoelectronic devices.

Vibrational Properties in Highly Strained Hexagonal Boron Nitride Bubbles.

Hexagonal boron nitride (hBN) is widely used as a protective layer for few-atom-thick crystals and heterostructures (HSs), and it hosts quantum emitters working up to room temperature. In both instances, strain is expected to play an important role, either as an unavoidable presence in the HS fabrication or as a tool to tune the quantum emitter electronic properties. Addressing the role of strain and exploiting its tuning potentiality require the development of efficient methods to control it and of reliable tools to quantify it. Here we present a technique based on hydrogen irradiation to induce the formation of wrinkles and bubbles in hBN, resulting in remarkably high strains of ∼2%. By combining infrared (IR) near-field scanning optical microscopy and micro-Raman measurements with numerical calculations, we characterize the response to strain for both IR-active and Raman-active modes, revealing the potential of the vibrational properties of hBN as highly sensitive strain probes.

Mixed Dimethylammonium/Methylammonium Lead Halide Perovskite Crystals for Improved Structural Stability and Enhanced Photodetection.

The solvent acidolysis crystallization technique is utilized to grow mixed dimethylammonium/methylammonium lead tribromide (DMA/MAPbBr3 ) crystals reaching the highest dimethylammonium incorporation of 44% while maintaining the 3D cubic perovskite phase. These mixed perovskite crystals show suppression of the orthorhombic phase and a lower tetragonal-to-cubic phase-transition temperature compared to MAPbBr3 . A distinct behavior is observed in the temperature-dependent photoluminescence properties of MAPbBr3 and mixed DMA/MAPbBr3 crystals due to the different organic cation dynamics governing the phase transition(s). Furthermore, lateral photodetectors based on these crystals show that, at room temperature, the mixed crystals possess higher detectivity compared to MAPbBr3 crystals caused by structural compression and reduced surface trap density. Remarkably, the mixed-crystal devices exhibit large enhancement in their detectivity below the phase-transition temperature (at 200 K), while for the MAPbBr3 devices only insignificant changes are observed. The high detectivity of the mixed crystals makes them attractive for visible-light communication and for space applications. The results highlight the importance of the synthetic technique for compositional engineering of halide perovskites that governs their structural and optoelectronic properties.

Mechanical switching of orientation-related photoluminescence in deep-blue 2D layered perovskite ensembles.

The synergy between the organic component of two-dimensional (2D) metal halide layered perovskites and flexible polymers offers an unexplored window to tune their optical properties at low mechanical stress. Thus, there is a significant interest in exploiting their PL anisotropy by controlling their orientation and elucidating their interactions. Here, we apply this principle to platelet structures of micrometre lateral size that are synthesized in situ into free-standing polymer films. We study the photoluminescence of the resulting films under cyclic mechanical stress and observe an enhancement in the emission intensity up to ∼2.5 times along with a switch in the emission profile when stretching the films from 0% to 70% elongation. All the films recovered their initial emission intensity when releasing the stress throughout ca. 15 mechanical cycles. We hypothesize a combined contribution from reduced reabsorption, changes on in-plane and out-of-plane dipole moments that stem from different orientation of the platelets inside the film, and relative sliding of platelets within oriented stacks while stretching the films. Our results reveal how low-mechanical stress affects 2D layered perovskite aggregation and orientation, an open pathway toward the design of strain-controlled emission.

Phase Transitions in Low-Dimensional Layered Double Perovskites: The Role of the Organic Moieties.

Halide double perovskites are an interesting alternative to Pb-containing counterparts as active materials in optoelectronic devices. Low-dimensional double perovskites are fabricated by introducing large organic cations, resulting in organic/inorganic architectures with one or more inorganic octahedra layers separated by organic cations. Here, we synthesized layered double perovskites based on 3D Cs2AgBiBr6, consisting of double (2L) or single (1L) inorganic octahedra layers, using ammonium cations of different sizes and chemical structures. Temperature-dependent Raman spectroscopy revealed phase transition signatures in both inorganic lattice and organic moieties by detecting variations in their vibrational modes. Changes in the conformational arrangement of the organic cations to an ordered state coincided with a phase transition in the 1L systems with the shortest ammonium moieties. Significant changes of photoluminescence intensity observed around the transition temperature suggest that optical properties may be affected by the octahedral tilts emerging at the phase transition.

