Mn-doped Nanocrystals Research Articles

Tailoring Auger Recombination Dynamics in CsPbI3 Perovskite Nanocrystals via Transition Metal Doping.

Auger recombination is a pivotal process for semiconductor nanocrystals (NCs), significantly affecting charge carrier generation and collection in optoelectronic devices. This process depends mainly on the NCs' electronic structures. In our study, we investigated Auger recombination dynamics in manganese (Mn2+)-doped CsPbI3 NCs using transient absorption (TA) spectroscopy combined with theoretical and experimental structural characterization. Our results show that Mn2+ doping accelerates Auger recombination, reducing the biexciton lifetime from 146 to 74 ps with increasing Mn doping concentration up to 10%. This accelerated Auger recombination in Mn-doped NCs is attributed to increased band edge wave function overlap of excitons and a larger density of final states of Auger recombination due to Mn orbital involvement. Moreover, Mn doping reduces the dielectric screening of the excitons, which also contributes to the accelerated Auger recombination. Our study demonstrates the potential of element doping to regulate Auger recombination rates by modifying the materials' electronic structure.

Optical regulation by localized states of Cu2+ ions with highly sensitive to trap density and thermalization in manganese-doped perovskite nanocrystals

Mn2+-doped perovskites nanocrystals (NCs) have already been extensively studied in fascinating optical, electronic, and magnetic properties. Such interesting traits make them paid considerable attention in light emitting diodes, solar cells, etc. However, the underlying thermal and photophysical processes governing the overall charge carrier dynamics in Mn-doped NCs are far from clear. Herein, trap concentration and thermalization-dependent optical properties of Mn–Cu co-doped CsPbCl3 NCs were investigated via using steady-state, time-resolved PL spectra, variable-temperature PL spectra, and ultrafast transient absorption spectra. The combined experimental and theoretical studies reveal that Cu2+, as an effective hole trap, can trap the holes from Mn2+ and emit the holes to Mn2+ level at lighter and higher doping, respectively. Moreover, this hole trap is highly thermally sensitive, which is responsible for the abnormal thermal effect of Mn2+ emission with increasing temperature. These findings demonstrate an approach of charge regulation through ion doping, which is meaningful for fabricating efficient photoelectric materials and devices.

Alkaline surface treatment and time-resolved reading of mn-doped nanocrystal signal transducer for enhanced bioassay sensitivity

Recently, Mn-doped semiconductor nanocrystals (NCs) with high brightness, long lifetimes, and low-energy excitation are emerging for time-resolved luminescence biosensing/imaging. Following our previous work on Mn-doped NCs, in this work we developed poly(styrene-co-maleic anhydride) (PSMA)-encapsulated Mn-doped AgZnInS/ZnS NCs as signal transducers for immunoassay of capsular polysaccharide (CPS), a surface antigen and also a biomarker of Burkholderia pseudomallei which causes a fatal disease called melioidosis. To enhance the assay sensitivity, a surface treatment for PSMA-encapsulated NCs (NC-probes) was performed to promote the presence of carboxyl groups that help conjugate more anti-CPS antibodies to the surface of NC-probes and thus enhance bioassay signals. Meanwhile, time-resolved reading on the luminescence of NC-probes was adopted to minimize the assay background autofluorescence. Both strategies essentially enhance the assay signal-to-background ratio (or equivalently the assay sensitivity) by increasing the signal and decreasing the background, respectively. Through performing and comparing immunoassays with different NC-probes (with and without surface treatment) and different signal reading methods (time-resolved reading and non-time-resolved reading), it was proven that the immunoassay adopting surface-treated NC-probes and time-resolved reading achieved a lower limit-of-detection (LOD) than the ones adopting non-surface-treated NC-probes or non-time-resolved reading. Moreover, the achieved LOD is comparable to the LOD of immunoassay using enzyme horseradish peroxidase as a signal transducer.

