Magneto-Optical Stark Effect in Fe-Doped CdS Nanocrystals.

Fe2+ doping in II-VI semiconductors, due to the absence of energetically accessible multiple spin state configurations, has not given rise to interesting spintronic applications. In this work, we demonstrate for the first time that the interaction of homogeneously doped Fe2+ ions with the host CdS nanocrystal with no clustering is different for the two spin states and produces two magnetically inequivalent excitonic states upon optical perturbation. We combine ultrafast transient absorption spectroscopy and density functional theoretical analysis within the ground and excited states to demonstrate the presence of the magneto-optical Stark effect (MOSE). The energy gap between the spin states arising due to MOSE does not decay within the time frame of observation, unlike optical and electrical Stark shifts. This demonstration provides a stepping-stone for spin-dependent applications.

Solvent Adaptive Dynamic Metal-Organic Soft Hybrid for Imaging and Biological Delivery.

A solvent responsive dynamic nanoscale metal-organic framework (NMOF) [Zn(1 a)(H2 O)2 ] has been devised based on the self-assembly of ZnII and asymmetric bola-amphiphilic oligo-(p-phenyleneethynylene) (OPE) dicarboxylate linker 1 a having dodecyl and triethyleneglycolmonomethylether (TEG, polar) side chains. In THF solvent, NMOF showed nanovesicular morphology (NMOF-1) with surface decorated dodecyl chains. In water and methanol, NMOF exhibited inverse-nanovesicle (NMOF-2) and nanoscroll (NMOF-3) morphology, respectively, with surface projected TEG chains. The pre-formed NMOFs also unveiled reversible solvent responsive transformation of different morphologies. The flexible NMOF showed cyan emission and no cytotoxicity, allowing live cell imaging. Cisplatin (14.4 wt %) and doxorubicin (4.1 wt %) were encapsulated in NMOF-1 by non-covalent interactions and, in vitro and in vivo drug release was studied. The drug loaded NMOFs exhibited micromolar cytotoxicity.

Ligand assisted digestion and formation of monodisperse FeCoS2 nanocrystals.

Digestive ripening of bimetallic magnetic nanocrystals from uniform microsheets to spherical nanocrystals was observed in FeCoS2 nanocrystals leading to the formation of monodisperse nanocrystals. Earlier examples of digestive ripening are associated with the transformation of polydisperse particles to monodisperse particles deriving energetic stabilization from the monodispersity. However, it is interesting to note that in the current case, not only did we observe a transformation from uniform sheets to spherical particles but we also observed it in the absence of thiol, the most commonly used digestive ripening agent. We have then studied the effect of ligands such as oleic acid and oleylamine responsible for this ripening process. Long chain acids were found to be majorly responsible for digestive ripening while the amines assist in the formation of microsheets. A plausible mechanism has then been proposed.

Tuning radiative recombination in Cu-doped nanocrystals via electrochemical control of surface trapping.

The incorporation of copper dopants into II-VI colloidal nanocrystals (NCs) leads to the introduction of intragap electronic states and the development of a new emission feature due to an optical transition which couples the NC conduction band to the Cu-ion state. The mechanism underlying Cu-related emission and specifically the factors that control the branching between the intrinsic and impurity-related emission channels remain unclear. Here, we address this problem by conducting spectro-electrochemical measurements on Cu-doped core/shell ZnSe/CdSe NCs. These measurements indicate that the distribution of photoluminescence (PL) intensity between the intrinsic and the impurity bands as well as the overall PL efficiency can be controlled by varying the occupancy of surface defect sites. Specifically, by activating hole traps under negative electrochemical potential (the Fermi level is raised), we can enhance the Cu band at the expense of band-edge emission, which is consistent with the predominant Cu(2+) character of the dopant ions. Furthermore, we observe an overall PL "brightening" under negative potential and "dimming" under positive potential, which we attribute to changes in the occupancy of the electron trap sites (that is, the degree of their electronic passivation) that control nonradiative losses due to electron surface trapping.

