Low Amplified Spontaneous Emission Research Articles

Extremely Low Threshold Quasi‐CW Amplified Spontaneous Emission Achieving and Its Mechanism Study

AbstractThe development of lasing materials with weak pile‐up effect from triplet excitons, low lasing threshold, and long operational lifetime is much significant for truly continuous wave operation and electrically pumping organic lasers. However, most of organic gain media has been verified to have extreme quenching effect from triplet excitons due to its wide‐band distribution of triplet absorption spectrum. Here, it is found that the phenanthroimidazole derivatives as gain media have congenital advantages on handling triplet's issues. A very low amplified spontaneous emission (ASE) threshold of 0.56 µJ cm−2 and a long operational lifetime of 5.77 × 105 pump pulses in air atmosphere are well obtained. When increasing the pump repetition frequency from 20 Hz to 20 kHz, the operational lifetimes of the thin films have small reduction. Under a high pump repetition frequency of 200 kHz, which is quasi‐continuous wave operational regime, the PI2PhDPO thin film exhibits very low ASE threshold of 0.78 µJ cm−2 due to the tiny overlap between triplet absorption and ASE spectra.

Mixing Dion–Jacobson and Ruddlesden–Popper Structures in Quasi‐2D Perovskite Films for Thermal‐ and Photo‐Stable Stimulated Emission

AbstractQuasi‐two–dimensional (2D) perovskite films are promising candidates as a gain medium for stimulated emission owing to their hydrophobicity and efficient energy funneling that facilitates the population inversion. However, the commonly used Ruddlesden–Popper (R–P) perovskites still suffer from instability induced by high‐density pumping as well as the resulting heating effect. Here, quasi‐2D perovskite films with mixed Dion–Jacobson (D–J) and R–P phases are demonstrated with both excellent amplified spontaneous emission (ASE) properties and thermal‐ and photo‐stabilities under ambient conditions. In these films, octyl ammonium bulky organic cations are used to obtain the preferred crystal orientation and highly smooth surface for low‐threshold ASE, while 1,8‐octanedi ammonium cations contribute to the greatly improved stability. The films containing the D–J phase exhibit good structural stability even after 130 °C heat treatment for 48 h. The mixed‐ligands film maintains a low ASE threshold of 11.6 µJ cm−2 and a high optical gain of 413 cm−1 after environmental annealing. It is demonstrated that it is the diammonium that firmly bonds to the perovskite layer,allowing the maintenance of quasi‐2D perovskite structure and good ASE performances.

Air-sensitive amplified spontaneous emission in lecithin-capped CsPbBr3 nanocrystals thin films

Fully inorganic lead halide perovskite nanocrystals (NCs) are receiving great attention as active materials for photonic and optoelectronic devices. While the lack of long-term stability, due to their sensitivity to ambient air exposure, currently prevents their application to commercial devices, the presence of reversible environmental effects opens the way for possible applications of lead halide perovskites in resistive or optical sensors. In this work we investigate the Amplified Spontaneous Emission (ASE) properties and their dependence on the surrounding environment of lecithin-capped CsPbBr3 NCs thin films. We demonstrate low ASE threshold under nanosecond pumping, both in air and in vacuum, with emission intensity lower in air than in vacuum. We also show that the emission quenching induced by ambient air exposure, ascribed to moisture-induced surface solvation, is reversible and it is fully restored by a suited vacuum stint application. The ASE sensitivity is up to 6.5 larger than the spontaneous emission one, making lecithin-capped CsPbBr3 NCs thin films promising systems for the development of optical humidity sensors with high sensitivity.

Aprotic Solvent Effect in Preparation of Organo Lead Iodide Perovskite Nanowires by Two-Step Spin-Coating Procedure