Mn-doped AgZnInS/ZnS nanocrystals (NCs): Effects of Zn etching on the NC optical properties

Mn-doped I(II)-III-VI NCs (e.g., Mn-doped AgZnInS/ZnS NCs) possessing low-energy excitation, high brightness and long fluorescence lifetimes have been desired for time-gated fluorescence biosensing/imaging. In this type of NCs, their optical properties are significantly affected by the microscopic interactions between Mn and Mn and between Mn and host NC, the compositions of NCs, and the defects in NCs. On the other hand, it is known that Zn etching to core I(II)-III-VI NCs in NC synthesis can significantly enhance the NC brightness because Zn can exchange surface atoms (e.g., Ag and In) in NCs to minimize NC surface-defects. But for Mn-doped I(II)-III-VI NCs, Zn etching could etch out not only surface-atoms of host NCs (e.g., Ag and In) but also Mn in NCs. As a result, it could significantly affect the NC compositions and the microscopic interactions between Mn and Mn as well as between Mn and host NC, and thus the optical properties of NCs (like lifetime and absorption/emission spectra). Therefore, it is needed to investigate how Zn etching would affect the optical properties of such Mn-doped NCs. In this study, a series of Mn-doped AgZnInS NCs with different Mn doping levels were prepared through nucleation doping, and then Zn etching was applied to etch these core NCs. To identify the effects of Zn etching on NC optical properties, ZnS coating (a different ZnS shelling approach by injecting Zn precursor and S precursor alternately in synthesis) was performed on the same Mn:AgZnInS NCs, and the optical properties of NCs with these two different ZnS shelling approaches were compared. Experimental results showed that under appropriate Mn doping levels in synthesis, Zn etching instead of ZnS coating can produce low-energy excitable NCs with higher QYs and longer lifetimes, which would further facilitate the use of such NCs in time-gated fluorescence measurement. To understand the reasons for the different optical properties under different ZnS shelling approaches, the material characteristics of the prepared NCs were further measured/analyzed and the possible fluorescence mechanisms were discussed.

Electron Transfer Going the Distance: Mn-Doped ZnSe as a Model Photocatalytic System

Time-resolved photoluminescence and transient absorption spectroscopy are used to examine the influence that long excited state lifetimes of Mn-doped nanocrystals have on the mechanisms of photoind...

Recent Progress of Electron Storage Mn Center in Doped Nanocrystals

Mn doping in semiconductor nanocrystals (NCs) has been reviewed for its unequivocal relevance to solar energy harvesting in terms of both mechanistic approaches of electron storage in the Mn center and improved power conversion efficiency (PCE). Mn-doped NCs have been measured to have significantly higher PCE than the undoped counterpart, which has been reviewed for a number of different host NCs including different alloy and core–shell structures. Such increment of PCE has been attributed to electron relaxation from the hot states of the host NCs via the Mn state (that occurs at hundreds of picosecond time scale) which acts as electron-storage center. This can avoid the detrimental charge recombination significantly, and at the same time, fast electron injection from the Mn state to TiO2 leads to enhancement of PCE performance. These phenomena are clearly demonstrated by analyzing the feedback from femtosecond transient absorption, time-resolved photoluminescence, and impedance spectroscopy.

Microstructural, optical, magnetic and photocatalytic properties of Mn doped ZnO nanocrystals of different sizes

