All-Perovskite Multicomponent Nanocrystal Superlattices.

Nanocrystal superlattices (NC SLs) have long been sought as promising metamaterials, with nanoscale-engineered properties arising from collective and synergistic effects among the constituent building blocks. Lead halide perovskite (LHP) NCs come across as outstanding candidates for SL design, as they demonstrate collective light emission, known as superfluorescence, in single- and multicomponent SLs. Thus far, LHP NCs have only been assembled in single-component SLs or coassembled with dielectric NC building blocks acting solely as spacers between luminescent NCs. Here, we report the formation of multicomponent LHP NC-only SLs, i.e., using only CsPbBr3 NCs of different sizes as building blocks. The structural diversity of the obtained SLs encompasses the ABO6, ABO3, and NaCl structure types, all of which contain orientationally and positionally locked NCs. For the selected model system, the ABO6-type SL, we observed efficient NC coupling and Förster-like energy transfer from strongly confined 5.3 nm CsPbBr3 NCs to weakly confined 17.6 nm CsPbBr3 NCs, along with characteristic superfluorescence features at cryogenic temperatures. Spatiotemporal exciton dynamics measurements reveal that binary SLs exhibit enhanced exciton diffusivity compared to single-component NC assemblies across the entire temperature range (from 5 to 298 K). The observed coherent and incoherent NC coupling and controllable excitonic transport within the solid NC SLs hold promise for applications in quantum optoelectronic devices.

Strong coupling in mechanically flexible free-standing organic membranes.

Strong coupling of a confined optical field to the excitonic or vibronic transitions of a molecular material results in the formation of new hybrid states called polaritons. Such effects have been extensively studied in Fabry-Pèrot microcavity structures where an organic material is placed between two highly reflective mirrors. Recently, theoretical and experimental evidence has suggested that strong coupling can be used to modify chemical reactivity as well as molecular photophysical functionalities. However, the geometry of conventional microcavity structures limits the ability of molecules "encapsulated" in a cavity to interact with their local environment. Here, we fabricate mirrorless organic membranes that utilize the refractive index contrast between the organic active material and its surrounding medium to confine an optical field with Q-factor values up to 33. Using angle-resolved white light reflectivity measurements, we confirm that our structures operate in the strong coupling regime, with Rabi-splitting energies between 60 and 80 meV in the different structures studied. The experimental results are matched by transfer matrix and coupled oscillator models that simulate the various polariton states of the free standing membranes. Our work demonstrates that mechanically flexible and easy-to-fabricate free standing membranes can support strong light-matter coupling, making such simple and versatile structures highly promising for a range of polariton applications.

Boosting the Photoluminescence Efficiency of InAs Nanocrystals Synthesized with Aminoarsine via a ZnSe Thick-Shell Overgrowth.

InAs-based nanocrystals can enable restriction of hazardous substances (RoHS) compliant optoelectronic devices, but their photoluminescence efficiency needs improvement. We report an optimized synthesis of InAs@ZnSe core@shell nanocrystals allowing to tune the ZnSe shell thickness up to seven mono-layers (ML) and to boost the emission, reaching a quantum yield of ≈70% at ≈900 nm. It is demonstrated that a high quantum yield can be attained when the shell thickness is at least ≈3ML. Notably, the photoluminescence lifetimeshows only a minor variation as a function of shell thickness, whereas the Auger recombination time (a limiting aspect in technological applications when fast) slows down from 11 to 38 ps when increasing the shell thickness from 1.5 to 7MLs. Chemical and structural analyses evidence that InAs@ZnSe nanocrystals do not exhibit any strain at the core-shell interface, likely due to the formation of an InZnSe interlayer. This is supported by atomistic modeling, which indicates the interlayer as being composed of In, Zn, Se and cation vacancies, alike to the In2 ZnSe4 crystal structure. The simulations reveal an electronic structure consistent with that of type-I heterostructures, in which localized trap states can be passivated by a thick shell (>3ML) and excitons are confined in the core.

Colloidal Quantum Dot Infrared Lasers Featuring Sub-Single-Exciton Threshold and Very High Gain.

