Rapid, Micron-Resolution 3D Printing of Nd:YAG Ceramic with Optical Gain.

Polycrystalline yttrium aluminum garnet (YAG) ceramic doped with neodymium (Nd), referred to as Nd:YAG, is widely used in solid-state lasers. However, conventional powder metallurgy methods suffer from expenses, time consumption, and limitations in customizing structures. This study introduces a novel approach for creating Nd:YAG ceramics with 3D free-form structures from micron (∼70 µm) to centimeter scales. Firstly, sol-gel synthesis is employed to form photocurable colloidal solutions. Subsequently, by utilizing a home-built micro-continuous liquid interface printing process, precursors are printed into 3D poly(acrylic acid) hydrogels containing yttrium, aluminum, and neodymium hydroxides, with a resolution of 5.8 µm pixel-1 at a speed of 10 µm s-1. After the hydrogels undergo thermal dehydration, debinding, and sintering, polycrystalline Nd:YAG ceramics featuring distinguishable grains are successfully produced. By optimizing the concentrations of the sintering aids (tetraethyl orthosilicate) and neodymium trichloride (NdCl3), the resultant samples exhibit satisfactory photoluminescence, emitting light concentrated at 1064 nm when stimulated by a 532 nm laser. Additionally, Nd:YAG ceramics with various 3D geometries (e.g., cone, spiral, and angled pillar) are printed and characterized, which demonstrates the potential for applications, such as laser and amplifier fibers, couplers, and splitters in optical circuits, as well as gain metamaterials or metasurfaces.

Two-Dimensional Electron-Hole Plasma in Colloidal Quantum Shells Enables Integrated Lasing Continuously Tunable in the Red Spectrum.

Combining integrated optical platforms with solution-processable materials offers a clear path toward miniaturized and robust light sources, including lasers. A limiting aspect for red-emitting materials remains the drop in efficiency at high excitation density due to non-radiative quenching pathways, such as Auger recombination. Next to this, lasers based on such materials remain ill characterized, leaving questions about their ultimate performance. Here, we show that colloidal quantum shells (QSs) offer a viable solution for a processable material platform to circumvent these issues. We first show that optical gain in QSs is mediated by a 2D plasma state of unbound electron-hole pairs, opposed to bound excitons, which gives rise to broad-band and sizable gain across the full red spectrum with record gain lifetimes and a low threshold. Moreover, at high excitation density, the emission efficiency of the plasma state does not quench, a feat we can attribute to an increased radiative recombination rate. Finally, QSs are integrated on a silicon nitride platform, enabling high spectral contrast, surface emitting, and TE-polarized lasers with ultranarrow beam divergence across the entire red spectrum from a small surface area. Our results indicate QS materials are an excellent materials platform to realize highly performant and compact on-chip light sources.

A PDMS-encapsulated cylindrical non-closed-packed photonic crystals composite with Bragg-enhanced Fresnel reflectance for optical gain and spectral selection.

According to the Fresnel theory, the reflectivity intensity of spherical and cylindrical convex surfaces decreases from their edge to center, and it is noteworthy and interesting for optical gain to study the enhancement of center reflectance. In this paper, a polydimethylsiloxane (PDMS) - encapsulated cylindrical non-closed-packed photonic crystals (NPCs) composite with Bragg-enhanced Fresnel reflectance was designed for spectral selectivity and optical gain. Theoretically and experimentally, the periodically ordered structure of NPCs achieved high-reflection of light in photonic bandgap and high-transmission in other bands, which enhanced Fresnel reflectivity of the convex center to specific bands. Furtherly, the cylindrical NPCs hydrogel with stretchability was applied for the dynamic tuning of optical signals. The reflection peak of the PDMS-encapsulated cylindrical NPCs composite blue-shifted from 608 nm to 413 nm with 50 % tensile strain and achieved a rapid transition of structural color from orange to blue-violet in 60 cycles. The new kind of photonic crystals composite for optical gain and spectral selection broke through the limitations of traditional Fresnel curved mirrors with the lowest central reflectivity and inability to perform spectral selectivity, and have great significance and application prospects in fields of signal transmission, optical measurement, and instrument design.

