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Here, we report mode-specific resonance Raman enhancements of ligands covalently bound to the surface of colloidal CdSe nanocrystals (NCs). By the systematic comparison of a set of structural derivatives, the extent of resonance Raman enhancement is shown to be directly related to the molecular symmetry of the bound ligands. The enhancement dependence on molecular symmetry is further discussed in terms of Franck-Condon and Herzberg-Teller contributions and their associated selection rules. We further show that resonance Raman may be used to distinguish between possible surface binding motifs of bidentate ligands under continuous wave excitation. More generally, this work demonstrates the usefulness of resonance Raman as a characterization tool when characterizing adsorbed molecular species on semiconductor NC surfaces.

Despite the impressive abilities of coherent multi-dimensional spectroscopy (CMDS), its’ implementation is limited due to the complexity of continuum generation and required phase stability between the pump pulse pair. In light of this, we have implemented a system producing sub-10 fs pulses with tunable central wavelength. Using a commercial OPA to drive a hollow-core fiber, the system is extremely simple. Output pulse energies lie in the 40-80 μJ range, more than sufficient for transmission through the pulse shaping optics and beam splitters necessary for CMDS. Power fluctuations are minimal, mode quality is excellent, and spectral phase is well behaved at the output. To demonstrate the strength of this source, we measure the two-dimensional spectrum of CdSe quantum dots over a range of population times and find clean signals and clear phonon vibrations. This combination of OPA and hollow-core fiber provides a substantial extension to the capabilities of CMDS.

Semiconductor nanocrystals have seen much use for their narrow emission line widths for display and lighting applications. Recent progress on semiconductor nanocrystals has suggested the possibilit...

Semiconductor nanocrystals are known to have properties of bulk semiconductors as well as molecules. Two rules that govern molecules are that there is no dual emission (Kasha) and there is no spectrum to the emission quantum yield (Vavilov). We show that the latter rule of molecular spectroscopy is generally violated in semiconductor nanocrystals. Through experiments and theory on CdSe and perovskite nanocrystals, these violations are shown to arise via hot carrier effects. Experiments and simple phenomenology reveal that quantum yield spectra arise because of enhanced hot carrier trapping rates. A semiclassical electron-transfer theory rationalizes a microscopic picture of the carrier kinetics. These effects are especially significant when quantifying syntheses of bright emitters such as perovskite nanocrystals. These effects are also a general approach to simple steady-state measurements of the action of hot carrier kinetics.

Excitonic-state-resolved pump/probe spectroscopy is performed on semiconductor dot-in-rod nanocrystals. Using excitonic-state-resolved pumping we are able to resolve effects of the rod upon exciton...

Semiconductor nanocrystals have been extensively studied for optoelectronic applications including light emission, the focus of this review. Historically, the core of the nanocrystal was the main aspect of the system as it gives rise to the confined excitons and multiexcitons which absorb and emit light. In addition to the core, the surface or interface of these nanocrystals is also important by virtue of their small size. Yet, our understanding of the surface is in its early stages in terms of both chemical and electronic structure. Here, we review the ways in which the interface can control the excitonics, which gives rise to optoelectronic function. We focus our discussion on the ways in which the interface can control optical gain for nanocrystal lasers and white light generation for nanocrystal based light emitting diodes. These processes are connected to different interfacial structures. Finally, we discuss two new applications based on surface electronic structure control: optical switching and opt...

Coherent Multi-dimensional Spectroscopy is ideally suited to investigate many-body effects in semiconductor nanostructures. Here we employ 2D optical spectroscopy on the model system of CdSe quantum dots to reveal the structure of the bandedge biexciton.

