Blue-shifted Photoluminescence Research Articles

Visualization and Estimation of 0D to 1D Nanostructure Size by Photoluminescence.

We elaborate a method for determining the 0D-1D nanostructure size by photoluminescence (PL) emission spectrum dependence on the nanostructure dimensions. As observed, the high number of diamond-like carbon nanocones shows a strongly blue-shifted PL spectrum compared to the bulk material, allowing for the calculation of their top dimensions of 2.0 nm. For the second structure model, we used a sharp atomic force microscope (AFM) tip, which showed green emission localized on its top, as determined by confocal microscopy. Using the PL spectrum, the calculation allowed us to determine the tip size of 1.5 nm, which correlated well with the SEM measurements. The time-resolved PL measurements shed light on the recombination process, providing stretched-exponent decay with a τ0 = 1 ns lifetime, indicating a gradual decrease in exciton lifetime along the height of the cone from the base to the top due to surface and radiative recombination. Therefore, the proposed method provides a simple optical procedure for determining an AFM tip or other nanocone structure sharpness without the need for sample preparation and special expensive equipment.

Encapsulation-induced hypsochromic shift of emission properties from a cationic Ir(III) complex in a hydrogen-bonded organic cage: A theoretical study.

Encapsulation of coordination complexes within the confined spaces of self-assembled hosts is an effective method for creating supramolecular assemblies with distinct chemical and physical properties. Recent studies with calix-resorcin[4]arene hydrogen-bonded hexameric capsules revealed that encapsulated metal complexes exhibit enhanced and blue-shifted photoluminescence compared to their unencapsulated forms. The photophysical change has been hypothetically attributed to encapsulation-induced confinement, which isolates the metal complex from the solvent, suppressing stabilization of the excited state of the guest by solvent reorganization and structural relaxation, and altering the local environment, such as solvent polarity and viscosity, around the guest. In this study, density-functional theory calculations were conducted to explore how encapsulation affects the photophysical properties of a cationic iridium complex within a hydrogen-bonded hexameric capsule. The encapsulation-induced emission shift was analyzed by separating it into three factors: suppression of solvent reorganization, suppression of structural relaxation of the complex, and electronic interactions between the complex and the capsule. The findings indicate that the photoluminescence modulation is driven by the electronic interaction between the host and guest, which affects the energy levels of the molecular orbitals involved in the T1 excited state and the suppression of excited-state structural relaxation of the Ir complex due to the presence of the host. This study advances our understanding of the photophysical dynamics of coordination complexes within the confined spaces of hexameric capsules, providing a valuable approach for tuning the excited state properties of guest molecules.

Coexistence of the Band Filling Effect and Trap-State Filling in the Size-Dependent Photoluminescence Blue Shift of MAPbBr3 Nanoparticles.

The size-dependent photoluminescence (PL) blue shift in organometal halide perovskite nanoparticles has traditionally been attributed to quantum confinement effects (QCEs), irrespective of nanoparticle size. However, this interpretation lacks rigor for nanoparticles with diameters exceeding the exciton Bohr radius (rB). To address this, we investigated the PL of MAPbBr3 nanoparticles (MNPs) with diameters ranging from ~2 to 20 nm. By applying the Brus equation and Burstein-Moss theory to fit the PL and absorption blue shifts, we found that for MNPs larger than rB, the blue shift is not predominantly governed by QCEs but aligns closely with the band filling effect. This was further corroborated by a pronounced excitation-density-dependent PL blue shift (Burstein-Moss shift) at high photoexcitation densities. Additionally, trap-state filling was also found to be not a negligible origin of the PL blue shift, especially for the smaller MNPs. The time-resolved PL spectra (TRPL) and excitation-density-dependent TRPL are collected to support the coexistence of both filling effects by the high initial carrier density (~1017-1018 cm-3) and the recombination dynamics of localized excitons and free carriers in the excited state. These findings underscore the combined role of the band filling and trap-state filling effects in the size-dependent PL blue shift for solution-prepared MNPs with diameters larger than rB, offering new insights into the intrinsic PL blue shift in organometal halide perovskite nanoparticles.