Electronic structure study of dual-doped II-VI semiconductor quantum dots towards single-source white light emission.

Single-source white light emitting colloidal semiconductor quantum dots (QDs) is one of the most exciting and promising high-quality solid-state light sources to meet the current global demand for sustainable resources. While most of the previous methods involve dual (green-red) emissive nanostructures coated on blue LEDs to achieve white light, this work describes a single-source white light emitter of robust and superior quality using dual-doping. A modified synthesis method for intense white light emitting Cu, Mn dual-doped ZnSe QDs is engineered such that the extent of doping and concentration of ligands can alter their electronic structures. This is then customized to obtain various types of white light emissions ranging from warm white to cool white. Further, the composition-driven change in the electronic structure of the host QDs is exploited to achieve emission tunability over the entire visible range.

Copper-doped inverted core/shell nanocrystals with "permanent" optically active holes.

We have developed a new class of colloidal nanocrystals composed of Cu-doped ZnSe cores overcoated with CdSe shells. Via spectroscopic and magneto-optical studies, we conclusively demonstrate that Cu impurities represent paramagnetic +2 species and serve as a source of permanent optically active holes. This implies that the Fermi level is located below the Cu(2+)/Cu(1+) state, that is, in the lower half of the forbidden gap, which is a signature of a p-doped material. It further suggests that the activation of optical emission due to the Cu level requires injection of only an electron without a need for a valence-band hole. This peculiar electron-only emission mechanism is confirmed by experiments in which the titration of the nanocrystals with hole-withdrawing molecules leads to enhancement of Cu-related photoluminescence while simultaneously suppressing the intrinsic, band-edge exciton emission. In addition to containing permanent optically active holes, these newly developed materials show unprecedented emission tunability from near-infrared (1.2 eV) to the blue (3.1 eV) and reduced losses from reabsorption due to a large Stokes shift (up to 0.7 eV). These properties make them very attractive for applications in light-emission and lasing technologies and especially for the realization of novel device concepts such as "zero-threshold" optical gain.

Breakdown of volume scaling in Auger recombination in CdSe/CdS heteronanocrystals: the role of the core-shell interface.

Spatial confinement of electronic excitations in semiconductor nanocrystals (NCs) results in a significant enhancement of nonradiative Auger recombination (AR), such that AR processes can easily dominate the decay of multiexcitons. AR is especially detrimental to lasing applications of NCs, as optical gain in these structures explicitly relies on emission from multiexciton states. In standard NCs, AR rates scale linearly with inverse NC volume. Here, we investigate multiexciton dynamics in hetero-NCs composed of CdSe cores and CdS shells of tunable thickness. We observe a dramatic decrease in the AR rates at the initial stage of shell growth, which cannot be explained by traditional volume scaling alone. Rather, fluorescence-line-narrowing studies indicate that the suppression of AR correlates with the formation of an alloy layer at the core-shell interface suggesting that this effect derives primarily from the "smoothing" of the confinement potential associated with interfacial alloying. These data highlight the importance of NC interfacial structure in the AR process and provide general guidelines for the development of new nanostructures with suppressed AR for future lasing applications.

Insights into the Oxidation State of Cu Dopants in II-VI Semiconductor Nanocrystals.

Luminescent Cu-doped semiconductor nanocrystals have played a pivotal role in the emergence of lighting and display applications for a long time. However, consensus regarding the Cu oxidation state and hence their emission mechanism has not been attained. Distinction between seemingly simple optically and magnetically active Cu2+ and inactive Cu1+ has surprisingly been the subject matter of debate in the literature for more than a decade. In this Perspective, we first discuss the fundamental quantum mechanical phenomenon explaining the optical properties of the monovalent and divalent Cu dopants. We then focus down on various techniques used to differentiate between these two fundamental mechanisms, their benefits, and their pitfalls arising in large part because of the lack of spatial separation. Hence, to obtain a cohesive story consistent with all the observations, we discuss recent results from single-molecule spectroscopy to understand the optical properties and hence the oxidation state of internally doped Cu in doped nanocrystals.