"Giant" Colloidal Quantum Well Heterostructures of CdSe@CdS Core@Shell Nanoplatelets from 9.5 to 17.5 Monolayers in Thickness Enabling Ultra-High Gain Lasing.

Semiconductor colloidal quantum wells (CQWs) have emerged as a promising class of gain materials to be used in colloidal lasers. Although low gain thresholds are achieved, the required high gain coefficient levels are barely met for the applications of electrically-driven lasers which entails a very thin gain matrix to avoid charge injection limitations. Here, "giant" CdSe@CdS colloidal quantum well heterostructures of 9.5 to 17.5 monolayers (ML) in total with corresponding vertical thickness from 3.0 to 5.8 nm that enable record optical gain is shown. These CQWs achieve ultra-high material gain coefficients up to ≈140 000 cm-1 , obtained by systematic variable stripe length (VSL) measurements and independently validated by transient absorption (TA) measurements, owing to their high number of states. This exceptional gain capacity is an order of magnitude higher than the best levels reported for the colloidal quantum dots. From the dispersion of these quantum wells, low threshold amplified spontaneous emission in water providing an excellent platform for optofluidic lasers is demonstrated. Also, employing these giant quantum wells, whispering gallery mode (WGM) lasing with an ultra-low threshold of 8 µJ cm-2 is demonstrated. These findings indicate that giant CQWs offer an exceptional platform for colloidal thin-film lasers and in-solution lasing applications.

Amplified Spontaneous Emission from Electron-Hole Quantum Droplets in Colloidal CdSe Nanoplatelets.

Two-dimensional cadmium selenide nanoplatelets (NPLs) exhibit large absorption cross sections and homogeneously broadened band-edge transitions that offer utility in wide-ranging optoelectronic applications. Here, we examine the temperature-dependence of amplified spontaneous emission (ASE) in 4- and 5-monolayer thick NPLs and show that the threshold for close-packed (neat) films decreases with decreasing temperature by a factor of 2-10 relative to ambient temperature owing to extrinsic (trapping) and intrinsic (phonon-derived line width) factors. Interestingly, for pump intensities that exceed the ASE threshold, we find development of intense emission to lower energy in particular provided that the film temperature is ≤200 K. For NPLs diluted in an inert polymer, both biexcitonic ASE and low-energy emission are suppressed, suggesting that described neat-film observables rely upon high chromophore density and rapid, collective processes. Transient emission spectra reveal ultrafast red-shifting with the time of the lower energy emission. Taken together, these findings indicate a previously unreported process of amplified stimulated emission from polyexciton states that is consistent with quantum droplets and constitutes a form of exciton condensate. For studied samples, quantum droplets form provided that roughly 17 meV or less of thermal energy is available, which we hypothesize relates to polyexciton binding energy. Polyexciton ASE can produce pump-fluence-tunable red-shifted ASE even 120 meV lower in energy than biexciton ASE. Our findings convey the importance of biexciton and polyexciton populations in nanoplatelets and show that quantum droplets can exhibit light amplification at significantly lower photon energies than biexcitonic ASE.

Boosting the Downconversion Luminescence of Tm3+-Doped Nanoparticles for S-Band Polymer Waveguide Amplifier.

Polymer waveguide devices have attracted increasing interest in several rapidly developing areas of broadband communications since they are easily adaptable to on-chip integration and promise low propagation losses. As a key member of the waveguide gain medium, lanthanide doped nanoparticles have been intensively studied to improve the downconversion luminescence. However, current research efforts are almost confined to erbium-doped nanoparticles and amplifiers operating at the C-band; boosting the downconversion luminescence of Tm3+ for S-band optical amplification still remains a challenge. Here we report a Tb3+-induced deactivation control to enhance Tm3+ downconversion luminescence in a stoichiometric Yb lattice without suffering from concentration quenching. We also demonstrate their potential application in an S-band waveguide amplifier and record a maximum optical gain of 18 dB at 1464 nm. Our findings provide valuable insights into the fundamental understanding of deactivation-controlled luminescence enhancement and open up a new avenue toward the development of an S-band polymer waveguide amplifier with high gain.