The interface of semiconductor nanocrystals is a critical factor for determining their performance in light emissive applications. Traditional nanocrystals have an abrupt termination of the core/shell interface. Recent synthetic work has focused upon developing graded core/shell interfaces via alloying. Here, we employ femtosecond state-resolved pump/probe spectroscopy, temperature-dependent photoluminescence spectroscopy, and a microscopic theory of interfacial charge trapping to reveal the manner in which a graded interface controls the main optical gain metrics: threshold, bandwidth, and lifetime in the CdSe/Cd,Zn,S core/shell system. Photoluminescence spectroscopy in conjunction with semiclassical electron transfer theory reveals the absence of an interfacial electronic state. This absence of a surface/interfacial state is unique to these nanocrystals with a graded shell structure, enabling trap free performance. Excitonic state-resolved pump/probe spectroscopy reveals that the higher excitons do not ...

We report on the performance of Ar-filled hollow-core fibers (HCFs) capillary driven by long pulses ( > 100 fs) of moderate energy ( < 600 μ J) for coherent multidimensional spectroscopy in the visible range. The source is characterized by high overall transmission and excellent spatial mode. Broadening is achieved by self-phase modulation. Notably, the uncompressed visible output is shorter than the input pulse. This peculiar observation is explained by the structure of self-phase modulated pulses, coupled with spectral filtering. By virtue of its simplicity, low requirements, spectral stability, and the excellent properties of its spatial output, HCFs can provide an interesting alternative to achieve broadband visible pulses for broadband optical excitation and multidimensional spectroscopy applications.

Semiconductor nanostructures have shown promise for light emission across various intensity regimes. Desired performance objectives of photoluminescence efficiency, low gain threshold, large gain lifetime and bandwidth have not been met by any one nanocrystal. A physical understanding of the design principles governing these objectives is also lacking. We show that a carefully engineered CdSe/Cd,Zn,S core/shell nanocrystal uniquely meets all criteria. The key factor allowing for these improvements is the gradual core/shell boundary, which decouples the surface electronic states.

We present a detailed analysis of a setup capable of arbitrary amplitude, phase, and polarization shaping of broadband visible femtosecond pulses at 1 kHz via a pair of actively phase stabilized acousto-optic programmable dispersive filters arranged in a Mach-Zehnder interferometer geometry. The setup features phase stability values around λ/225 at 580 nm as well as degrees of polarization of at least 0.9 for any polarization state. Both numbers are important metrics to evaluate a setup's potential for applications based on polarization-shaped femtosecond pulses, such as fully coherent multi-dimensional electronic spectroscopy.

Semiconductor based light generation is of enormous contemporary interest, given that a large fraction of global energy is used for lighting. White-light semiconductor colloidal quantum dots may find application in future solid state lighting technologies. These dots possess two inherent emission bands, a narrow emissive band attributed to a quantum confined exciton, and a broad emission associated with surface trapping. White light CdSe colloidal semiconductor nanocrystals passivated with phosphonic acids were synthesized by a hot-injection method. Aliquots of this sample are then ligand exchanged with amine and thiol ligands. These samples are embedded in polystyrene films, and a series of temperature dependent photoluminescence measurements are performed. The spectral width as a function of temperature is plotted for all samples. These data are then analyzed in terms of three models. The results suggest that surface line shape broadness may be tied to strong electron-phonon coupling and is largely ligand dependent. The amine and phosphonic acid passivated samples showed large temperature dependence over the range studied, whereas the thiol passivated sample had a lower dependence. This is tentatively explained in terms of hole delocalization in the case of thiol passivation.

The realistic electronic structure of semiconductor nanocrystals is characterized by excitonic fine structure and atomistic symmetry breakings that are challenging to resolve experimentally. Exciton-phonon coupling is one of the most sensitive measures of the excitonic wave functions of the nanocrystals. Here, we exploit this sensitivity via chirped pulse and polarization resolved femtosecond pump/probe spectroscopy of colloidal CdSe nanocrystals. Pulse chirp measurements and simulations are used to explore the contributions of excited- and ground-state vibrational wavepackets to the observed coherent phonons in the pump/probe signals. Polarization resolved pump/probe spectroscopy is used to explore electronic and vibrational polarization anisotropies. We find no electronic polarization anisotropy, whereas vibrational anisotropy is preserved.