Controlling curcumin/acrylic polymer interactions for tailored delivery systems

In this work, we investigate the interaction between curcumin and biocompatible polymethacrylates (methyl, ethyl, and n-butyl side groups). Blend samples were produced using the salt leaching technique to increase the contact area in the ionic medium with pH 2.0, 5.0, 7.4, and 8.0. Using curcumin photoluminescence (PL) spectra to determine release profiles, we found a 6-fold higher quantity and a 3-fold higher release ratio for poly(n-butyl methacrylate) (PnBMA). Changes in the ionic form of curcumin were observed with PL blue shift and decrease in the characteristic time, from ca. 435 min at pH 2.0 and 5.0 to 192 min at pH 7.4 for PnBMA. The relative importance of curcumin interactions with the side and main polymer chains could be determined by interpreting the release profiles. With curcumin interaction controlled by pH and the length of the polymer side chain, one may envisage tailored drug delivery systems focusing on prolonged release.

A 30-nm-tunable photoluminescence caused by remote Γ-X-mixings in a GaAs/AlAs asymmetric seven-folded quantum-well superlattice separating with very thin barriers

We investigated the photoluminescence (PL) properties of a GaAs/AlAs asymmetric seven-folded quantum well (ASFQW) superlattices (SLs) with thin separating barriers within the ASFQW period. The linearly blue-shifted PL was proportional to the applied bias voltage. By performing a numerical analysis of the electric-field dependence of subband energies in the ASFQW, we concluded that this PL originated from consecutive Γ-X mixings between spatially long-range-separated Γ-subband states and an X-state in this ASFQW. These results indicate that various phenomena appear in ASFQW-SLs due to the increased degree of freedom of carrier transport paths, but a precise analysis of the electric field dependence of subband resonances is required. Therefore, the integrated study of AMQW-SLs definitely reveals new physical properties and leads to the development of new devices.

Light-induced transformation of all-inorganic mixed-halide perovskite nanoplatelets: ion migration and coalescence.

When exposed to light, the colloidal perovskite nanoplatelets (NPLs) in the film can fuse into larger grains, and this phenomenon was thought to be closely related to ion migration. However, the available CsPbBr3 NPLs are not conducive to directly distinguishing this hypothesis. Herein, we prepare mixed-halide perovskite CsPbBr2.7I0.3 NPLs by a ligand-assisted reprecipitation method and investigate the photoluminescence evolution of NPLs under laser irradiation. At a low-irradiation intensity, 4.5-monolayer NPLs exhibit blue-shifted photoluminescence peaks due to the migration of iodide ions. Under higher laser fluence, a new photoluminescence component appears in the long wavelength region after the spectral blue shift, which is attributed to the coalescence of NPLs according to transmission electron microscopy analysis. A similar spectral evolution is also observed in 8-monolayer NPLs, while only the spectral blue shift caused by ion migration is detected in cuboidal CsPbBr2.7I0.3 nanocrystals. The use of strong bonding ligands can inhibit the fusion process of the NPLs, but not to impede ion migration, suggesting that fusion requires ligand detachment rather than ion migration. Similar suppression effects can be achieved in a vacuum atmosphere. Moreover, we demonstrate that mixed-halide NPLs can be used to realize anti-counterfeiting applications with superior photosensitivity.

Electron irradiation effects on the optical properties of Hf- and Zn-doped β-Ga2O3

Optical and electrical properties of Hf- and Zn-doped β-Ga2O3 samples, which are n-type and insulating, respectively, were altered via high-energy electron irradiation at 2.5 or 0.5 MeV. The β-Ga2O3:Hf samples irradiated with 2.5 MeV electrons experienced a color change from blue to yellow and a large drop in conductivity, attributed to the creation of gallium vacancies, which compensate donors. This irradiation resulted in the absence of free carrier absorption and the presence of Cr3+ photoluminescence (PL). PL mapping prior to irradiation revealed optically active ZnO precipitates that formed during the growth of β-Ga2O3:Zn. These precipitates have a 384 nm (3.23 eV) stacking fault emission in the core; in the outer shell of the precipitate, the PL blue-shifts to 377 nm (3.29 eV) and a broad defect band is observed. After 0.5 MeV electron irradiation, the defect band broadened and increased in intensity. The blue PL band (435 nm) of β-Ga2O3 was enhanced for both Hf- and Zn-doped samples irradiated with 0.5 MeV. This enhancement is correlated with an increase in oxygen vacancies.