Two-Color Amplified Spontaneous Emission from Auger-Suppressed Quantum Dots in Liquids.

Colloidal quantum-dot (QD) lasing is normally achieved in close-packed solid-state films, as a high QD volume fraction is required for stimulated emission to outcompete fast Auger decay of optical-gain-active multiexciton states. Here a new type of liquid optical-gain medium is demonstrated, in which compact compositionally-graded QDs (ccg-QDs) that feature strong suppression of Auger decay are liquefied using a small amount of solvent. Transient absorption measurements of ccg-QD liquid suspensions reveal broad-band optical gain spanning a wide spectral range from 560 (green) to 675 nm (red). The gain magnitude is sufficient to realize a two-color amplified spontaneous emission (ASE) at 637 and 594 nm due to the band-edge (1S) and the excited-state (1P) transition, respectively. Importantly, the ASE regime is achieved using quasicontinuous excitation with nanosecond pulses. Furthermore, the ASE is highly stable under prolonged excitation, which stands in contrast to traditional dyes that exhibit strong degradation under identical excitation conditions. These observations point toward a considerable potential of high-density ccg-QD suspensions as liquid, dye-like optical gain media that feature readily achievable spectral tunability and stable operation under intense photoexcitation.

Long-Lived and Bright Biexcitons in Quantum Dots with Parabolic Band Potentials.

Multiple exciton physics in semiconductor nanocrystals play an important role in optoelectronic devices. This work investigates radially alloyed CdZnSe/CdS nanocrystals with suppressed Auger recombination due to the spatial separation of carriers, which also underpins their performance in optical gain and scintillation experiments. Due to suppressed Auger recombination, the biexciton lifetime is greater than 10 ns, much longer than most nanocrystals. The samples show optical gain, amplified spontaneous emission, and lasing at thresholds <2 excitons per particle. They also show broad gain bandwidth (>500 meV) encompassing 4 amplified spontaneous emission bands. Similarly enabled by slowed multiple exciton relaxation, the samples display strong performance in scintillating films under X-ray illumination. The CdZnSe/CdS samples have fast radioluminescence rise (<80 ps) and decay times (<5 ns), light yields up to 6700 photons·MeV-1, and the demonstrated capacity for incorporation into large area films for scintillation imaging.

Aggregation-Induced Stimulated Emission of 100% Dye Microspheres.

Dyes with aggregation-induced emission (AIE) properties have gained interests due to their bright luminescence in solid-state aggregates. While fluorescence from AIE dyes have been widely exploited, relatively little is known about aggregation-induced stimulated emission. Here, we investigated stimulated emission of tetraphenylethene (TPE)-based organoboron AIE dyes, TPEQBN, in thin films and in microcavity lasers. Using femtosecond pump-probe spectroscopy, gain coefficients up to 230 cm-1 at 500 nm were measured. Using rate equations, we analyzed concentration- and pump-dependent gain dynamics as well as laser build up dynamics. During laser oscillation, radiative stimulated emission allows high instantaneous quantum yield greater than 90% to be achieved. We fabricated solid-state microspheres made of 100% AIE dyes via microfluidic emulsion and solvent evaporation method. Coupled with high gain and high refractive index of 1.76, microspheres as small as 2 µm in diameter showed lasing by nanosecond pumping with a threshold of ~10 pJ µm-2. Polymer coated, but not bare, microspheres were internalized by live cells and generated narrowband cavity mode emission from within the cytoplasm. Our work shows the potential of AIE dyes as laser materials.

Nanoscatterer-Assisted Fluorescence Amplification Technique.

Weak fluorescence signals, which are important in research and applications, are often masked by the background. Different amplification techniques are actively investigated. Here, a broadband, geometry-independent and flexible feedback scheme based on the random scattering of dielectric nanoparticles allows the amplification of a fluorescence signal by partial trapping of the radiation within the sample volume. Amplification of up to a factor of 40 is experimentally demonstrated in ultrapure water with dispersed TiO2 nanoparticles (30 to 50 nm in diameter) and fluorescein dye at 200 µmol concentration (pumped with 5 ns long, 3 mJ laser pulses at 490 nm). The measurements show a measurable reduction in linewidth at the emission peak, indicating that feedback-induced stimulated emission contributes to the large gain observed.