Optical pumping of semiconductor nanocrystals with femtosecond pulse sequences was performed in order to modulate multiexciton populations. We show for the first time that control of multiexciton populations produces high speed modulation of stimulated emission. Upon the basis of the speed of multiexcitonic processes in nanocrystals, we show modulation rates approaching 1 THz by virtue of strong quantum confinement effects. Employing femtosecond optical pulse sequences, we demonstrate all-optical logic using these nanocrystals in two forms: an AND gate, and an inverter, a key step toward all optical signal processing.

It is well-known that the shape, size, and composition of semiconductor nanocrystals give rise to a quantized manifold of electronic states, that is, excitons. In addition, these nanocrystals can support multiple excitations per particle under relatively modest conditions. Beyond a laboratory curiosity, these multiexcitons dictate a wide variety of optoelectronic properties of semiconductor nanocrystals including those from lasers, light-emitting diodes, photon sources, and possibly photovoltaics. Whereas their existence has been known for some time, observation of the structure and dynamics of multiexcitons has remained elusive due to their ultrafast lifetimes. In this Perspective, we discuss the first glimpses of the structural dynamics of multiexcitons in CdSe semiconductor nanocrystals as revealed by excitonic state-resolved femtosecond pump/probe spectroscopy. These measurements of multiexciton formation, cooling, and recombination are related to the optical gain performance of nanocrystals. In parti...

Semiconductor quantum dots are of interest as optical gain media for lasing applications. Here we report on efficient, broad bandwidth optical gain in the CdSe/ZnS/CdSe quantum dot/barrier/quantum shell nanocrystal. These nanocrystals are known to support spontaneous emission from both CdSe phases, offering promise for lasing applications via wave function engineering. The CdSe/ZnS/CdSe nanocrystals were found to have enhanced optical gain characteristics relative to CdSe quantum dots, as shown using femtosecond transient absorption spectroscopy. The enhancement of gain metrics such as bandwidth and efficiency arises from stimulated emission from quantum shell-enabled excitations. These shell-enabled excitations increase gain bandwidth via emission from new transitions and increase efficiencies via tailored biexciton interactions. This unique two-color character in both spontaneous emission and optical gain is rationalized by slow exciton cooling from the core/shell states into the core localized quantum ...

The quantum dot, one of the central materials in nanoscience, is a semiconductor crystal with a physical size on the nanometer length scale. It is often called an "artificial atom" because researchers can create nanostructures which yield properties similar to those of real atoms. By virtue of having a size in between molecules and solids, the quantum dot offers a rich palette for exploring new science and developing novel technologies. Although the physical structure of quantum dots is well known, a clear understanding of the resultant electronic structure and dynamics has remained elusive. However, because the electronic structure and dynamics of the dot, the "excitonics", confer its function in devices such as solar cells, lasers, LEDs, and nonclassical photon sources, a more complete understanding of these properties is critical for device development. In this Account, we use colloidal CdSe dots as a test bed upon which to explore four select issues in excitonic processes in quantum dots. We have developed a state-resolved spectroscopic approach which has yielded precise measurements of the electronic structural dynamics of quantum dots and has made inroads toward creating a unified picture of many of the key dynamic processes in these materials. We focus on four main topics of longstanding interest and controversy: (i) hot exciton relaxation dynamics, (ii) multiexcitons, (iii) optical gain, and (iv) exciton-phonon coupling. Using this state-resolved approach, we reconcile long standing controversies related to phenomena such as exciton cooling and exciton-phonon coupling and make surprising new observations related to optical gain and multiexcitons.

By direct observation of coherent acoustic phonons, we demonstrate a novel extrinsic piezoelectric response in colloidal CdSe semiconductor quantum dots. This response is driven by the migration of charges to the surface of the quantum dot on a vibrationally impulsive time scale. Surface- and fluence-dependent studies reveal that the observed carrier capture based piezo response is controllable and is at least an order of magnitude larger than the intrinsic piezo response of wurtzite CdSe.