Photoluminescence Quenching in CsPbCl3 upon Fe Doping: Colloidal Synthesis, Structural and Optical Properties.

Doped perovskite lead halide nanocrystals (PHNCs) are promising materials for various optoelectronic applications, but the major challenge faced by the researchers is the inability to dope foreign elements into perovskite lattice because of the strong lead-halide bond energies. In this work, we have used Fe as a dopant in CsPbCl3 to explore different doping techniques based on the colloidal synthesis of PHNCs to investigate the advantages and disadvantages of different techniques. We are able to dope a relatively higher amount of Fe (∼10%) than reported and observe clear optical signatures when the precursor does not have pre-existing Pb-Cl bonds. We prove that there are two competing processes inside a doped PHNC - one is the effect of dopant energy levels, and the other is surface passivation by halide ions. Using the most optimal synthesis strategy, we show that although Fe does act as a luminescence quencher in perovskite similar to II-VI quantum dots (QDs), the quenching requires much more Fe compared to trace amounts of Fe required in traditional QDs. Our work will assist in giving an overall comparative idea of doping and finding the most optimized strategy and help identify the underlying physical processes in perovskite based QDs.

Experimental Determination of the Molar Absorption Coefficient of Cesium Lead Halide Perovskite Quantum Dots.

Lead halide perovskite (CsPbX3, where X = Cl, Br, or I) quantum dots (QDs), with tunable optical and electronic properties, have attracted attention because of their promising applications in solar cells and next-generation optoelectronic devices. Hence, it is crucial to investigate in detail the fundamental size-dependent properties of these perovskite QDs to obtain high-quality nanocrystals for practical use. We propose a direct method for determining the concentration of solution-processed CsPbX3 QDs by means of spectrophotometry, in which the molar absorption coefficient (ε) is obtained using absorption and the Beer-Lambert law. By tuning the size of CsPbX3 QDs, we obtain their corresponding ε leading to a calibration curve for calculating the nanocrystal concentrations. The ε at the band edge for CsPbX3 (X = Cl, Br, or I) nanocrystals was found to be strongly dependent on the bandgap of the nanocrystals. We also obtained a reliable size dependence of the bandgap calibration curves to estimate the size of QDs from the absorption spectra.

Study of the Interface and Radial Dopant Position in Semiconductor Heterostructures Using X-ray Absorption Spectroscopy.

Two questions that remain a challenge in the field of colloidal doped core/shell nanomaterials of different morphologies are the nature of the interface and the radial location of the dopant ion due to the diffusion within the lattice. Using a model system of Cu-doped CdSe/CdS quantum dots, we develop an in-depth understanding of the extended X-ray absorption fine structure (EXAFS) spectra of the dopant and host atoms to address both issues. Our findings suggest that the interface is not sharp, in agreement with the nonstructural studies in the literature. Local structure analysis around the Cu dopant ion confirms that Cu drifts out from the core toward the outer region in the absence of the shell but stays mostly in the core after the formation of a sufficiently thick interfacial barrier (∼2 monolayers). This study highlights the significance of EXAFS spectroscopy in understanding the nature of the interface in nanomaterials.

Polaronic Signatures in Doped and Undoped Cesium Lead Halide Perovskite Nanocrystals through a Photoinduced Raman Mode.