Lead-iodide perovskite (CH3NH3PbI3 ≡ MAPbI3) nanowires (NWs) were prepared by a two-step spin-coating technique by modifying one of the perovskite precursors with a small amount of aprotic solvent. In the two-step spin-coating technique, the perovskite precursors are MAI and PbI2. The first MAI powder is dissolved in isopropanol (IPA) to produce an isopropanol-MAI solution, while the second PbI2 is used in N, N-dimethylformamide (DMF) as an aprotic solvent. Here, a small amount of DMF was used with an IPA solution of MAI to grow 1D NWs based on MAPbI3 perovskite. Then, the film was formed directly from the MAPbI3 perovskite nanowires (PNWs) by coating the PbI2 layer with an IPA solution of MAI modified by DMF. The amount of DMF in the MAI/IPA solution was adjusted in the range between 0 and 50 μl. One-dimensional (1D) PNWs (∼100 nm diameter) and three-dimensional (3D) perovskite nanocrystals are compared. The structural and optical properties of the PNWs films are systematically investigated using X-ray diffraction patterns (XRD), scanning electron microscopy images (SEM), UV–vis absorption, and photoluminescence (PL). The result is that the presence of an additional solvent and its optimized amount in the MAI/IPA solution can increase the length and efficiency of charge transfer by facilitating perovskite transformation, as evidenced by the intensity of PL and the formation of a high-quality perovskite film. Compact, hole-free films with low trap states (crystal defects) were obtained. Further investigation of the lead iodide perovskite showed that reducing the dimensionality from 3D to 1D resulted in shorter wavelengths of the absorption edge and the PL peak in both the absorption and PL spectra. The shorter wavelengths indicate more localized exciton states in NWs. Finally, the amplified spontaneous emission (ASE) properties were obtained under picosecond laser excitation and a low ASE threshold was found at 10 and 53 μJ/cm2 for 1D and 3D, respectively, at about 300 nm film thickness.

Tailoring D-π-A architectures with hybridized local and charge transfer fluorophores exhibiting high electroluminescence exciton utilization and low threshold amplified spontaneous emission.

Novel amorphous compounds which could simultaneously use 25% singlet excitons and 75% triplet excitons as the energy source for light amplification enable the reduction of the threshold current density for electrically pumped organic semiconductor laser diodes (OSLDs); however, there is always a trade-off between the high radiative decay rate of the local excited (LE) state that is required for amplified spontaneous emission (ASE) and high exciton utilization benefiting from the charge-transfer (CT) state during electroluminescence (EL). Herein, we have explored a delicate balance to achieve both low ASE threshold and high EL exciton utilization by adopting a carefully tailored hybridized local and charge-transfer (HLCT) molecular design. A series of donor-π-acceptor (D-π-A) molecules (SBz-1, SBz-2 and SBz-3) are synthesized, and the structural change mainly refers to the spatial distance between D and A which could regulate the excited-state character via adjusting the CT length. Notably, the ASE phenomenon with a low threshold (2.97 μJ cm-2) and a high exciton utilization of 57.6% are achieved at the same time for SBz-2 with an appropriate CT length. The results provide guidance for molecular design toward harvesting triplet excitons in organic laser materials.

Optical Properties of Perovskite-Organic Multiple Quantum Wells.

A comprehensive study of the optical properties of CsPbBr3 perovskite multiple quantum wells (MQW) with organic barrier layers is presented. Quantum confinement is observed by a blue‐shift in absorption and emission spectra with decreasing well width and agrees well with simulations of the confinement energies. A large increase of emission intensity with thinner layers is observed, with a photoluminescence quantum yield up to 32 times higher than that of bulk layers. Amplified spontaneous emission (ASE) measurements show very low thresholds down to 7.3 µJ cm−2 for a perovskite thickness of 8.7 nm, significantly lower than previously observed for CsPbBr3 thin‐films. With their increased photoluminescence efficiency and low ASE thresholds, MQW structures with CsPbBr3 are excellent candidates for high‐efficiency perovskite‐based LEDs and lasers.

Amplified Spontaneous Emission Threshold Dependence on Determination Method in Dye-Doped Polymer and Lead Halide Perovskite Waveguides.