The use of colloidal quantum dots (CQDs) as a gain medium in infrared laser devices has been underpinned by the need for high pumping intensities, very short gain lifetimes, and low gain coefficients. Here, PbS/PbSSe core/alloyed-shell CQDs are employed as an infrared gain medium that results in highly suppressed Auger recombination with a lifetime of 485 ps, lowering the amplified spontaneous emission (ASE) threshold down to 300 µJ cm-2 , and showing a record high net modal gain coefficient of 2180 cm-1 . By doping these engineered core/shell CQDs up to nearly filling the first excited state, a significant reduction of optical gain threshold is demonstrated, measured by transient absorption, to an average-exciton population-per-dot 〈Nth 〉g of 0.45 due to bleaching of the ground state absorption. This in turn have led to a fivefold reduction in ASE threshold at 〈Nth 〉ASE  = 0.70 excitons-per-dot, associated with a gain lifetime of 280 ps. Finally, these heterostructured QDs are used to achieve near-infrared lasing at 1670 nm at a pump fluences corresponding to sub-single-exciton-per-dot threshold (〈Nth 〉Las  = 0.87). This work brings infrared CQD lasing thresholds on par to their visible counterparts, and paves the way toward solution-processed infrared laser diodes.

Flexible, Free-Standing Polymer Membranes Sensitized by CsPbX3 Nanocrystals as Gain Media for Low Threshold, Multicolor Light Amplification.

Lead halide perovskite nanocrystals (NCs) are highly suitable active media for solution-processed lasers in the visible spectrum, owing to the wide tunability of their emission from blue to red via facile ion-exchange reactions. Their outstanding optical gain properties and the suppressed nonradiative recombination losses stem from their defect-tolerant nature. In this work, we demonstrate flexible waveguides combining the transparent, bioplastic, polymer cellulose acetate with green CsPbBr3 or red-emitting CsPb(Br,I)3 NCs in simple solution-processed architectures based on polymer-NC multilayers deposited on polymer micro-slabs. Experiments and simulations indicate that the employment of the thin, free-standing membranes results in confined electrical fields, enhanced by 2 orders of magnitude compared to identical multilayer stacks deposited on conventional, rigid quartz substrates. As a result, the polymer structures exhibit improved amplified emission characteristics under nanosecond excitation, with amplified spontaneous emission (ASE) thresholds down to ∼95 µJ cm-2 and ∼70 µJ cm-2 and high net modal gain up to ∼450 and ∼630 cm-1 in the green and red parts of the spectrum, respectively. The optimized gain properties are accompanied by a notable improvement of the ASE operational stability due to the low thermal resistance of the substrate-less membranes and the intimate thermal contact between the polymer and the NCs. Their application potential is further highlighted by the membrane's ability to sustain dual-color ASE in the green and red parts of the spectrum through excitation by a single UV source, activate underwater stimulated emission, and operate as efficient white light downconverters of commercial blue LEDs, producing high-quality white light emission, 115% of the NTSC color gamut.

Low-Threshold, Highly Stable Colloidal Quantum Dot Short-Wave Infrared Laser enabled by Suppression of Trap-Assisted Auger Recombination.

Pb-chalcogenide colloidal quantum dots (CQDs) are attractive materials to be used as tuneable laser media across the infrared spectrum. However, excessive nonradiative Auger recombination due to the presence of trap states outcompetes light amplification by rapidly annihilating the exciton population, leading to high gain thresholds. Here, a binary blend is employed of CQDs and ZnO nanocrystals in order to passivate the in-gap trap states of PbS-CQD gain medium. Using transient absorption, a fivefold increase is measured in Auger lifetime demonstrating the suppression of trap-assisted Auger recombination. By doing so, a twofold reduction is achieved in amplified spontaneous emission (ASE) threshold. Finally, by integrating the proposed binary blend to a distributed feedback (DFB) resonator, single-mode lasing emission is demonstrated at 1650 nm with a linewidth of 1.23 nm (0.62 meV), operating at a low lasing threshold of ≈385 µJ cm-2 . The Auger suppression in this system has allowed to achieve unprecedented lasing emission stability for a CQD laser with recorded continuous operation of 5 h at room temperature and ambient conditions.

