Direct-Patterning ZnO Deposition by Atomic-Layer Additive Manufacturing Using a Safe and Economical Precursor.

Area-selective atomic layer deposition (AS-ALD) is a bottom-up nanofabrication method delivering single atoms from a molecular precursor. AS-ALD enables self-aligned fabrication and outperforms lithography in terms of cost, resistance, and equipment prerequisites, but it requires pre-patterned substrates and is limited by insufficient selectivity and finite choice of substrates. These challenges are circumvented by direct patterning with atomic-layer additive manufacturing (ALAM) - a transfer of 3D-printing principles to atomic-layer manufacturing where a precursor supply nozzle enables direct patterning instead of blanket coating. The reduced precursor vapor consumption in ALAM as compared with ALD calls for the use of less volatile precursors by replacing diethylzinc used traditionally in ALD with bis(dimethylaminopropyl)zinc, Zn(DMP)2 . The behavior of this novel ZnO ALAM process follows that of the corresponding ALD in terms of deposit quality and growth characteristics. The temperature window for self-limiting growth of stoichiometric, crystalline material is 200-250 °C. The growth rates are 0.9 Å per cycle in ALD (determined by spectroscopic ellipsometry) and 1.1 Å per pass in ALAM (imaging ellipsometry). The preferential crystal orientation increases with temperature, while energy-dispersive X-ray spectroscopic and XPS show that only intermediate temperatures deliver stoichiometric ZnO. A functional thin-film transistor is created from an ALAM-deposited ZnO line and characterized.

Deep-Red-Emitting Colloidal Quantum Well Light-Emitting Diodes Enabled through a Complex Design of Core/Crown/Double Shell Heterostructure.

Extending the emission peak wavelength of quasi-2D colloidal quantum wells has been an important quest to fully exploit the potential of these materials, which has not been possible due to the complications arising from the partial dissolution and recrystallization during growth to date. Here, the synthetic pathway of (CdSe/CdS)@(1-4 CdS/CdZnS) (core/crown)@(colloidal atomic layer deposition shell/hot injection shell) hetero-nanoplatelets (NPLs) using multiple techniques, which together enable highly efficient emission beyond 700 nm in the deep-red region, is proposed and demonstrated. Given the challenges of using conventional hot injection procedure, a method that allows to obtain sufficiently thick and passivated NPLs as the seeds is developed. Consequently, through the final hot injection shell coating, thick NPLs with superior optical properties including a high photoluminescence quantum yield of 88% are achieved. These NPLs emitting at 701 nm exhibit a full-width-at-half-maximum of 26 nm, enabled by the successfully maintained quasi-2D shape and minimum defects of the resulting heterostructure. The deep-red light-emitting diode (LED) device fabricated with these NPLs has shown to yield a high external quantum efficiency of 6.8% at 701 nm, which is on par with other types of LEDs in this spectral range.

Near-Field Energy Transfer into Silicon Inversely Proportional to Distance Using Quasi-2D Colloidal Quantum Well Donors.

Silicon is the most prevalent material system for light-harvesting applications; however, its inherent indirect bandgap and consequent weak absorption limits its potential in optoelectronics. This paper proposes to address this limitation by combining the sensitization of silicon with extraordinarily large absorption cross sections of quasi-2D colloidal quantum well nanoplatelets (NPLs) and to demonstrate excitation transfer from these NPLs to bulk silicon. Here, the distance dependency, d, of the resulting Förster resonant energy transfer from the NPL monolayer into a silicon substrate is systematically studied by tuning the thickness of a spacer layer (of Al2 O3 ) in between them (varied from 1 to 50 nm in thickness). A slowly varying distance dependence of d-1 with 25% efficiency at a donor-acceptor distance of 20 nm is observed. These results are corroborated with full electromagnetic solutions, which show that the inverse distance relationship emanates from the delocalized electric field intensity across both the NPL layer and the silicon because of the excitation of strong in-plane dipoles in the NPL monolayer. These findings pave the way for using colloidal NPLs as strong light-harvesting donors in combination with crystalline silicon as an acceptor medium for application in photovoltaic devices and other optoelectronic platforms.

Self-Resonant Microlasers of Colloidal Quantum Wells Constructed by Direct Deep Patterning.