Water-Resistant Subwavelength Perovskite Lasing from Transparent Silica-Based Nanocavity.

Great research efforts are devoted to exploring the miniaturization of chip-scale coherent light sources possessing excellent lasing performance. Despite the indispensable role in Si photonics, SiO2 is generally considered not contributing to the starting up and operation of integrated lasers. Here, this work demonstrates an extraordinary-performance subwavelength-scale perovskite vertical cavity laser with all-transparent SiO2 cavity, whose cavity is ultra-simple and composed of only two parallel SiO2 plates. By introducing a ligand-assisted thermally co-evaporation strategy, highly luminescent perovskite film with high reproducibility and excellent optical gain is grown directly on SiO2 . Benefitting from their high-refractive-index contrast, low-threshold, high-quality factor, and single-mode lasing is achieved in subwavelength range of ≈120 nm, and verified by long-range coherence distance (115.6 µm) and high linear polarization degree (82%). More importantly, the subwavelength perovskite laser device could operate in water for 20 days without any observable degradation, exhibiting ultra-stable water-resistant performance. These findings would provide a simple but robust and reliable strategy for the miniaturized on-chip lasers compatible with Si photonics.

Colloidal CdSe/CdS Core/Crown Nanoplatelets for Efficient Blue Light Emission and Optical Amplification.

The application of CdSe nanoplatelets (NPLs) in the ultraviolet/blue region remains an open challenge due to charge trapping typically leading to limited photoluminescence quantum efficiency (PL QE) and sub-bandgap emission in core-only NPLs. Here, we synthesized 3.5 monolayer core/crown CdSe/CdS NPLs with various crown dimensions, exhibiting saturated blue emission and PL QE up to 55%. Compared to core-only NPLs, the PL intensity decays monoexponentially over two decades due to suppressed deep trapping and delayed emission. In both core-only and core/crown NPLs we observe biexciton-mediated optical gain between 470 and 510 nm, with material gain coefficients up to 7900 cm-1 and consistently lower gain thresholds in crowned NPLs. Gain lifetimes are limited to 40 ps, due to residual ultrafast trapping and higher exciton densities at threshold. Our results provide guidelines for rational optimization of thin CdSe NPLs toward lighting and light-amplification applications.

Broadband Tunable Optical Gain from Ecofriendly Semiconductor Quantum Dots with Near-Half-Exciton Threshold.

Optical gain in solution-processable quantum dots (QDs) has attracted intense interest toward next-generation optoelectronics; however, the development of optical gain in heavy-metal-free QDs remains challenging. Herein, we reveal that the ZnSe1-xTex-based QDs show excellent optical gain covering the violet to near-red regime. A new gain mechanism is established in the alloy QDs, which promotes a theoretically threshold-less optical gain thanks to the ultrafast carrier localization and suppression of ground-state absorption by the Te-derived isoelectronic state. Further, we disclose that the hot-carrier trapping represents the main culprit to exacerbate the gain performance. With the increase of Te-to-Se ratio, a sub-band-gap photoinduced absorption (PA) appears and extinguishes the optical gain. To overcome this issue, we modulate the inner ZnSe shell thickness, and the gain is recovered by reducing the overlap between the gain and PA regions in the Te-rich QDs. Our finding represents a significant step toward sustainable QD-based optoelectronics.

Transport Layer Engineering Toward Lower Threshold for Perovskite Lasers.

Charge-transport layers are essential for achieving electrically pumped perovskite lasers. However, their role in perovskite lasing is not fully understood. Here, the role of charge-transport layers on the lasing actions of perovskite films is explored by investigating the amplified spontaneous emission (ASE) thresholds. A largely reduced ASE threshold and enhanced ASE intensity is demonstrated by introducing an additional hole transport layer poly(triaryl amine) (PTAA). It is shown that the key role of the PTAA layer is to accelerate the hot-carrier cooling process by extracting holes in perovskites. With reduced hot holes, the Auger recombination loss is largely suppressed, resulting in decreased ASE threshold. This argument is further supported by the fact that the ASE threshold can be further reduced from 25.7 to 7.2 µJ cm-2 upon switching the pumping wavelength from 400 to 500 nm to directly avoid excess hot-hole generation. This work exemplifies how to further reduce the ASE threshold with transport layer engineering through hot-hole manipulation. This is critical to maintaining the excellent gain properties of perovskites when integrating them into electrical devices, paving the way for electrically pumped perovskite lasers.