Nowadays, the search for novel active materials for laser devices is proceeding faster and faster thanks to the development of innovative materials able to combine excellent stimulated emission properties with low-cost synthesis and processing techniques. In this context, amplified spontaneous emission (ASE) properties are typically investigated to characterize the potentiality of a novel material for lasers, and a low ASE threshold is used as the key parameter to select the best candidate. However, several different methods are currently used to define the ASE threshold, hindering meaningful comparisons among various materials. In this work, we quantitatively investigate the ASE threshold dependence on the method used to determine it in thin films of dye-polymer blends and lead halide perovskites. We observe a systematic ASE threshold dependence on the method for all the different tested materials, and demonstrate that the best method choice depends on the kind of information one wants to extract. In particular, the methods that provide the lowest ASE threshold values are able to detect the excitation regime of early-stage ASE, whereas methods that are mostly spread in the literature return higher thresholds, detecting the excitation regime in which ASE becomes the dominant process in the sample emission. Finally, we propose a standard procedure to properly characterize the ASE threshold, in order to allow comparisons between different materials.

Amplified spontaneous emission of perovskite in water: Towards under-water lasing

The application of halide perovskite materials as lasing devices has recently attracted great attention. However, the instability of such materials against moisture significantly restrict the application in many occasions. In order to protect the unstable perovskite materials against oxygen and moisture, various encapsulation strategies have been proposed. Regrettably, few of them are designed for aqueous environments. Herein, we demonstrate a photo-polymerized acrylic acid (ADCP) acting as substrate and encapsulation layer to fabricate (CH3NH3)PbBr3 (MAPbBr3) films and realize amplified spontaneous emission (ASE) with low threshold in water. Lasing threshold from MAPbBr3 films sandwiched by ADCP decreases slightly from 12 μJ/cm2 in air to ∼9 μJ/cm2 in water. The specific morphology, superb wettability and high-water stability are expected to contribute to the low ASE threshold. The aqueous environment with higher refractive index is speculated to be one of the origins of the slightly lower ASE threshold. Our results demonstrate a strong potential for applications of perovskite materials in lasing devices in aqueous environment and a new path to realize low threshold lasing.

Ultrastable Gd3+ doped CsPbCl1.5Br1.5 nanocrystals blue glass for regulated and low thresholds amplified spontaneous emission

Here, Gd-doped CsPbCl 1.5 Br 1.5 nanocrystals (NCs) in borosilicate glass matrix ( B 2 O 3 − SiO 2 − ZnO ) were prepared by melting quenching and in-situ crystallization. The optical performance of CsPbCl 1.5 Br 1.5 NCs glasses under different heat-treatment temperatures and the content of Gd 3 + were analyzed in detail. After CsPbCl 1.5 Br 1.5 NCs glass is doped with Gd 3 + ions, the photoluminescence intensity increases and the synthesized Gd-doped CsPbCl 1.5 Br 1.5 NCs glasses have excellent water stability and thermal cycling performance. In addition, the influence of Gd-doped concentrations and heat-treatment temperatures on the amplified spontaneous emission (ASE) thresholds of CsPbCl 1.5 Br 1.5 NCs glasses was studied, and the Gd-doped CsPbCl 1.5 Br 1.5 NCs glasses achieve controllable ASE thresholds at room temperature. The ASE threshold can be as low as 0.39 mJ / cm 2 . This work offers a neoteric reference for the research in the application of metal ion-doped perovskite NCs and a new idea for the realization of controllable and low ASE thresholds on perovskite NCs.

Light Amplification and Efficient Electroluminescence from a Solution‐Processable Diketopyrrolopyrrole Derivative via Triplet‐to‐Singlet Upconversion

AbstractOver the years, achieving efficient electroluminescence (EL) while simultaneously having low light amplification thresholds under optical excitation has been the key to progression toward the long‐thought objective of electrically pumped organic lasers. While significant progress in this regard has been made for organic semiconductors emitting in the blue–green region of the visible spectrum, organic laser dyes with low‐energy emission (>600 nm) still suffer from high amplified spontaneous emission (ASE) thresholds and low external quantum efficiencies (EQEs) in devices. Herein, low ASE thresholds and efficient EL are reported from a solution‐processable organic laser dye dithiophenyl diketopyrrolopyrrole (DT‐DPP). The ASE threshold of 4 µJ cm−2 at the wavelength of 620 nm is obtained while making constructive use of triplet excitons by doping DT‐DPP in a green‐emitting host matrix, which exhibits thermally activated delayed fluorescence (TADF). The organic light‐emitting diode fabricated from this system gives a high EQE of 7.9% due to the efficient utilization of triplet excitons. Transient EL studies further show that a high reverse intersystem crossing rate is crucial in achieving lasing under electrical pumping from such TADF‐assisted fluorescent systems.