Unraveling Exciton-Plasmon Coupling and the PIRET Mechanism in Decorated Silicon Nanowires.

Exciton-plasmon coupling is a fascinating physical phenomenon that has been investigated in various metal semiconductor systems. Intentionally chosen silicon nanowires (SiNWs) systems act as a host material for providing exciton as well as silicon oxide as a thin dielectric. A clear blue-shift in photoluminescence (PL) peak and a significant increase in visible range absorption were observed for metal nanoparticle (MNP) decorated SiNWs (D-SiNWs) which signifies the presence of exciton-plasmon coupling. A further investigation reveals that the possibility of the occurrence of the plasmon-induced resonance energy transfer (PIRET) mechanism is higher. The PL intensity enhancement in Au-decorated SiNWs is higher (∼38 times) in comparison to that in Pt due to the presence of a strong and localized electric field of plasmons near the interface of metal and semiconductors. Moreover, splitting in PL for gold-decorated SiNWs might be due to the presence of dipole-quadrupole coupling along with dipole-dipole coupling, which further increases the strength of the PIRET mechanism.

Highly luminescent CsPbX3@MIL-53(Al) nanoarchitectonics with anomalous stability towards flexible emitting films

The poor stability of perovskite nanomaterials exposed in high temperature, moisture, light radiation, and polar solvent conditions severely restrict their commercial application. To address this issue, the growth in situ of CsPbX3 (X = Cl, Br, I) nanocrystals (NCs) is carried out by using the stable aluminum (Al)-based metal-organic frameworks to create CsPbX3@MIL-53(Al) composites. Compared with pristine CsPbX3 NCs prepared using room temperature ligand assisted re-precipitation synthesis, the CsPbX3@MIL-53(Al) composites exhibit narrow photoluminescence (PL) spectra and greatly improved stability. The green emitting CsPbBr3@MIL-53(Al) composite exhibit narrowed PL spectrum (the full width at half-maximum of PL spectra: 20 nm for the composite and 28 nm for CsPbBr3 NCs) and a blue-shifted PL peak wavelength (517.6 nm for the composite and 527.6 nm for the CsPbBr3 NCs). The relationship of microstructure, components, PL, fluorescence lifetime, and stability are discussed systematically. Anomalous stability against heat-treatment, polar solvent and humidity conditions indicated the composites retained their initial PL intensity after storge more than 4 months in ambient conditions and heat-treated to 120ºC for 5 cycles. The emitting color of CsPbBr3@MIL-53(Al) composites are easily adjusted from blue, green to red by controlling the halide components of precursors. The composite was used to create emitting coating and highly bright flexible emitting films which also reveal high stability, suggesting that in situ encapsulation of CsPbX3 NCs in MIL-53(Al) would supply a novel platform for various emitting devices.

(Invited) Formation and Characterization of Fe-Silicide Nanodots for Optoelectronic Application

We have demonstrated the formation of high areal-density β-FeSi2nanodots (NDs) on SiO2 by remote H2-plasma induced self-assembly of Fe-NDs and subsequent SiH4-exposure at 400°C. Under either 976- or 514.5-nm light excitation of NDs after the SiH4-exposure, stable photoluminescence (PL) signals, being characteristic of the semiconducting phase as β-FeSi2, were observed even at room temperature in the energy region over the indirect bandgap of bulk β-FeSi2 (~0.7 eV). The temperature dependence of PL was confirmed to be weak significantly in comparison to that of bulk bandgap, implying light emission from tightly confined NDs. And also, with a decrease in the average dot size by controlling the initial Fe-film thickness, a clear blue shift in PL was observed. The results are associated with quantum size effect in radiative recombination of photoexcited electron-hole pairs.