Ultralong-Range Polariton-Assisted Energy Transfer in Organic Microcavities.

Non-radiative energy transfer between spatially-separated molecules in a microcavity can occur when an excitonic state on both molecules are strongly-coupled to the same optical mode, forming so-called "hybrid" polaritons. Such energy transfer has previously been explored when thin-films of different molecules are relatively closely spaced (≈100 nm). In this manuscript, we explore strong-coupled microcavities in which thin-films of two J-aggregated molecular dyes were separated by a spacer layer having a thickness of up to 2 µm. Here, strong light-matter coupling and hybridisation between the excitonic transition is identified using white-light reflectivity and photoluminescence emission. We use steady-state spectroscopy to demonstrate polariton-mediated energy transfer between such coupled states over "mesoscopic distances", with this process being enhanced compared to non-cavity control structures.

Single-Exciton Gain and Stimulated Emission Across the Infrared Telecom Band from Robust Heavily Doped PbS Colloidal Quantum Dots.

Materials with optical gain in the infrared are of paramount importance for optical communications, medical diagnostics, and silicon photonics. The current technology is based either on costly III-V semiconductors that are not monolithic to silicon CMOS technology or Er-doped fiber technology that does not make use of the full fiber transparency window. Colloidal quantum dots (CQDs) offer a unique opportunity as an optical gain medium in view of their tunable bandgap, solution processability, and CMOS compatibility. The 8-fold degeneracy of infrared CQDs based on Pb-chalcogenides has hindered the demonstration of low-threshold optical gain and lasing, at room temperature. We demonstrate room-temperature, infrared, size-tunable, band-edge stimulated emission with a line width of ∼14 meV. Leveraging robust electronic doping and charge-exciton interactions in PbS CQD thin films, we reach a gain threshold at the single exciton regime representing a 4-fold reduction from the theoretical limit of an 8-fold degenerate system, with a net modal gain in excess of 100 cm-1.

Unraveling the Radiative Pathways of Hot Carriers upon Intense Photoexcitation of Lead Halide Perovskite Nanocrystals.

The slowdown of carrier cooling in lead halide perovskites (LHP) may allow the realization of efficient hot carrier solar cells. Much of the current effort focuses on the understanding of the mechanisms that retard the carrier relaxation, while proof-of-principle demonstrations of hot carrier harvesting have started to emerge. Less attention has been placed on the impact that the energy and momentum relaxation slowdown imparts on the spontaneous and stimulated light-emission process. LHP nanocrystals (NCs) provide an ideal testing ground for such studies as they exhibit bright emission and high optical gain, while the carrier cooling bottleneck is further pronounced compared to their bulk analogues due to confinement. Herein, the luminescent properties of CsPbBr3, FAPbBr3, and FAPbI3 NCs in the strong photoexcitation regime are investigated. In the former two NC systems, amplified spontaneous emission is found to dominate over the radiative recombination at average carrier occupancy per nanocrystal larger than 5-10. On the other hand, under the same photoexcitation conditions in the FAPbI3 NCs, a longer lived population of hot carriers results in a competition between hot luminescence, stimulated emission, and defect recombination. The dynamic interplay between the aforementioned three emissive channels appears to be influenced by various experimental and material parameters that include temperature, material purity, film morphology, and excitation pulse width and wavelength.

Core-shell PbS/Sn:In2O3 and branched PbIn2S4/Sn:In2O3 nanowires in quantum dot sensitized solar cells.