The effects of ASE contrast and beams mutual alignment on the γ-ray yield in laser-plasma interactions with artificial prepulse

We present experimental study of the bremsstrahlung γ-rays generation in a plasma interacting with 50 fs laser pulse in slightly relativistic regime (intensity ∼2-1018 W/cm2). A pre-plasma layer on the surface of the molybdenum target is formed by an additional laser pulse with a duration of 8 ns and an intensity of ∼2-1012 W/cm2. The energy and intensity of the artificial pre-pulse exceed those of the amplified spontaneous emission (ASE) pedestal of the main pulse by ∼103 and 10 times (for contrast 10−7), respectively. It was shown that the low ASE contrast (>10−7) is the crucial condition for increasing (in comparison to the case without artificial pre-pulse) of the integral γ-rays yield when the nanosecond pulse is ahead of the femtosecond one by >20 ns. Interferometry data show that the reason of the γ-rays yield increasing is a pre-plasma layer initially produced by artificial pre-pulse and re-created by the ASE. The optimum conditions for γ-rays yield achieved if (i) the pre-pulse comes ∼25 ns in advance, (ii) ASE contrast is 10−7 and lower and (iii) the femtosecond focal point is shifted by ∼100 μm from the center of the nanosecond pre-pulse focal spot and by ∼100 μm above the target surface.

Deep‐Red Lasing and Amplified Spontaneous Emission from Nature Inspired Bay‐Annulated Indigo Derivatives

AbstractWhile noteworthy progress has been made on organic solid‐state lasers with low amplified spontaneous emission (ASE) thresholds and high optical gains in blue and green colors, the same advancement has not been achieved for red laser dyes. This is mainly due to their low photoluminescence quantum yields (PLQYs) because of “energy bandgap law.” Here, a new family of solution‐processable organic semiconductor laser dyes based on a bay‐annulated indigo derivative (Cibalackrot) with deep‐red emission is reported. They exhibit excellent PLQYs and low ASE thresholds (9.6 µJ cm−2) with deep‐red emission when blended in a mixed host of 1,3‐bis(N‐carbazolyl)benzene (mCP) and 2‐hydroxyphenylbenzothiazole (HBT). In contrast to a single blend in mCP, the co‐blend films are found to significantly enhance the photostability by retaining 90% of initial ASE intensity even after continuous pumping with over 9000 pulses at a pump input energy twice that of the ASE threshold, which can be attributed to efficient cascade energy transfer from mCP to HBT and then to the Cibalackrot chromophore. Low lasing threshold of 6 µJ cm−2 is further achieved at 641 nm by using distributed feedback gratings. Transient absorption spectroscopy measurements indicate that the dye has extremely low yield of triplet excited‐state under optical excitation. The results show Cibalackrot derivatives to be a promising new family of organic deep‐red laser dyes.

Low-Threshold Non-Doped Deep Blue Lasing from Monodisperse Truxene-Cored Conjugated Starbursts with High Photostability.

Herein, the photophysical, morphological, optical gain characteristics of a set of trigonal monodisperse starburst conjugated macromolecules (Tr1-Tr4) have been systematically investigated in order to elucidate the influence of the molecular structures on their optoelectronic performance. With increasing the oligofluorene arm length, absorption spectra were red-shifted progressively, whereas an increase in photoluminescence quantum yields (PLQYs) and optical gain coefficients, and a corresponding reduction in amplified spontaneous emission (ASE) thresholds and loss coefficients were observed for Tr1-Tr3 except for Tr4. The results indicate that the effective conjugation length become saturated for Tr3 in this system. Impressively, the resulting molecules manifested very low ASE thresholds (4.4-11.6 μJ cm-2 ) with high photostability, as well as high thermal stability. One dimensional distributed feedback (DFB) lasers exhibited a minimum lasing threshold of 10.38 nJ pulse-1 (0.86 kW cm-2 , 4.325 μJ cm-2 ) for Tr3. It should be emphasized that the ASE threshold of Tr1-Tr4 was nearly unchanged from room temperature to 200 °C. The results suggest that this kind of truxene-cored conjugated starbursts with high photostability and low lasing thresholds are rather promising gain media for organic semiconductor lasers.