Revealing the enhanced crystalline quality mechanism of perovskites produced by microwave-assisted synthesis: toward the fabrications in a fully ambient air environment

The conventional stirring method (CSM) in a nitrogen-controlled glovebox has been widely used to synthesize the Cs/MA/FA precursor solution. However, it involves a long preparation time and limits the fabrication conditions in an ambient environment, hindering their potential for high-end applications and environmental stability. Herein, we systematically developed a fast and efficient microwave-assisted synthesis (MAS) method to produce a high-quality and stable triple cation perovskite (Cs0.1(MA0.17FA0.83)0.9Pb(Br0.17I0.83)3) solution and fabricated a device in ambient conditions. The superiority of using the MAS compared to CSM is manifested by comparing the improvements in crystal nucleation, enhanced optical properties, and its excellent stability with time, owing to the homogeneous heating of the precursor solution during the synthesis method. The MAS-prepared perovskite films showed anomalous photoluminescence blue-shift and linewidth broadening with increasing temperature, emphasizing the unique properties of the triple cation perovskite fabricated. These results were later interpreted and fitted to discuss the induced lattice thermal expansion, structural phase transition, and electron–phonon interactions that highlighted the enhanced crystal quality from the MAS-perovskite films. Considering the substantial fabrication parameters and conditions, the structural and optical stability of the MAS-perovskite films were maintained over time during exposure to air and ultraviolet light, even without encapsulation. To further elucidate the crystal quality improvements from using the MAS-perovskite solution, the fabrication of perovskite transistors in a completely ambient environment resulted in a 10-fold increase in electron carrier mobility compared to the CSM-perovskite devices. The developed synthesis method has contributed significant advantages to enhance the structural and environmental stability of perovskites, making a promising approach for larger-scale and more efficient future optoelectronic device applications.

Gram-scale synthesis of highly doped chlorine graphene quantum dots: Synthesis and photoluminescence properties

Band-gap engineering of graphene-based nanomaterials has a huge influence on their optical and structural properties. Our contribution reports the successful gram-scale synthesis of highly chlorinated graphene quantum dots (Cl-GQDs) via a two-step preparation method. X-ray photoelectron spectroscopy (XPS) proved the successful doping of chlorine atoms into the as-prepared graphene oxide quantum dots (O-GQDs). Time-resolved fluorescence revealed a high decrease in the relaxation lifetime from 690 ps for O-GQDs to 5.3–4 ps for Cl-GQDs. Transmission electron microscopy (TEM) confirms that all nanoparticles are on the quantum scale (4–6 nm). The large blueshift in photoluminescence (PL) 150 nm from the original O-GQD (440 → 290 nm) supports the chlorination effect which enables tuning the band gap of O-GQD.

Photophysical Characterization of Ru Nanoclusters on Nanostructured TiO2 by Time-Resolved Photoluminescence Spectroscopy.

Despite the promising performance of Ru nanoparticles or nanoclusters on nanostructured TiO2 in photocatalytic and photothermal reactions, a mechanistic understanding of the photophysics is limited. The aim of this study is to uncover the nature of light-induced processes in Ru/TiO2 and the role of UV versus visible excitation by time-resolved photoluminescence (PL) spectroscopy. The PL at a 267 nm excitation is predominantly due to TiO2, with a minor contribution of the Ru nanoclusters. Relative to TiO2, the PL of Ru/TiO2 following a 267 nm excitation is significantly blue-shifted, and the bathochromic shift with time is smaller. We show by global analysis of the spectrotemporal PL behavior that for both TiO2 and Ru/TiO2 the bathochromic shift with time is likely caused by the diffusion of electrons from the TiO2 bulk toward the surface. During this directional motion, electrons may recombine (non)radiatively with relatively immobile hole polarons, causing the PL spectrum to red-shift with time following excitation. The blue-shifted PL spectra and smaller bathochromic shift with time for Ru/TiO2 relative to TiO2 indicate surface PL quenching, likely due to charge transfer from the TiO2 surface into the Ru nanoclusters. When deposited on SiO2 and excited at 532 nm, Ru shows a strong emission. The PL of Ru when deposited on TiO2 is completely quenched, demonstrating interfacial charge separation following photoexcitation of the Ru nanoclusters with a close to unity quantum yield. The nature of the charge-transfer phenomena is discussed, and the obtained insights indicate that Ru nanoclusters should be deposited on semiconducting supports to enable highly effective photo(thermal)catalysis.