Amplified Spontaneous Emission and Lasing from Zn-Processed AgIn5S8 Core/Shell Quantum Dots.

I-III-VI ternary quantum dots (QDs) have emerged as favorable alternatives to the toxic II-VI QDs for optoelectronic and biological applications. However, their use as optical gain media for microlasers is still limited by a low fluorescence efficiency. Here, we demonstrate amplified spontaneous emission (ASE) and lasing from colloidal QDs of Zn-processed AgIn5S8 (AIS) for the first time. The passivation treatment on the AIS QDs yields a 3.4-fold enhancement of fluorescence quantum efficiency and a 30% increase in the two-photon absorption cross section. ASE is achieved from the AIS/ZnS core/shell QD films under both one- and two-photon pumping with a threshold fluence of ∼84.5 µJ/cm2 and 3.1 mJ/cm2, respectively. These thresholds are comparable to the best optical gain performance of Cd based-QDs reported in the literature. Moreover, we demonstrate a facile whispering-gallery-mode microlaser of the core/shell QDs with a lasing threshold of ∼233 µJ/cm2. The passivated AIS QDs can be promising optical gain media for photonic applications.

High-Gain of NdIII Complex Doped Optical Waveguide Amplifiers at 1.06 and 1.31 µm Wavelengths Based on Intramolecular Energy Transfer Mechanism.

Chelate phosphine oxide ligand (9,9-dimethyl-9H-xanthene-4,5-diyl) bis (diphenylphosphineoxide) (XPO) is prepared as a neutral ligand to synthesize complex Nd (TTA)3 (XPO) (TTA = 2-thenoyltrifluoroacetone). An appropriate energy gap between the XPO and TTA ligands, which can support two additional energy transfer routines from the first excited triplet state (T1 ) energy level of the XPO to that of the TTA, improves energy transfer in the Nd complex. Based on intramolecular energy transfer mechanism, optical gains at 1.06 and 1.31 µm are demonstrated in Nd (TTA)3 (XPO)-doped polymer waveguides with the excitation of low-power light-emitting diodes (LEDs) instead of semiconductor lasers as pump sources. Using the vertical top-pumping mode of a 365 nm LED, relative gains of 22.5 and 8.4 dB cm-1 are obtained at 1.06 and 1.31 µm, respectively, in a 0.2 cm long embedded waveguide with a cross-section of 8 × 5 µm2 . The active core layer is Nd (TTA)3 (XPO)-doped SU-8 polymer. Moreover, relative gains are achieved in evanescent-field waveguide with a cross-section of 6 × 4 µm2 . The 21.0 and 5.6 dB cm-1 relative gains are achieved at 1.06 and 1.31 µm, respectively, with a net gain of 13.8 ± 0.3 dB cm-1 obtained at 1.06 µm in a 0.9 cm long SU-8 waveguide with Nd (TTA)3 (XPO)-doped polymethylmethacrylate as upper cladding.

An NIR-Driven Upconversion/C3N4/CoP Photocatalyst for Efficient Hydrogen Production by Inhibiting Electron-Hole Pair Recombination for Alzheimer's Disease Therapy.