Author Correction: Graphene Plasmonic Fractal Metamaterials for Broadband Photodetectors.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Nanocrystals of Lead Chalcohalides: A Series of Kinetically Trapped Metastable Nanostructures.

We report the colloidal synthesis of a series of surfactant-stabilized lead chalcohalide nanocrystals. Our work is mainly focused on Pb4S3Br2, a chalcohalide phase unknown to date that does not belong to the ambient-pressure PbS-PbBr2 phase diagram. The Pb4S3Br2 nanocrystals herein feature a remarkably narrow size distribution (with a size dispersion as low as 5%), a good size tunability (from 7 to ∼30 nm), an indirect bandgap, photoconductivity (responsivity = 4 ± 1 mA/W), and stability for months in air. A crystal structure is proposed for this new material by combining the information from 3D electron diffraction and electron tomography of a single nanocrystal, X-ray powder diffraction, and density functional theory calculations. Such a structure is closely related to that of the recently discovered high-pressure chalcohalide Pb4S3I2 phase, and indeed we were able to extend our synthesis scheme to Pb4S3I2 colloidal nanocrystals, whose structure matches the one that has been published for the bulk. Finally, we could also prepare nanocrystals of Pb3S2Cl2, which proved to be a structural analogue of the recently reported bulk Pb3Se2Br2 phase. It is remarkable that one high-pressure structure (for Pb4S3I2) and two metastable structures that had not yet been reported (for Pb4S3Br2 and Pb3S2Cl2) can be prepared on the nanoscale by wet-chemical approaches. This highlights the important role of colloidal chemistry in the discovery of new materials and motivates further exploration into metal chalcohalide nanocrystals.

Graphene Plasmonic Fractal Metamaterials for Broadband Photodetectors.

Metamaterials have recently established a new paradigm for enhanced light absorption in state-of-the-art photodetectors. Here, we demonstrate broadband, highly efficient, polarization-insensitive, and gate-tunable photodetection at room temperature in a novel metadevice based on gold/graphene Sierpinski carpet plasmonic fractals. We observed an unprecedented internal quantum efficiency up to 100% from the near-infrared to the visible range with an upper bound of optical detectivity of 1011 Jones and a gain up to 106, which is a fingerprint of multiple hot carriers photogenerated in graphene. Also, we show a 100-fold enhanced photodetection due to highly focused (up to a record factor of |E/E0| ≈ 20 for graphene) electromagnetic fields induced by electrically tunable multimodal plasmons, spatially localized in self-similar fashion on the metasurface. Our findings give direct insight into the physical processes governing graphene plasmonic fractal metamaterials. The proposed structure represents a promising route for the realization of a broadband, compact, and active platform for future optoelectronic devices including multiband bio/chemical and light sensors.

Temperature-Driven Transformation of CsPbBr3 Nanoplatelets into Mosaic Nanotiles in Solution through Self-Assembly.

Two-dimensional colloidal halide perovskite nanocrystals are promising materials for light-emitting applications. Recent studies have focused on nanoplatelets that are able to self-assemble and transform on solid substrates. However, the mechanism behind the process and the atomic arrangement of their assemblies remain unclear. Here, we present a detailed analysis of the transformation of self-assembled stacks of CsPbBr3 nanoplatelets in solution over a period of a few months by using ex situ transmission electron microscopy and surface analysis. We demonstrate that the transformation mechanism can be understood as oriented attachment, proceeding through the following steps: (i) desorption of the ligands from the surfaces of the particles, causing the seamless atomic merging of nanoplatelet stacks into nanobelts; (ii) merging of neighboring nanobelts that form more extended nanoplates; and (iii) attachment of nanobelts and nanoplates, forming objects with an atomic structure that resembles a mosaic made of broken nanotiles. We reveal that aged nanobelts and nanoplates, which are mainly stabilized by amine/ammonium ions, link through a bilayer of CsBr, with the atomic columns of neighboring perovskite lattices shifted by a half-unit-cell, forming Ruddlesden-Popper planar faults. We also show, via in situ monitoring of the nanocrystal photoluminescence combined with transmission electron microscopy analysis, that the transformation is temperature driven and that it can take place within tens of minutes in solution and in spin-coated films. Understanding this process gives crucial information for the design and fabrication of perovskite materials, where control over the type and density of defects is desired, stimulating the development of perovskite nanocrystal structures with tailored electronic properties.