Low Amplified Spontaneous Emission Threshold and Efficient Electroluminescence from a Carbazole Derivatized Excited-State Intramolecular Proton Transfer Dye

The search for new classes of efficient electroluminescent organic laser dyes with low amplified spontaneous emission (ASE) threshold (Eth) and low optical losses is crucial toward the realization of organic injection lasers. In this work, we report in-depth studies of an organic semiconducting laser dye, benzo[d]thiazol-2-yl)-5-(9H-carbazol-9-yl)phenol (HBT-Cz), and compare the photophysical study with its parent HBT dye. While HBT is not laser-active in solution, the carbazole derivatized dye (i.e., HBT-Cz) showed a low solution ASE threshold of 21 mJ/cm2, which is comparable to a common high-performing commercial laser dye, Rhodamine 6G (Rh-6G). HBT-Cz also exhibited a low film ASE threshold of 2.4 μJ/cm2 with a low optical loss coefficient of 1.5 cm–1, which is the lowest waveguide loss coefficient reported for solution-processed organic semiconductors. Organic light-emitting diodes based on this material showed a high maximum EQE of 1.9%, which is close to the theoretical EQE limit of the emitter, an...

Enhancing Optical Gain Stability for a Deep-Blue Emitter Enabled by a Low-Loss Transparent Matrix

Efficient organic gain media with high optical gain and good photostability are highly desirable for organic semiconductor lasers. To shed light on the rational molecular design, in this work, a novel deep-blue organic emitter consisting of a carbazole core substituted by a diphenylamine-functionalized triazine unit and two arms of bifluorene with flexible alkyl chains (denoted as C2) was designed and synthesized. Various basic photophysics and amplified spontaneous emission (ASE) characterizations were conducted with a particular focus to unravel the impact of the molecular structure on the photostability. Relatively low ASE threshold of 7.0 μJ/cm2, high net gain coefficient of 79.9 cm–1 (under 40-fold threshold pump fluence), and low optical loss coefficient of 7.0 cm–1 were recorded for C2 in neat films. For comparison, C2 was also dispersed into polystyrene (PS), a low-loss transparent matrix, with various ratios to form PS-C2 blend films. Among them, a 50 wt % PS-C2 blend film exhibited a high gain c...

Two-photon pumped amplified spontaneous emission based on all-inorganic perovskite nanocrystals embedded with gold nanorods

CsPbBr3 nanocrystals have attracted great interest owing to their high fluorescence quantum efficiency, adjustable photoluminescence wavelength, and good stability. We report a device that consists of disordered gold nanorods underneath a film of CsPbBr3 nanocrystals. Two-photon pumping using femtosecond laser pulses at 800 nm enables amplified spontaneous emission (ASE) at about 523 nm. In this work, a narrow peak with linewidth of 5 nm is observed when the pump fluence reaches a low threshold of 0.65 mJ/cm2. The results show that plasmonic resonance of gold nanorods improves the emission transition rate and enables low threshold ASE.

Preferential Orientation of Crystals Induced by Incorporation of Organic Ligands in Mixed‐Dimensional Hybrid Perovskite Films

AbstractOrganic–inorganic perovskites demonstrate great potential for optical applications due to their intriguing optical and optoelectronic properties. Dedicated efforts have been carried out to understand the energy landscape and charge carrier mobilities for perovskite materials. In order to further boost these materials toward large‐scale applications, an alternative “bottom‐up” route for the understanding about correlation between the morphology of high‐quality planar films and their optical properties is essential. Here, mixed‐dimensional bromide‐based hybrid perovskite thin films are prepared from a simple one‐step solution processing route using mixtures of methylammonium bromide (MABr) and octylammonium bromide (OABr). Grazing incidence scattering data statistically reveal that the development of thin‐film morphology as well as crystal orientation depends on the orientation of the OABr crystallites. This study opens up further insight into the morphology of perovskite thin films. In combination, the occurrence of amplified spontaneous emission (ASE) in perovskite films with low ASE thresholds with values approaching 17.8 µJ cm−2 is demonstrated and appears to be closely correlated to the tailored morphology, highlighting its importance for realizing optical gain media.