Octahedron distortion-triggered dipole–spin interaction in multiferroic magnetoelectric perovskites

The design of perovskite structures with multiferroic magnetoelectric coupling effects opens up new opportunities in fields such as the creation of next-generation spin-dependent multistate information storage technologies. In this work, we prepared a transition metal-implanted perovskite with multiferroic magnetoelectric coupling, in which both magnetoelectric coupling and a blueshift of photoluminescence were observed. The introduction of transition metal-generated polarized spin interacts with the electronic orbit through spin–orbital coupling to lead to a pronounced octahedron distortion, where the temperature dependence of the dielectric constant undergoes a ferroelectric polarization transition. An external magnetic field could enhance the strength of spin polarization to further affect the magnitude of electric polarization. Moreover, applying an electric field tunes the distortion of the octahedron dependence of electric polarization to feed back to the change in spin polarization. Overall, the spin polarization-induced electric polarization in perovskites provides a unique approach to realizing the room-temperature magnetoelectric coupling of multiferroic materials.

Bottom-up self-assembly of macroporous ZnO nanostructures for photovoltaic applications

The present study utilized a template-assisted electrodeposition route for the bottom-up epitaxial growth of macroporous zinc oxide nanostructures. To this end, the ZnO seed layer was coated on the p-type silicon substrates using a radio frequency magnetron sputtering technique to form a p-n heterojunction. Then, polymer microspheres were implanted on ZnO/Si substrates to act as a template. Subsequently, ZnO nanostructures were electrodeposited through the interstitial spaces between the microspheres. After the deposition, the microspheres were removed by dissolving in chloroform solvent, forming a porous structure. The planar and cross-sectional electron microscopy analyses exhibited a uniform macroporous morphology with an average pore diameter of ∼1 μm. The pores were homogeneously distributed on the surface of the electrodeposited ZnO layer. The advantage of this technique over the top-down approaches, such as electrochemical etching, is that the porosity and size of pores can be easily adjusted by varying the concentration and diameter of microsphere templates. The optical investigations revealed enhancement in photon absorption and photoluminescence (PL) intensity due to multiple light scattering in the pore walls of the deposited ZnO nanostructures. For the templated sample, a PL blue shift was observed due to the reduction in crystallite size of ZnO nanostructures. A heterojunction thin film solar cell was designed by the metallization of ZnO/p-Si samples to study the power conversion capability of macroporous ZnO nanostructures. The photovoltaic performance of the developed devices was evaluated under a solar light simulator. The device based on the templated sample showed increased shunt resistance and reduced series resistance compared to the flat sample. The optoelectrical results indicated an efficiency improvement for the fabricated solar cells based on the macroporous ZnO sample due to its higher exposed area and increased rate of electron-hole generation.

Passivation capping of InAs surface quantum dots by TMA/Al2O3: PL enhancement and blueshift suppression

Passivation capping that enhances the photoluminescence (PL) of molecular beam epitaxy (MBE)-grown InAs surface quantum dots (SQDs) is realized by ex situ low-temperature atomic layer deposition (ALD)-grown Al2O3. As the Al2O3 cap thickness increased from 2 to 30 nm, the PL intensity was enhanced by 2.7-fold and the blue shift was suppressed. This is in strong contrast to wet chemistry passivation and in situ GaAs capping by MBE, both of which resulted in significant PL blueshift, due to etching in the former, and In/Ga intermixing and strain in the latter. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) reveal that the Al2O3 cap layer mimics the shape of the underlying SQDs. The cross-sectional transmission electron microscopy (TEM) further reveals that the SQD size and shape remained unchanged after Al2O3 capping, which is in strong contrast to MBE-capping. The passivation mechanisms and native oxide reduction by trimethylaluminum (TMA), including self-clean-up reaction through ligand exchange, are discussed based on the results by x-ray photoelectron spectroscopy (XPS). A detailed comparison between Al2O3 and ZnO cap layers reveals the significance of the cap properties on the SQD size/shape and PL blueshift. While the size/shape of SQDs is preserved by Al2O3 capping, the apex is slightly removed by ZnO capping, resulting in a stronger PL blueshift compared to Al2O3.