Here, the first account of self-resonant fully colloidal µ-lasers made from colloidal quantum well (CQW) solution is reported. A deep patterning technique is developed to fabricate well-defined high aspect-ratio on-chip CQW resonators made of grating waveguides and in-plane reflectors. The fabricated waveguide-coupled laser, enabling tight optical confinement, assures in-plane lasing. CQWs of the patterned layers are closed-packed with sharp edges and residual-free lifted-off surfaces. Additionally, the method is successfully applied to various nanoparticles including colloidal quantum dots and metal nanoparticles. It is observed that the patterning process does not affect the nanocrystals (NCs) immobilized in the attained patterns and the different physical and chemical properties of the NCs remain pristine. Thanks to the deep patterning capability of the proposed method, patterns of NCs with subwavelength lateral feature sizes and micron-scale heights can possibly be fabricated in high aspect ratios.

Optical Microfluidic Waveguides and Solution Lasers of Colloidal Semiconductor Quantum Wells.

The realization of high-quality lasers in microfluidic devices is crucial for numerous applications, including biological and chemical sensors and flow cytometry, and the development of advanced lab-on-chip (LOC) devices. Herein, an ultralow-threshold microfluidic single-mode laser is proposed and demonstrated using an on-chip cavity. CdSe/CdS@Cdx Zn1- x S core/crown@gradient-alloyed shell colloidal semiconductor quantum wells (CQWs) dispersed in toluene are employed in the cavity created inside a poly(dimethylsiloxane) (PDMS) microfluidic device using SiO2 -protected Ag mirrors to achieve in-solution lasing. Lasing from such a microfluidic device having CQWs solution as a microfluidic gain medium is shown for the first time with a record-low optical gain threshold of 17.1 µJ cm- ² and lasing threshold of 68.4 µJ cm- ² among all solution-based lasing demonstrations. In addition, air-stable SiO2 protected Ag films are used and designed to form highly tunable and reflective mirrors required to attain a high-quality Fabry-Pérot cavity. These realized record-low thresholds emanate from the high-quality on-chip cavity together with the core/crown@gradient-alloyed shell CQWs having giant gain cross-section and slow Auger rates. This microfabricated CQW laser provides a compact and inexpensive coherent light source for microfluidics and integrated optics covering the visible spectral region.

Optical Gain in Ultrathin Self-Assembled Bi-Layers of Colloidal Quantum Wells Enabled by the Mode Confinement in their High-Index Dielectric Waveguides.

This study demonstrates an ultra-thin colloidal gain medium consisting of bi-layers of colloidal quantum wells (CQWs) with a total film thickness of 14 nm integrated with high-index dielectrics. To achieve optical gain from such an ultra-thin nanocrystal film, hybrid waveguide structures partly composed of self-assembled layers of CQWs and partly high-index dielectric material are developed and shown: in asymmetric waveguide architecture employing one thin film of dielectric underneath CQWs and in the case of quasi-symmetric waveguide with a pair of dielectric films sandwiching CQWs. Numerical modeling indicates that the modal confinement factor of ultra-thin CQW films is enhanced in the presence of the adjacent dielectric layers significantly. The active slabs of these CQW monolayers in the proposed waveguide structure are constructed with great care to obtain near-unity surface coverage, which increases the density of active particles, and to reduce the surface roughness to sub-nm scale, which decreases the scattering losses. The excitation and propagation of amplified spontaneous emission (ASE) along these active waveguides are experimentally demonstrated and numerically analyzed. The findings of this work offer possibilities for the realization of ultra-thin electrically driven colloidal laser devices, providing critical advantages including single-mode lasing and high electrical conduction.

Thickness-Tunable Self-Assembled Colloidal Nanoplatelet Films Enable Ultrathin Optical Gain Media.

We propose and demonstrate construction of highly uniform, multilayered superstructures of CdSe/CdZnS core/shell colloidal nanoplatelets (NPLs) using liquid interface self-assembly. These NPLs are sequentially deposited onto a solid substrate into slabs having monolayer-precise thickness across tens of cm2 areas. Because of near-unity surface coverage and excellent uniformity, amplified spontaneous emission (ASE) is observed from an uncharacteristically thin film having 6 NPL layers, corresponding to a mere 42 nm thickness. Furthermore, systematic studies on optical gain of these NPL superstructures having thicknesses ranging from 6 to 15 layers revealed the gradual reduction in gain threshold with increasing number of layers, along with a continuous spectral shift of the ASE peak (∼18 nm). These observations can be explained by the change in the optical mode confinement factor with the NPL waveguide thickness and propagation wavelength. This bottom-up construction technique for thickness-tunable, three-dimensional NPL superstructures can be used for large-area device fabrication.