Nano- and microscale apertures in metal films fabricated by colloidal lithography with perovskite nanocrystals.

We demonstrate patterning of metal surfaces based on lift-off of perovskite nanocrystals that enables the fabrication of nanometer-size features without the use of resist-based nanolithography. The perovskite nanocrystals act as templates for defining the shape of the apertures in metal layers, and we exploit the variety of sizes and shapes that can be controlled in the colloidal synthesis to demonstrate the fabrication of nanoholes, nanogaps and guides with size smaller than the wavelength of light in the visible spectrum. The process can be readily integrated with standard lithography and etching techniques for the creation of more complex structures.

Metastable CdTe@HgTe Core@Shell Nanostructures Obtained by Partial Cation Exchange Evolve into Sintered CdTe Films Upon Annealing.

Partial Hg2+ → Cd2+ cation exchange (CE) reactions were exploited to transform colloidal CdTe nanocrystals (NCs, 4-6 nm in size) into CdTe@HgTe core@shell nanostructures. This was achieved by working under a slow CE rate, which limited the exchange to the surface of the CdTe NCs. In such nanostructures, when annealed at mild temperatures (as low as 200 °C), the HgTe shell sublimated or melted and the NCs sintered together, with the concomitant desorption of their surface ligands. At the end of this process, the annealed samples consisted of ligand-free CdTe sintered films containing an amount of Hg2+ that was much lower than that of the starting CdTe@HgTe NCs. For example, the CdTe@HgTe NCs that initially contained 10% of Hg2+, after being annealed at 200 °C were transformed to CdTe sintered films containing only traces of Hg2+ (less than 1%). This procedure was then used to fabricate a proof-of-concept CdTe-based photodetector exhibiting a photoresponse of up to 0.5 A/W and a detectivity of ca. 9 × 104 Jones under blue light illumination. Our strategy suggests that CE protocols might be exploited to lower the overall costs of production of CdTe thin films employed in photovoltaic technology, which are currently fabricated at high temperatures (above 350 °C), using post-process ligand-stripping steps.

Extending the Colloidal Transition Metal Dichalcogenide Library to ReS2 Nanosheets for Application in Gas Sensing and Electrocatalysis.

Among the large family of transition metal dichalcogenides, recently ReS2 has stood out due to its nearly layer-independent optoelectronic and physicochemical properties related to its 1T distorted octahedral structure. This structure leads to strong in-plane anisotropy, and the presence of active sites at its surface makes ReS2 interesting for gas sensing and catalysts applications. However, current fabrication methods use chemical or physical vapor deposition (CVD or PVD) processes that are costly, time-consuming and complex, therefore limiting its large-scale production and exploitation. To address this issue, a colloidal synthesis approach is developed, which allows the production of ReS2 at temperatures below 360 °C and with reaction times shorter than 2h. By combining the solution-based synthesis with surface functionalization strategies, the feasibility of colloidal ReS2 nanosheet films for sensing different gases is demonstrated with highly competitive performance in comparison with devices built with CVD-grown ReS2 and MoS2 . In addition, the integration of the ReS2 nanosheet films in assemblies together with carbon nanotubes allows to fabricate electrodes for electrocatalysis for H2 production in both acid and alkaline conditions. Results from proof-of-principle devices show an electrocatalytic overpotential competitive with devices based on ReS2 produced by CVD, and even with MoS2 , WS2 , and MoSe2 electrocatalysts.

CsPbX3/SiOx (X = Cl, Br, I) monoliths prepared via a novel sol-gel route starting from Cs4PbX6 nanocrystals.

We developed a facile synthesis of nanocomposite powders of CsPbX3 nanocrystals (NCs) embedded in silica. The synthesis starts from colloidal Cs4PbX6 NCs that are mixed with tetraethyl orthosilicate in the presence of nitric acid, which triggers the sol-gel reaction yielding the formation of SiOx and the conversion of starting NCs into CsPbX3 ones. The overall reaction delivers CsPbX3 NCs encased in a silica matrix. The resulting CsPbX3/SiOx nano-composite powders exhibited enhanced moisture and thermal stability in air. Also, when mixing different CsPbX3/SiOx samples having diverse anion compositions, no interparticle anion exchange processes were observed, which is a further indication that the silica matrix acts as a robust barrier surrounding the NCs. Finallly, we used these composites as down-converter phosphors on top of a blue light-emitting diode (LED), delivering nearly ideal white light emission with the Commission Internationale de l'Eclairage (CIE) color coordinates (0.32, 0.33).