First Experimental Evidence of Anti-Stokes Laser-Induced Fluorescence Emission in Microdroplets and Microfluidic Systems Driven by Low Thermal Conductivity of Fluorocarbon Carrier Oil

With the advent of many optofluidic and droplet microfluidic applications using laser-induced fluorescence (LIF), the need for a better understanding of the heating effect induced by pump laser excitation sources and good monitoring of temperature inside such confined microsystems started to emerge. We developed a broadband highly sensitive optofluidic detection system, which enabled us to show for the first time that Rhodamine-B dye molecules can exhibit standard photoluminescence as well as blue-shifted photoluminescence. We demonstrate that this phenomenon originates from the interaction between the pump laser beam and dye molecules when surrounded by the low thermal conductive fluorocarbon oil, generally used as a carrier medium in droplet microfluidics. We also show that when the temperature is increased, both Stokes and anti-Stokes fluorescence intensities remain practically constant until a temperature transition is reached, above which the fluorescence intensity starts to decrease linearly with a thermal sensitivity of about −0.4%/°C for Stokes emission or −0.2%/°C for anti-Stokes emission. For an excitation power of 3.5 mW, the temperature transition was found to be about 25 °C, whereas for a smaller excitation power (0.5 mW), the transition temperature was found to be about 36 °C.

Second harmonic generation in air-exposed few-layer black phosphorus

Black phosphorus (BP) shows significant saturable absorption and other unique properties in nonlinear optical effects, and it can be used for nonlinear optical elements and other photonic devices. However, the second harmonic generation (SHG) emission is prohibited due to its inversion symmetry. Here we report emerging SHG emission in BP by exposing BP to oxygen so as to break the inversion symmetry. The intensity of SHG signal shows a dependence on thickness and exposure time. It is interesting to find that the thinner BP flakes have faster SHG intensity change rate. Our results demonstrate that the intensity of SHG signal is attributed to oxidation degree. Air exposure also causes a blue shift of photoluminescence (PL) peaks, which is consistent with our calculation results. Our study demonstrates a feasible approach to modulate the SHG emission of BP, which may provide insights to other inversion symmetric crystals like BP. • We report emerging SHG emission in BP by exposing BP to oxygen so as to break the inversion symmetry. • It is founded that the intensity of SHG signal shows a dependence on thickness and exposure time. • It is founded that air exposure causes a blue shift of PL peaks, which is consistent with our calculation results. The results demonstrate that the intensity of SHG signal is attributed to oxidation degree. • To the best of our knowledge, there is no report on the SHG in BP before. This work demonstrates a feasible approach to modulate the SHG emission of BP, which may provide insights to other inversion symmetric crystals like BP.

Enhanced optoelectrical performance of ultraviolet detectors based on self-assembled porous zinc oxide nanostructures

A templated self-assembly technique was utilized in the present study to grow porous zinc oxide nanostructures. The nanostructures were formed by the electrochemical deposition of ZnO through the interstitial spaces between polymer microsphere templates. After the deposition, polymer microspheres were removed by dissolving in chloroform solvent, leaving porous ZnO nanostructures. This technique is benefited from facile controllability of the pore morphology and size by varying the diameter of microspheres. X-ray diffraction analysis showed a dominant peak corresponding to the hexagonal ZnO structure. Moreover, no significant structural strain was observed after the removal of spheres unlike the other synthesis methods of porous materials. The improved photoluminescence (PL) properties revealed an enhancement in the light capturing capability of the systems due to the multiple scattering of light in the pore walls. The porous sample showed a PL blue-shift compared to the flat one, indicating a reduction in crystallite size of ZnO nanostructures. To assess the photonic applications of synthesized porous ZnO substrates, a metal-semiconductor-metal photodetector was developed via the metallization of ZnO nanostructures, and their optoelectrical properties were tested under UV radiation. The results showed an improvement in photosensitivity and quantum efficiency of devices based on porous ZnO substrates which can be assigned to the larger exposed area and elevated rates of electron-hole generation in this sample.

Piezochromic Tetracoordinate Boron Complex: Blue-Shifted and Enhanced Luminescence.

Achieving blueshifted and enhanced emission from purely organic luminophors remains a major challenge. Herein, we report a tetracoordinate boron complex with polymorphism (Y-phase and O-phase)-dependent luminescence. Impressively, the Y-phase crystals exhibited rare piezochromic luminescent properties such as pressure-induced blue-shifted and enhanced emission. The results of theoretical and experimental tests demonstrated that this phenomenon results from the cooperative effect between the restriction of intramolecular motions and alterable charge transfer (CT) behavior during compression. This work provides an ideal model to investigate the optoelectronic properties of boron complexes. Importantly, manipulating the CT behavior through the electrophilicity of boron atoms may become a new principle for the design of piezochromic materials with blueshifted and enhanced emission.