Semiconductor nanocrystals have been synthesized that support intrinsic dual emission from the excitonic core as well as the surface. By virtue of chemical control of the thermodynamics of the core/surface equilibria, these nanocrystals support ratiometric temperature sensing over a broad temperature scale. This surface-chemistry-based approach for creating intrinsic dual emission enables a completely new strategy for application of these nanocrystals in optical nanothermometry.

Excitation transfer pathways in colloidal core/barrier/shell nanomaterials were investigated in the CdSe/ZnS/CdSe system. Absorption of light in the outer CdSe shell results in emission from the band edge of the CdSe core. The CdSe quantum shell acts as a light harvester that indirectly increases the brightness of the CdSe quantum-dot core. Spectroscopic evidence suggesting that the CdSe core and shell are coupled by tunneling of excitons through the ZnS barrier is provided. Competition kinetic analysis shows that charge transport competes effectively with hole capture by pyridine at the outer CdSe shell and exciton relaxation within the outer CdSe shell.

Ultrafast coherent multi-dimensional spectroscopies form a powerful set of techniques to unravel complex processes, ranging from light-harvesting, chemical exchange in biological systems to many-body interactions in quantum-confined materials. Yet these spectroscopies remain complex to implement at the high frequencies of vibrational and electronic transitions, thereby limiting their widespread use. Here we demonstrate the feasibility of two-dimensional spectroscopy at optical frequencies in a single beam. Femtosecond optical pulses are spectrally broadened to a relevant bandwidth and subsequently shaped into phase coherent pulse trains. By suitably modulating the phases of the pulses within the beam, we show that it is possible to directly read out the relevant optical signals. This work shows that one needs neither complex beam geometries nor complex detection schemes in order to measure two-dimensional spectra at optical frequencies. Our setup provides not only a simplified experimental design over standard two-dimensional spectrometers but its optical readout also enables novel applications in microscopy.

We report on a setup for coherent multidimensional spectroscopy based on visible continuum generation obtained by propagating 130 fs

Small CdSe semiconductor nanocrystals with diameters below 2 nm are thought to emit white light due to random surface defects which result in a broad distribution of midgap emitting states, thereby preventing rational design of small nanocrystal white light emitters. We perform temperature dependent photoluminescence experiments before and after ligand exchange and electron transfer simulations to reveal a very simple microscopic picture of the origin of the white light. These experiments and simulations reveal that these small nanocrystals can be physically modeled in precisely the same way as normal-sized semiconductor nanocrystals; differences in their emission spectra arise from their surface thermodynamics. The white light emission is thus a consequence of the thermodynamic relationship between a core excitonic state and an optically bright surface state with good quantum yield. By virtue of this understanding of the surface and the manner in which it is coupled to the core excitonic states of these nanocrystals, we show both chemical and thermodynamic control of the photoluminescence spectra. We find that using both temperature and appropriate choice in ligands, one can rationally control the spectra so as to engineer the surface to target color rendering coordinates for displays and white light emitters.

We demonstrate a dual pulse-shaper setup capable of independent polarization, phase, and amplitude control over each pulse. By using active phase stabilization, we achieve a phase stability of ~λ/314 between the two pulse shapers, making the dual-shaper setup suitable for both two-quantum and one-quantum measurements. The setup is compact and easily switchable between pump-probe and collinear geometries. We further illustrate the functionality of the dual-shaper setup by performing two-color 2D visible spectroscopy on colloidal CdSe quantum dots in pump-probe geometry.

In this chapter, the influence of quantum confinement upon light amplification is reviewed. Emphasis is placed upon the two broad classes of three-dimensionally confined nanostructures: self-assembled quantum dots and colloidal quantum dots. Fabrication, carrier dynamics, and state-of-the-art-device results for these classes of quantum dots are reviewed.