Planar Aperiodic Arrays as Metasurfaces for Optical Near-Field Patterning.

Plasmonic metasurfaces have spawned the field of flat optics using nanostructured planar metallic or dielectric surfaces that can replace bulky optical elements and enhance the capabilities of traditional far-field optics. Furthermore, the potential of flat optics can go far beyond far-field modulation and can be exploited for functionality in the near-field itself. Here, we design metasurfaces based on aperiodic arrays of plasmonic Au nanostructures for tailoring the optical near-field in the visible and near-infrared spectral range. The basic element of the arrays is a rhomboid that is modulated in size, orientation, and position to achieve the desired functionality of the micron-size metasurface structure. Using two-photon-photoluminescence as a tool to probe the near-field profiles in the plane of the metasurfaces, we demonstrate the molding of light into different near-field intensity patterns and active pattern control via the far-field illumination. Finite element method simulations reveal that the near-field modulation occurs via a combination of the plasmonic resonances of the rhomboids and field enhancement in the nanoscale gaps in between the elements. This approach enables optical elements that can switch the near-field distribution across the metasurface via wavelength and polarization of the incident far-field light and provides pathways for light matter interaction in integrated devices.

Simple fabrication of layered halide perovskite platelets and enhanced photoluminescence from mechanically exfoliated flakes.

Rapid progress on the fabrication of lead halide perovskite crystals has led to highly promising performance in optoelectronic devices, particularly from three-dimensional crystals. Recently, these efforts have been extended to layered perovskite structures, motivated in part by their good environmental stability. Furthermore, layered perovskites represent a nanocrystal system with micron-size extensions and strong confinement in one dimension that is highly appealing for studying fundamental photophysics. Here, we report a facile route for the growth of single-layered perovskite platelets, which is demonstrated using four different organic cations acting as spacers, providing a layer interdistance from approx. 1.3 nm to 2.4 nm. The resulting ensembles of platelets exhibit a strong emission band in the deep blue spectral region characterized by two emission peaks and a photoluminescence quantum yield (PLQY) up to 15%. Thin 2D layered perovskite flakes can be readily obtained by mechanical exfoliation, and their emission shows a PLQY as high as 42%, which can be related to reduced reabsorption in the exfoliated crystals. Furthermore, the low energy peak that was observed in the double peak emission from the platelet ensembles is suppressed in the exfoliated flakes. Therefore, the exfoliated flakes manifest a more colour-pure blue emission with strongly increased radiative rate as compared to the dried platelet aggregates obtained directly from the synthesis. The straightforward fabrication strategy that employs solely polar solvents with low environmental impact provides a highly appealing route towards two-dimensional perovskite systems with bright and stable emission in the blue spectral range.

Revealing Photoluminescence Modulation from Layered Halide Perovskite Microcrystals upon Cyclic Compression.

Halide perovskites show promise for high-efficiency solar energy conversion and light-emitting diode devices owing to their bandgap, which falls within the visible optical range. However, due to their rigidity, GPa pressures are necessary to control the complex interplay between their electronic and crystallographic structure. Layered perovskites are likely to be controlled using much lower pressures by exploiting the optical anisotropy of the embedded organic molecules in the structure. This work introduces layered perovskite microplatelets and demonstrates the extreme sensitivity of their emission to cyclic mechanical loading in the range of tens of MPa. A drastic change in their emission is observed in situ, from near-white to an enhanced blue color. This process is reversible, as is evident from a hysteresis loop in the photoluminescence (PL) intensity of the microplatelets. A combination of experimental analysis and computational modelling shows that such behavior cannot be attributed to changes in the crystallographic structure of the flakes. Instead, it suggests that, thanks to their structural anisotropy, microplate alignment and reorientation are responsible for the observed PL modulation. The possibility to tune the optical emission of layered perovskite crystals via low pressures makes them highly interesting as active materials in applications where stress sensing or light modulation is desired.