Lead halide perovskites (LHPs) are promising candidates for photovoltaic applications as they exhibit large carrier diffusion lengths and long carrier lifetimes among many other interesting properties. One of the widely accepted mechanisms for these properties is polaron formation, which is mainly driven by octahedral distortions of the inorganic framework. Since structure modifications of the framework largely affect associated distortions, we investigated Mn-doped and undoped CsPbX3 (where X = Cl, Br, Cl/Br) using a local probe via micro-Raman spectroscopy and density functional theory (DFT) calculations for polaron formation. Our results highlight a new vibrational lattice mode at 132 cm-1 due to polaronic distortion upon photoinduction. From the DFT studies, we have shown that the polaronic states are dominated by the B-site cation in the perovskite structure, but it is the strong covalent overlap of the halide which determines its stability. This elucidation to map polaronic signatures with excellent spatial resolution using traditional Raman spectroscopy can be used as a simple tool to understand the structural changes and their impacted electronic properties and thus design superior devices using its in situ applications.

Visible-Blind ZnMgO Colloidal Quantum Dot Downconverters Expand Silicon CMOS Sensors Spectral Coverage into Ultraviolet and Enable UV-Band Discrimination.

Selective spectral detection of ultraviolet (UV) radiation is highly important across numerous fields from health and safety to industrial and environmental monitoring applications. Herein, a nontoxic, visible-blind, quantum dot (QD)-based sensing scheme that expands the spectral coverage of silicon complementary metal-oxide-semiconductor (CMOS) sensors into the UV, enabling efficient UV detection without affecting the sensor performance in the visible and UV-band discrimination, is reported. This scheme uses zinc magnesium oxide (ZnMgO) QDs with compositionally tunable absorption across UV and high photoluminescence quantum yield in the visible. The efficient luminescence and large Stokes shift of these QDs are exploited herein to act as an efficient downconverting material that enhances the UV sensitivity of Si-photodetectors (Si-PDs). A Si-PD integrated with the QDs results in a ninefold improvement in photoresponsivity from 0.83 to 7.5 mA W-1 at 260 nm. Leveraging the tunability of these QDs, a simple UV-band identification scheme is further reported, which uses two distinct-bandgap ZnMgO QDs stacked in a tandem architecture whose spectral emission color depends on the UV-band excitation light. The downconverting stack enables facile discrimination of UV light using a standard CMOS image sensor (camera) or by the naked eye and avoids the use of complex optics.

Spin-polarized Mn2+ emission from Mn-doped colloidal nanocrystals.

We report magnetophotoluminescence studies of strongly quantum-confined 0D diluted magnetic semiconductors (DMS), realized in Mn(2+)-doped ZnSe/CdSe core-shell colloidal nanocrystals. In marked contrast to their 3D (bulk), 2D (quantum well), 1D (quantum wire), and 0D (self-assembled quantum dot) DMS counterparts, the ubiquitous yellow emission band from internal d-d ((4)T(1)→(6)A(1)) transitions of the Mn(2+) ions in these nanocrystals is not suppressed in applied magnetic fields and does become circularly polarized. This polarization tracks the Mn(2+) magnetization, and is accompanied by a sizable energy splitting between right- and left-circular emission components that scales with the exciton-Mn sp-d coupling strength (which, in turn, is tunable with nanocrystal size). These data highlight the influence of strong quantum confinement on both the excitation and the emission mechanisms of magnetic ions in DMS nanomaterials.

Crystal Facet Engineering of CoPt Quantum Dots for Diverse Colloidal Heterostructures.

Precise control of crystal orientation, and specifically the exposed surface, is critical for the engineering of heterostructures. Here, using CoPt as a model system, we explore the energetics to expose suitable facets to promote the required heterostructure formation. Different heterostructures are grown ranging from core/shell structure, diffused interface, dumbbell structured dimers, and embedded island structures wherein these hybrids are fabricated via micro/macrolevel facet-selective growth. The reaction conditions used to achieve such diversity starting from the same seed offer insights into the growth mechanisms of these heterostructures. Such a microscopic understanding of surface chemistry paves the way for the design of new heterostructures with exciting properties.

Growth mechanistic insights into perovskite nanocrystals: dimensional growth.