Core-shell PbS/Sn:In2O3 and branched PbIn2S4/Sn:In2O3 nanowires have been obtained via the deposition of Pb over Sn:In2O3 nanowires and post growth processing under H2S between 100 °C-200 °C and 300 °C-500 °C respectively. The PbS/Sn:In2O3 nanowires have diameters of 50-250 nm and consist of cubic PbS and In2O3 while the PbIn2S4/Sn:In2O3 nanowires consist of PbIn2S4 branches with diameters of 10-30 nm and an orthorhombic crystal structure. We discuss the growth mechanisms and also show that the density of electrons in the n-type Sn:In2O3 core is strongly dependent on the thickness of the p-type PbS shell, which must be smaller than 30 nm to prevent core depletion, via the self-consistent solution of the Poisson-Schrödinger equations in the effective mass approximation. The PbS/Sn:In2O3 and PbIn2S4/Sn:In2O3 nanowire networks had resistances of 100-200 Ω due to the large carrier densities and exhibited defect related photoluminescence at 2.2 eV and 1.5 eV respectively. We show that PbS in contact with polysulfide electrolyte has ohmic like behavior but the PbS/Sn:In2O3 nanowires gave, rectifying current voltage characteristics as a counter electrode in a quantum dot sensitized solar cell using a conventional ITO/TiO2/CdS/CdSe photo anode, an open circuit voltage of ≈0.5 V, and short circuit current density of ≈1 mA cm-2. In contrast the branched PbIn2S4/Sn:In2O3 nanowires exhibited a higher current carrying capability of ≈7 mA cm-2 and higher power conversion efficiency of ≈2%.

Ultrafast Spectroscopy and Red Emission from ß-Ga2O 3/ß-Ga 2S 3 Nanowires.

Ultrafast pump-probe and transient photoluminescence spectroscopy were used to investigate carrier dynamics in ß-Ga2O3 nanowires converted to ß-Ga2O3/Ga2S3 under H2S between 400 to 600 °C. The ß-Ga2O3 nanowires exhibited broad blue emission with a lifetime of 2.4 ns which was strongly suppressed after processing at 500-600 °C giving rise to red emission centered at 680 nm with a lifetime of 19 µs. Differential absorption spectroscopy reveals that state filling occurs in states located below the conduction band edge before sulfurization, but free carrier absorption is dominant in the ß-Ga2O3/Ga2S3 nanowires processed at 500 to 600 °C for probing wavelengths >500 nm related to secondary excitation of the photo-generated carriers from the mid-gap states into the conduction band of Ga2S3.

Structure, morphology, and photoluminescence of porous Si nanowires: effect of different chemical treatments.

The structure and light-emitting properties of Si nanowires (SiNWs) fabricated by a single-step metal-assisted chemical etching (MACE) process on highly boron-doped Si were investigated after different chemical treatments. The Si nanowires that result from the etching of a highly doped p-type Si wafer by MACE are fully porous, and as a result, they show intense photoluminescence (PL) at room temperature, the characteristics of which depend on the surface passivation of the Si nanocrystals composing the nanowires. SiNWs with a hydrogen-terminated nanostructured surface resulting from a chemical treatment with a hydrofluoric acid (HF) solution show red PL, the maximum of which is blueshifted when the samples are further chemically oxidized in a piranha solution. This blueshift of PL is attributed to localized states at the Si/SiO2 interface at the shell of Si nanocrystals composing the porous SiNWs, which induce an important pinning of the electronic bandgap of the Si material and are involved in the recombination mechanism. After a sequence of HF/piranha/HF treatment, the SiNWs are almost fully dissolved in the chemical solution, which is indicative of their fully porous structure, verified also by transmission electron microscopy investigations. It was also found that a continuous porous Si layer is formed underneath the SiNWs during the MACE process, the thickness of which increases with the increase of etching time. This supports the idea that porous Si formation precedes nanowire formation. The origin of this effect is the increased etching rate at sites with high dopant concentration in the highly doped Si material.

Zn3N2 nanowires: growth, properties and oxidation.

Zinc nitride (Zn3N2) nanowires (NWs) with diameters of 50 to 100 nm and a cubic crystal structure have been grown on 1 nm Au/Al2O3 via the reaction of Zn with NH3 including H2 between 500°C and 600°C. These exhibited an optical band gap of ≈ 3.2 eV, estimated from steady state absorption-transmission spectroscopy. We compared this with the case of ZnO NWs and discussed the surface oxidation of Zn3N2 NWs which is important and is expected to lead to the formation of a Zn3N2/ZnO core-shell NW, the energy band diagram of which was calculated via the self-consistent solution of the Poisson-Schrödinger equations within the effective mass approximation by taking into account a fundamental energy band gap of 1.2 eV. In contrast, only highly oriented Zn3N2 layers with a cubic crystal structure and an optical band gap of ≈ 2.9 eV were obtained on Au/Si(001) using the same growth conditions.