The present work explores the differences in the various properties of Mn doped ZnO nanocrystals when the sizes of the doped nanocrystals are significantly different. Mn doped ZnO nanocrystals of sizes ≈20 nm and ≈5 nm were synthesized by the chemical co-precipitation method. The targeted Mn doping concentrations were 2%, 6% and 10% (atomic), however, the observed doping concentrations were low (≈0.5%, ≈1% and ≈2%). The microstructural, morphological, optical and magnetic properties as well as the photocatalytic activities of the nanocrystals were investigated. The variations of the lattice strain and lattice volume with increasing Mn concentrations were found to be correlated. The un-doped and Mn doped ZnO nanocrystals were found to be ferromagnetic at room temperature. Variation of band gap with increasing Mn concentrations was observed. Significant/insignificant quenching of the photoluminescence emissions was observed for sizes ≈20 nm/≈ 5 nm after doping. The saturation magnetization was found to depend on the Mn concentrations as well as on the nanocrystal sizes. Agglomerated Mn2+ resulted in a decrease in saturation magnetization of the ≈2% Mn doped nanocrystals of sizes ≈5 nm. Correlation between the photoluminescence properties and photocatalytic activities was observed.

The Photoluminescent and Magnetic Properties of Mn2+ Ions at the Interface of Core/Shell Mn-Doped Nanocrystals

The Photoluminescent and Magnetic Properties of Mn2+ Ions at the Interface of Core/Shell Mn-Doped Nanocrystals

Study of Structural Transformation in Mn Doped CuO Nanocrystals and Its Optical Properties

Study of Structural Transformation in Mn Doped CuO Nanocrystals and Its Optical Properties

Red-Tuned Mn d-d Emission in Doped Semiconductor Nanocrystals.

Light-emitting Mn-doped semiconductor nanocrystals have been extensively studied for the last three decades for their intense and stable Mn d-d emission. In principle, this emission should be fixed at 585 nm (yellow), but recent studies have shown that the emission can be widely tuned even to 650 nm (red). This is a spectacular achievement as this would make Mn-doped nanocrystals efficient and tunable light emitters. Keeping these developments in view, the chemistry of the synthesis of these materials, their photophysical processes and the expected origins of their red emission are summarized in this Minireview. All the related important studies from 1992 onwards are chronologically discussed, and one particular case is elaborated on in detail. As these materials are potentially important for biology, and photovoltaic, sensing and light-emitting devices, this Minireview is expected to help researchers investigating the chemistry, physics and applications of these materials.

Temperature dependence of properties of Mn-doped nanocrystals with different binding symmetry

We report the temperature dependence of photoluminescent properties of Mn-doped nanocrystals (NCs) with different binding symmetry. The photoluminescence peaks of Mn2+ ions shift to shorter wavelength with increasing temperatures, resulting from the reduction of crystal field. Further evidence for temperature-dependent crystal field variety is demonstrated by electronic paramagnetic resonance (EPR) spectra. Additionally, the inflexion temperature of the excited state lifetimes increases from 170K (Sample I) to 220K (Sample IV), which is speculated to be resulted from the easily affected wave function overlap due to thermal lattice expansion in more symmetrical binding Mn-doped NCs.

Grafting of ZnS:Mn-Doped Nanocrystals and an Anticancer Drug onto Graphene Oxide for Delivery and Cell Labeling.

A facile method for the synthesis of highly fluorescent manganese-doped zinc sulfide (ZnS:Mn) nanocrystals covalently functionalized with polyethylene glycol conjugated graphene oxide (GO-PEG) for drug delivery and cell labeling is reported. First, covalently functionalized GO with PEG-bis(amine) to enhance the solubility and biocompatibility in water and physiological buffers. Second, glutathione (GSH)-coated ZnS:Mn-doped nanocrystals were covalently grafted onto GO-PEG. An acid-amidation process was employed to obtain GO-PEG/ZnS:Mn nanocomposites, which were characterized by UV/Vis, photoluminescence, and Fourier transform infrared spectroscopies, and transmission electron microscopy. Finally, the anticancer drug doxorubicin (DOX) was noncovalently loaded onto these GO-PEG/ZnS:Mn composite particles. High drug entrapment efficiency (100 % due to more GO surface available for binding), slow in vitro release of drug (ca. 40 % at acidic pH), better HeLa cancer cell killing efficiency (ca. 85 %), and cell labeling capability are the important traits of these DOX-loaded nanocomposites. It is believed these novel fluorescent [GO-PEG/ZnS:Mn]-DOX composite particles have great potential as theranostic agents in cancer diagnosis and therapy.