The optical and electronic properties of lead halide perovskite nanocrystals have been explored extensively due to their increasing demand in photovoltaic and optoelectronic applications. But little is known about the growth kinetics of these nanocrystals. In this work, we demonstrate an interesting new mechanism using the method of arrested growth and precipitation to isolate the intermediates. We find that growth is driven by oriented attachment competing with the surface energetics. Hence, we observe a rare example of self-assembly driven dimensional growth characterized by suitable surface passivation that competes with the exposed surface facets through dimensional growth. This provides an explanation for not only the lack of size and shape tunability but also the emergence of a cubic shape rather than commonly observed spherical shapes in nanocrystals. Additionally, we find that this also corresponds to the observed phase transitions as well as correlating with pathways of decay of the photoluminescence spectra.

Copper Doping in II-VI Semiconductor Nanocrystals: Single-Particle Fluorescence Study.

Copper doping in II-VI semiconductor nanocrystals (NCs) has sparked enormous debate regarding the oxidation state of Cu ions and their hugely differing consequences in optoelectronic applications. The identity of a magnetically active Cu2+ ion or a magnetically inactive d10 Cu+ ion has generally been probed using optical techniques, and confusion arises from the spatial clutter that is part of the technique. One major probe that could declutter the data obtained from ensemble emission is single-particle fluorescence spectroscopy. In this work, using this very technique along with X-ray absorption spectroscopy probing the local environment of dopant ions, we study Cu-doped II-VI semiconductor NCs to find conclusive evidence on the oxidation state of Cu dopants and hence the mechanism of their emission. Detailed analysis of blinking properties has been used to study the single-particle nature of the NCs.

Temperature dependence of "elementary processes" in doping semiconductor nanocrystals.

Controlled doping is a critical step toward various unique nanostructures. This report shall demonstrate that doping chemistry of colloidal nanocrystals is much more complex than what has been proposed in the existing experimental and theoretical reports. Four individual processes, namely "surface adsorption", "lattice incorporation", "lattice diffusion", and "lattice ejection", will be identified, each of which possesses its own critical temperature. A given type of host nanocrystals can be switched from being impossible to dope to becoming successfully doped. The key is to program the reaction temperature to accommodate all elementary processes.

Investigation of the internal heterostructure of highly luminescent quantum dot-quantum well nanocrystals.

In this paper, we report on the growth and characterization of quantum dot-quantum well nanostructures with photoluminescence (PL) that is tunable over the visible range. The material exhibits a PL efficiency as high as approximately 60% and is prepared by reacting ZnS nanocrystals in turn with precursors for CdSe and ZnS in an attempt to form a simple "ZnS/CdSe/ZnS quantum-well structure". Through the use of synchrotron radiation-based photoelectron spectroscopy in conjunction with detailed overall compositional analysis and correlation with the size of the final composite nanostructure, the internal structure of the composite nanocrystals is shown to consist of a graded alloy core whose composition gradually changes from ZnS at the very center to CdSe at the onset of a CdSe layer. The outer shell is ZnS with a sharp interface, probably reflecting the relative thermodynamic stabilities of the parent binary phases. These contrasting aspects of the internal structure are discussed in terms of the various reactivities and are shown to be crucial for understanding the optical properties of such complex heterostructured nanomaterials.

Thermodynamics of Dual Doping in Quantum Dots.

Dual doping is a powerful way to tailor the properties of semiconductor quantum dots (QDs) arising out of host-dopant and dopant-dopant interactions. Nevertheless, it has seldom been explored due to a variety of thermodynamic challenges, such as the differential bonding strength and diffusion constant within the host matrix that integrates with the host in dissimilar ways. This work discusses the challenges involved in administering them within the constraints of one host under similar conditions of temperature, time, and chemical parameters such as solubility and reactivity using CoPt-doped CdS QDs as a model system. In addition, the various forces in play, such as Kirkendall diffusion, solid- and liquid-state diffusion, hard acid soft base interaction with the host, and the effect of lattice strain due to lattice mismatch, are studied to understand the feasibility of the core to doped transformation. These findings suggest a potential approach for manipulating the properties of semiconductors by dual doping engineering.