The nitridation of ZnO nanowires.

ZnO nanowires (NWs) with diameters of 50 to 250 nm and lengths of several micrometres have been grown by reactive vapour transport via the reaction of Zn with oxygen on 1 nm Au/Si(001) at 550°C under an inert flow of Ar. These exhibited clear peaks in the X-ray diffraction corresponding to the hexagonal wurtzite crystal structure of ZnO and a photoluminescence spectrum with a peak at 3.3 eV corresponding to band edge emission close to 3.2 eV determined from the abrupt onset in the absorption-transmission through ZnO NWs grown on 0.5 nm Au/quartz. We find that the post growth nitridation of ZnO NWs under a steady flow of NH3 at temperatures ≤600°C promotes the formation of a ZnO/Zn3N2 core-shell structure as suggested by the suppression of the peaks related to ZnO and the emergence of new ones corresponding to the cubic crystal structure of Zn3N2 while maintaining their integrity. Higher temperatures lead to the complete elimination of the ZnO NWs. We discuss the effect of nitridation time, flow of NH3, ramp rate and hydrogen on the conversion and propose a mechanism for the nitridation.

Ultrafast hole carrier relaxation dynamics in p-type CuO nanowires.

Ultrafast hole carrier relaxation dynamics in CuO nanowires have been investigated using transient absorption spectroscopy. Following femtosecond pulse excitation in a non-collinear pump-probe configuration, a combination of non-degenerate transmission and reflection measurements reveal initial ultrafast state filling dynamics independent of the probing photon energy. This behavior is attributed to the occupation of states by photo-generated carriers in the intrinsic hole region of the p-type CuO nanowires located near the top of the valence band. Intensity measurements indicate an upper fluence threshold of 40 µJ/cm2 where carrier relaxation is mainly governed by the hole dynamics. The fast relaxation of the photo-generated carriers was determined to follow a double exponential decay with time constants of 0.4 ps and 2.1 ps. Furthermore, time-correlated single photon counting measurements provide evidence of three exponential relaxation channels on the nanosecond timescale.

Gallium hydride vapor phase epitaxy of GaN nanowires.

Straight GaN nanowires (NWs) with diameters of 50 nm, lengths up to 10 µm and a hexagonal wurtzite crystal structure have been grown at 900°C on 0.5 nm Au/Si(001) via the reaction of Ga with NH3 and N2:H2, where the H2 content was varied between 10 and 100%. The growth of high-quality GaN NWs depends critically on the thickness of Au and Ga vapor pressure while no deposition occurs on plain Si(001). Increasing the H2 content leads to an increase in the growth rate, a reduction in the areal density of the GaN NWs and a suppression of the underlying amorphous (α)-like GaN layer which occurs without H2. The increase in growth rate with H2 content is a direct consequence of the reaction of Ga with H2 which leads to the formation of Ga hydride that reacts efficiently with NH3 at the top of the GaN NWs. Moreover, the reduction in the areal density of the GaN NWs and suppression of the α-like GaN layer is attributed to the reaction of H2 with Ga in the immediate vicinity of the Au NPs. Finally, the incorporation of H2 leads to a significant improvement in the near band edge photoluminescence through a suppression of the non-radiative recombination via surface states which become passivated not only via H2, but also via a reduction of O2-related defects.

An investigation into the conversion of In2O3 into InN nanowires.

Straight In2O3 nanowires (NWs) with diameters of 50 nm and lengths ≥2 µm have been grown on Si(001) via the wet oxidation of In at 850°C using Au as a catalyst. These exhibited clear peaks in the X-ray diffraction corresponding to the body centred cubic crystal structure of In2O3 while the photoluminescence (PL) spectrum at 300 K consisted of two broad peaks, centred around 400 and 550 nm. The post-growth nitridation of In2O3 NWs was systematically investigated by varying the nitridation temperature between 500 and 900°C, flow of NH3 and nitridation times between 1 and 6 h. The NWs are eliminated above 600°C while long nitridation times at 500 and 600°C did not result into the efficient conversion of In2O3 to InN. We find that the nitridation of In2O3 is effective by using NH3 and H2 or a two-step temperature nitridation process using just NH3 and slower ramp rates. We discuss the nitridation mechanism and its effect on the PL.