One-pot simple synthesis and characterisation of Mn2+-doped GaN nanorods by RAPET method

In this work, we display one-step reactions under autogenic pressure at elevated temperature (RAPET) method-based synthesis of Mn-doped GaN nanorods by varying the atomic ratio of Mn:Ga as 0, 0.02, 0.04, 0.06 and 0.08, respectively. The synthesised nanorods are characterised by X-ray diffraction, high-resolution transmission electron microscopy (HRTEM) and Raman spectral methods. It is observed that there is a decrease in the lattice constant with an increase in the concentration of Mn (from 0.02 to 0.08 wt%). Moreover, the smaller covalent radius of Mn is the key for the doping process. The Mn-doped GaN nanocrystals show rod-like morphology with a length of 40–50 nm and width of 8–12 nm. This size factor mainly depends on the doping of Mn [from transmission electron microscopy (TEM) analysis] into GaN components. Well-defined lattice fringes are elucidated for the growth of crystalline hexagonal GaN (wurtzite type) nanocrystals.

Magneto-optical Faraday rotation of semiconductor nanoparticles embedded in dielectric matrices.

Faraday rotation has been studied for CdS, CdTe, and CdS:Mn semiconductor nanoparticles synthesized by colloidal chemistry methods. Additionally these materials were prepared in a form of semiconductor nanoparticles embedded in polyvinyl alcohol films. Transmission electron microscopy and atomic force microscopy analyses served as confirmation of nanocrystallinity and estimation of the average size of the nanoparticles. Spectral dependence of the Faraday rotation for the studied nanocrystals and nanocomposites is correlated with a blueshift of the absorption edge due to the confinement effect in zero-dimensional structures. Faraday rotation spectra and their temperature behavior in Mn-doped nanocrystals demonstrates peculiarities, which are associated with s, p-d exchange interaction between Mn²⁺ ions and band carriers in diluted magnetic semiconductor nanostructures.

Synthesis, Crystallographic and Magnetic Properties of Mn Doped ZnO Nanocrystals Via Solid State Reaction Technique

The polycrystalline undoped and Mn doped ZnO (Zn 0.85 Mn 0.15 O) nanocrystals were successfully synthesized using solid state reaction technique. The X-ray diffraction (XRD) studies of pure ZnO and Mn doped ZnO nanocrystals exhibit the wurtzite structure (hexagonal phase, space group P6 3 mc) with high crystallinity and also without any impurity phases. Surface morphology and particle size were carried out using transmission electron microscopy (TEM). It shows that these nanoparticles are of hexagonal phase ZnO mostly in spherical shape with average diameter of the nanocrystals were in the range 30 -100 nm. The magnetic measurements by vibrating sample magnetometer (VSM) clearly indicate that the pure ZnO nanocrystals are in ferromagnetic nature and Mn doped ZnO nanocrystals exhibit co-existence of paramagnetic and ferromagnetic behavior at room temperature.

Doping by Diffusion

Materials Science The electronic properties of bulk semiconductors can be improved by doping, the deliberate introduction of impurity atoms that increase the number or mobility of charge carriers. Usually, just doping the surface of a bulk semiconductor is sufficient, but for semiconductor nanocrystals, the entire particle needs to be doped to achieve the desired properties. Vlaskin et al. report on the doping of CdSe nanocrystals with Mn ions, a process that has proven especially difficult at the high levels desired to impart magnetic properties. Hot-injection synthesis of Mn-doped CdSe nanocrystals (where the particles rapidly form in solution from precursors) results in particles that are depleted in Cd2+ at the surface. The authors were able to incorporate Mn2+ ions uniformly by starting with CdSe seed nanocrystals, which were injected as a solution along with selenium into a solution of manganese acetate at ∼300°C for times varying from seconds to several hours. This thermodynamically controlled process, which uniformly increased the size of the seeds, resulted in diffusion doping of the entire crystal without requiring Cd2+ ion ejection and allowed doping levels of Mn2+ as high as 20% to be achieved. J. Am. Chem. Soc. 135 , 10.1021/ja4072207 (2013).