Redox imbalance and abnormal amyloid protein (Aß) buildup are key factors in the etiology of Alzheimer's disease (AD). As an antioxidant, the hydrogen molecule (H2) has the potential to cure AD by specifically scavenging highly harmful reactive oxygen species (ROS) such as •OH. However, due to the low solubility of H2 (1.6 ppm), the traditional H2 administration pathway cannot easily achieve long-term and effective accumulation of H2 in the foci. Therefore, how to achieve the continuous release of H2 in situ is the key to improve the therapeutic effect on AD. As a corollary, we designed a rare earth ion doped g-C3N4 upconversion photocatalyst, which can respond to NIR and realize the continuous production of H2 by photocatalytic decomposition of H2O in biological tissue, which avoids the problem of the poor penetration of visible light. The introduction of CoP cocatalyst accelerates the separation and transfer of photogenerated electrons in g-C3N4, thus improving the photocatalytic activity of hydrogen evolution reaction. The morphology of the composite photocatalyst was shown by transmission electron microscopy, and the crystal structure was studied by X-ray diffractometry and Raman analysis. In addition, the ability of g-C3N4 to chelate metal ions and the photothermal properties of CoP can inhibit Aß and reduce the deposition of Aß in the brain. Efficient in situ hydrogen production therapy combined with multitarget synergism solves the problem of a poor therapeutic effect of a single target. In vivo studies have shown that UCNP@CoP@g-C3N4 can reduce Aß deposition, improve memory impairment, and reduce neuroinflammation in AD mice.

Balancing the Number of Quantum Wells in HgCdTe/CdHgTe Heterostructures for Mid-Infrared Lasing.

HgCdTe-based heterostructures with quantum wells (QWs) are a promising material for semiconductor lasers in the atmospheric transparency window (3-5 µm) thanks to the possibility of suppressing Auger recombination due to the no-parabolic law of carrier dispersion. In this work, we analyze the thresholds of stimulated emission (SE) under optical pumping from heterostructures with a different number of QWs in the active region of the structure. Total losses in structures are determined from the comparison of thresholds for the different number of QWs in the active region. It is shown that, thanks to the increased modal gain, a higher number of QWs results in lower threshold pumping intensity and, consequently, higher temperature of SE. These results indicate that improvements to the modal gain can result in a moderate uplift in the temperature of SE from mid-infrared HgCdTe-based heterostructures. On the other hand, at a high enough QW count threshold, the intensity no longer depends on the number of the QWs and is determined by the transparency concentration of a single QW.

Excitonic Mechanisms of Stimulated Emission in Low-Threshold ZnO Microrod Lasers with Whispering Gallery Modes.

Whispering gallery mode (WGM) ZnO microlasers gain attention due to their high Q-factors and ability to provide low-threshold near-UV lasing. However, a detailed understanding of the optical gain mechanisms in such structures has not yet been achieved. In this work, we study the mechanisms of stimulated emission (SE) in hexagonal ZnO microrods, demonstrating high-performance WGM lasing with thresholds down to 10-20 kW/cm2 and Q-factors up to ~3500. The observed SE with a maximum in the range of 3.11-3.17 eV at room temperature exhibits a characteristic redshift upon increasing photoexcitation intensity, which is often attributed to direct recombination in the inverted electron-hole plasma (EHP). We show that the main contribution to room-temperature SE in the microrods studied, at least for near-threshold excitation intensities, is made by inelastic exciton-electron scattering rather than EHP. The shape and perfection of crystals play an important role in the excitation of this emission. At lower temperatures, two competing gain mechanisms take place: exciton-electron scattering and two-phonon assisted exciton recombination. The latter forms emission with a maximum in the region near ~3.17 eV at room temperature without a significant spectral shift, which was observed only from weakly faceted ZnO microcrystals in this study.

Facet Engineering for Amplified Spontaneous Emission in Metal Halide Perovskite Nanocrystals.

Auger recombination and thermalization time are detrimental in reducing the gain threshold of optically pumped semiconductor nanocrystal (NC) lasers for future on-chip nanophotonic devices. Here, we report the design strategy of facet engineering to reduce the gain threshold of amplified spontaneous emission by manyfold in NCs of the same concentration and edge length. We achieved this hallmark result by controlling the Auger recombination rates dominated by processes involving NC volume and thermalization time to the emitting states by optimizing the number of facets from 6 (cube) to 12 (rhombic dodecahedron) and 26 (rhombicuboctahedrons) in CsPbBr3 NCs. For instance, we demonstrate a 2-fold reduction in Auger recombination rates and thermalization time with increased number of facets. The gain threshold can be further reduced ∼50% by decreasing the sample temperature to 4 K. Our systematic studies offer a new method to reduce the gain threshold that ultimately forms the basis of nanolasers.