Femtosecond Carrier Dynamics in In(2)O(3) Nanocrystals.

We have studied carrier dynamics in In(2)O(3) nanocrystals grown on a quartz substrate using chemical vapor deposition. Transient differential absorption measurements have been employed to investigate the relaxation dynamics of photo-generated carriers in In(2)O(3) nanocrystals. Intensity measurements reveal that Auger recombination plays a crucial role in the carrier dynamics for the carrier densities investigated in this study. A simple differential equation model has been utilized to simulate the photo-generated carrier dynamics in the nanocrystals and to fit the fluence-dependent differential absorption measurements. The average value of the Auger coefficient obtained from fitting to the measurements was gamma = 5.9 +/- 0.4 x 10(-31) cm(6) s(-1). Similarly the average relaxation rate of the carriers was determined to be approximately tau = 110 +/- 10 ps. Time-resolved measurements also revealed ~25 ps delay for the carriers to reach deep traps states which have a subsequent relaxation time of approximately 300 ps.

Low Temperature Growth of In2O3and InN Nanocrystals on Si(111) via Chemical Vapour Deposition Based on the Sublimation of NH4Cl in In.

Indium oxide (In2O3) nanocrystals (NCs) have been obtained via atmospheric pressure, chemical vapour deposition (APCVD) on Si(111) via the direct oxidation of In with Ar:10% O2at 1000 °C but also at temperatures as low as 500 °C by the sublimation of ammonium chloride (NH4Cl) which is incorporated into the In under a gas flow of nitrogen (N2). Similarly InN NCs have also been obtained using sublimation of NH4Cl in a gas flow of NH3. During oxidation of In under a flow of O2the transfer of In into the gas stream is inhibited by the formation of In2O3around the In powder which breaks up only at high temperatures, i.e.T > 900 °C, thereby releasing In into the gas stream which can then react with O2leading to a high yield formation of isolated 500 nm In2O3octahedrons but also chains of these nanostructures. No such NCs were obtained by direct oxidation forTG < 900 °C. The incorporation of NH4Cl in the In leads to the sublimation of NH4Cl into NH3and HCl at around 338 °C which in turn produces an efficient dispersion and transfer of the whole In into the gas stream of N2where it reacts with HCl forming primarily InCl. The latter adsorbs onto the Si(111) where it reacts with H2O and O2leading to the formation of In2O3nanopyramids on Si(111). The rest of the InCl is carried downstream, where it solidifies at lower temperatures, and rapidly breaks down into metallic In upon exposure to H2O in the air. Upon carrying out the reaction of In with NH4Cl at 600 °C under NH3as opposed to N2, we obtain InN nanoparticles on Si(111) with an average diameter of 300 nm.

Synthesis of Tin Nitride Sn(x)N(y) Nanowires by Chemical Vapour Deposition.

Tin nitride (Sn(x)N(y)) nanowires have been grown for the first time by chemical vapour deposition on n-type Si(111) and in particular by nitridation of Sn containing NH(4)Cl at 450 degrees C under a steady flow of NH(3). The Sn(x)N(y) nanowires have an average diameter of 200 nm and lengths >/=5 mum and were grown on Si(111) coated with a few nm's of Au. Nitridation of Sn alone, under a flow of NH(3) is not effective and leads to the deposition of Sn droplets on the Au/Si(111) surface which impedes one-dimensional growth over a wide temperature range i.e. 300-800 degrees C. This was overcome by the addition of ammonium chloride (NH(4)Cl) which undergoes sublimation at 338 degrees C thereby releasing NH(3) and HCl which act as dispersants thereby enhancing the vapour pressure of Sn and the one-dimensional growth of Sn(x)N(y) nanowires. In addition to the action of dispersion, Sn reacts with HCl giving SnCl(2) which in turn reacts with NH(3) leading to the formation of Sn(x)N(y) NWs. A first estimate of the band-gap of the Sn(x)N(y) nanowires grown on Si(111) was obtained from optical reflection measurements and found to be approximately 2.6 eV. Finally, intricate assemblies of nanowires were also obtained at lower growth temperatures.