Effect of a Boron Additive on the Microstructure and Dielectric Properties of BaTiO<sub>3</sub> Thin Films Formed by Nanocrystal Deposition

Highly crystallized BaTiO3 thin films were fabricated by a nanocrystal sintering process. Boron alkoxide was introduced into a slurry of Mn-doped BaTiO3 nanocrystals with particle sizes of 5-7 nm. The deposited nanocrystal film on a (111)-oriented Pt/TiO2/Al2O3 substrate was sintered at a low temperature of 800 °C and the obtained film had highly densified and oriented microstructures. We found that the boron additive enhanced the grain growth of nanoparticles and as a result the dielectric constant of the thin film increased to 1100 at 10 kHz, which is much higher than that of undoped BaTiO3 thin films.

Ligand-Free, Colloidal, and Luminescent Metal Sulfide Nanocrystals.

We report here a different kind of binary and ternary colloidal inorganic nanocrystals, where no capping ligand is used. The surfaces of these ligand-free nanocrystals were designed to exhibit negative charges and, therefore, electrostatically repel each other, forming a colloidal dispersion in a polar solvent. Undoped and Mn-doped ZnxCd1-xS nanocrystals were studied both in solution and close-packed films. While undoped samples exhibit poor luminescence because of surface defects, Mn-doped nanocrystals show strong luminescence both in solution (20% quantum efficiency) and the film. Strong Mn emission arises from the inner-core d electrons, which are less sensitive to nonradiative decay channels on the nanocrystal surface. Ligand-free AgInS2 nanocrystals exhibit donor-acceptor type luminescence. Our preliminary results suggest the possibility of electronic coupling between ligand-free nanocrystals in their film, and therefore, they are expected to be more suitable for electronic and optoelectronic applications compared to organic-capped nanocrystals.

Photoluminescence properties of Mn-doped ZnxCd1−xS nanocrystals synthesized via nucleation-doping strategy

Optical properties of Mn-doped ZnxCd1−xS nanocrystals were studied by steady-state and time-resolved photoluminescence (PL) spectroscopy. The doped nanocrystals with PL quantum yield up to 29% were synthesized by growing a thin ZnS layer on the MnS core and then growing a CdS layer with different thicknesses using nucleation-doping strategy. The absorption band edge of ZnxCd1−xS nanocrystals was tuned from 425 to 475nm by growing the CdS layer with various thicknesses under different Zn/Cd molar ratios to vary the composition. The PL band of Mn-doped nanocrystals was found to originate from emissions of Mn2+ ions and defect states.

Doping Location-Dependent Energy Transfer Dynamics in Mn-Doped CdS/ZnS Nanocrystals

Dynamics of energy transfer and charge carrier localization in Mn-doped CdS/ZnS core/shell nanocrystals correlated with doping location and concentration are studied via transient absorption measurement of exciton relaxation dynamics. The strong dependence of exciton-Mn energy transfer rate on doping location was directly resolved in the transient bleach recovery and electron intraband absorption data by using layer-by-layer synthesized Mn-doped nanocrystals. With 1.2 nm decrease in doping radius in the ZnS shell, energy transfer rate increases by 6 fold. We identified that hole trapping is the major competing process that inhibits the energy transfer in Mn-doped CdS/ZnS nanocrystals. From the branching ratio of the energy transfer and hole trapping, combined with luminescence quantum yield measurement, we also obtained doping location-dependent radiative relaxation quantum yield of Mn(2+) ions that is as high as 0.95.