Low-Threshold Light Amplification in Bifluorene Single Crystals: Role of the Trap States.

Organic single crystals (SCs) expressing long-range periodicity and dense molecular packing are an attractive amplifying medium for the realization of electrically driven organic lasers. However, the amplified spontaneous emission (ASE) threshold (1-10 kW/cm2) of SCs is still significantly higher compared to those of amorphous neat or doped films. The current study addresses this issue by investigating ASE properties of rigid bridging group-containing bifluorene SCs. Introduction of the rigid bridges in bifluorenes enables considerable reduction of nonradiative decay, which, along with enhanced fluorescence quantum yield (72-82%) and short excited state lifetime (1.5-2.5 ns), results in high radiative decay rates (∼0.5 × 109 s-1) of the SCs, making them highly attractive for lasing applications. The revealed ASE threshold of 400 W/cm2 in acetylene-bridged bifluorene SCs is found to be among the lowest ever reported for organic crystals. Ultrafast transient absorption spectroscopy enabled one to disclose pronounced differences in the excited state dynamics of the studied SCs, pointing out the essential role of radiative traps in achieving a record low ASE threshold. Although the origin of the trap states was not completely unveiled, the obtained results clearly evidence that the crystal doping approach can be successful in achieving extremely low ASE thresholds required for electrically pumped organic laser.

Triple cation mixed-halide perovskites for tunable lasers

Metal halide perovskites are recently attracting strong attention due to their potential in solar cells, LEDs, and lasers. Here, we demonstrate the broad spectral tuning of the optical gain characteristics of triple cation (containing methylammonium, formamidinium and cesium) mixed-halide perovskite thin films. We explicitly study the interrelation between amplified spontaneous emission (ASE) thresholds, the operational stability of the gain, and the material composition. The incorporation of cesium and a deficiency of lead in the precursor solutions is found to be crucial for low ASE thresholds and the improved stability of mixed-halide perovskites. We tune the photoluminescence in mixed-halide perovskites between peak wavelengths of 510 and 790 nm by exchanging the halide from iodide to bromide and chloride in small steps of 10%, while preserving the narrowband emission below a linewidth of 130 meV for all mixtures. The optical gain under ns-excitation can be tuned over a significant portion of this spectral window; we observe ASE emission in regions between 545 to 555 nm and 680 to 810 nm. This is a significant step towards perovskite lasers operating through a broad portion of the visible to near infrared spectrum.

Stimulated emission and optical properties of pyranyliden fragment containing compounds in PVK matrix

Organic solid state lasers are thoughtfully investigated due to their potential applications in communication, sensors, biomedicine, etc. Low amplified spontaneous emission (ASE) excitation threshold value is essential for further use of the material in devices. Intramolecular interaction limits high molecule density load in the matrix. It is the case of the well-known red light emitting laser dye - 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM). The lowest ASE threshold value of the mentioned laser dye could be obtained within the concentration range between 2 and 4wt%. At higher concentration threshold energy drastically increases. In this work optical and ASE properties of three original DCM derivatives in poly(N-vinylcarbazole) (PVK) at various concentrations will be discussed. One of the derivatives is modified DCM dye in which the methyl substituents in the electron donor part have been replaced with bulky trityloxyethyl groups (DWK-1). These sterically significant functional groups do not influence electron transitions in the dye but prevent aggregation of the molecules. The chemical structure of the second investigated compound is similar to DWK-1 where the methyl group is replaced with the tert-butyl substituent (DWK-1TB). The third derivative (DWK-2) consists of two N,N-di(trityloxyethyl)amino electron donor groups. All results were compared with DCM:PVK system. Photoluminescence quantum yield (PLQY) is up to ten times larger for DWK-1TB with respect to DCM systems. Bulky trityloxyethyl groups prevent aggregation of the molecules thus decreasing interaction between dyes and amount of non-radiative decays. The red shift of the photoluminescence and amplified spontaneous emission at higher concentrations were observed due to the solid state solvation effect. The increase of the investigated dye density in the matrix with a smaller reduction in PLQY resulted in low ASE threshold energy. The lowest threshold value was obtained around 21μJ/cm2 (2.1kW/cm2) in DWK-1TB:PVK films.