We report on the electronic structure of biexcitons in CdSe quantum dots using state-selective femtosecond pump/probe spectroscopy. The pump/probe experiments are compared to direct probing of biexcitons via two-dimensional electronic spectroscopy.

Optical gain in strongly confined colloidal semiconductor quantum dots is measured using state resolved pump/probe spectroscopy. Though size tunable optical amplification has been previously reported for these materials, the influence of confinement enhanced multiexcitonic interactions has limited prior demonstrations to specific particle sizes or host media. Here we show that the influence of the interfering multiexcitonic interactions, and hence the development of optical gain, is dependent on the identity of the initially prescribed excitonic state. By maintaining a constant excitonic state in the size tunable electronic structure of these materials, we recover the predicted universal development of optical gain, reflected by size-independent occupation thresholds, and differential gains. In addition, we explicitly compare the influence of surface passivation on the development and lifetime of the optical gain. Furthermore, we introduce a general, state-resolved pumping scheme which enables control over the optical gain spectrum. The capacity to manipulate the optical gain spectra of these spherically confined systems is evident in both the measured stimulated emission and amplified spontaneous emission. We anticipate that state-resolved optical excitation will be a useful method of enabling the development and manipulation of optical gain in any quantized nanostructure.

We report on the electronic structure of the band-edge biexciton in colloidal CdSe quantum dots using femtosecond spectroscopy and atomistic many-body pseudopotential calculations. Time-resolved spectroscopy shows that optical transitions between excitonic and biexcitonic states are distinct for absorptive and emissive transitions, leading to a larger Stokes shift for the biexciton than for the single exciton. The calculations explain the experimental results by showing that there is a previously unobserved electronic substructure to the band-edge biexciton which yields two distinct families of transitions.

Excitonic state-resolved optical pumping experiments were performed on strongly confined semiconductor quantum dots. We demonstrate for the first time that optical gain is dependent upon the initial excitonic state. By prescribing the specific multiexcitonic states which can create, block, and ultimately control optical gain spectra, we recover the theoretically predicted size independence, even in systems which previously showed zero gain. In addition, we show for the first time that stimulated emission in quantum dots can be controlled via specific multiexcitonic interactions.

Using state-selective excitation to tailor multi-exciton interactions, we have demonstrated that optical gain in strongly confined semiconductor quantum dots is a completely universal, size independent, and intrinsic property of these materials.

We analyze epitaxially grown InGaN/GaN dot-in-a-wire heterostructures to relate growth and design properties to trends seen in photoluminescence (PL) and resonance Raman spectra. Temperature-dependent PL measurement of these dot-in-a-wire heterostructures illustrate an expected decrease in integrated PL emission and an unusual narrowing of peak width with increasing temperature. Information extracted from Resonance Raman spectra was utilized in a time-dependent model to analyze and to simulate PL spectra. These spectra were found to be in good agreement with the experimental PL data and provided insight into the broadening mechanisms affecting the samples. PL measurements were taken as a function of position on the sample and radial variation of peak energies was observed. This variation was attributed to the radial temperature gradient present during nanowire growth. These additional characteristics of the nanowire heterostructures will allow for increased understanding of these systems potentials for applications in white light emitting diodes.

We demonstrate a pulse-shaper capable of independent polarization, phase and amplitude control over each pulse. The set-up is compact and easily switchable between pump-probe and collinear geometries.

Multiple exciton recombination (MER) and multiple exciton generation (MEG) are two of the main processes for assessing the usefulness of quantum dots (QDs) in photovoltaic devices. Recent experiments, however, have shown that a firm understanding of both processes is far from well established. By performing surface-dependent measurements on colloidal CdSe QDs, we find that surface-induced charge trapping processes lead to false MER and MEG signals resulting in an inaccurate measurement of these processes. Our results show that surface-induced processes create a significant contribution to the observed discrepancies in both MER and MEG experiments. Spectral signatures in the transient absorption signals reveal the physical origin of these false signals.