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1.
ACS Nano ; 2020 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-32584026

RESUMO

Quasi-two-dimensional (2D) semiconductor nanoplatelets manifest strong quantum confinement with exceptional optical characteristics of narrow photoluminescence peaks with energies tunable by thickness with monolayer precision. We employed scanning tunneling spectroscopy (STS) in conjunction with optical measurements to probe the thickness-dependent band gap and density of excited states in a series of CdSe nanoplatelets. The tunneling spectra, measured in the double-barrier tunnel junction configuration, reveal the effect of quantum confinement on the band gap taking place mainly through a blue-shift of the conduction band edge, along with a signature of 2D electronic structure intermixed with finite lateral-size and/or defects effects. The STS fundamental band gaps are larger than the optical gaps as expected from the contributions of exciton binding in the absorption, as confirmed by theoretical calculations. The calculations also point to strong valence band mixing between the light- and split-off hole levels. Strikingly, the energy difference between the heavy-hole and light-hole levels in the tunneling spectra are significantly larger than the corresponding values extracted from the absorption spectra. Possible explanations for this, including an interplay of nanoplatelet charging, dielectric confinement, and difference in exciton binding energy for light and heavy holes, are analyzed and discussed.

2.
J Phys Chem A ; 2020 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-32096402

RESUMO

Inorganic lead halide perovskite nanostructures show promise as the active layers in photovoltaics, light emitting diodes, and other optoelectronic devices. They are robust in the presence of oxygen and water, and the electronic structure and dynamics of these nanostructures can be tuned through quantum confinement. Here we create aligned bundles of CsPbBr3 nanowires with widths resulting in quantum confinement of the electronic wave functions and subject them to ultrafast microscopy. We directly image rapid one-dimensional exciton diffusion along the nanowires, and we measure an exciton trap density of roughly one per nanowire. Using transient absorption microscopy, we observe a polarization-dependent splitting of the band edge exciton line, and from the polarized fluorescence of nanowires in solution, we determine that the exciton transition dipole moments are anisotropic in strength. Our observations are consistent with a model in which splitting is driven by shape anisotropy in conjunction with long-range exchange.

3.
Bioconjug Chem ; 31(3): 567-576, 2020 03 18.
Artigo em Inglês | MEDLINE | ID: mdl-31894966

RESUMO

The photoactivation of plasma-membrane-tethered gold nanoparticles (AuNPs) for the photothermally driven depolarization of membrane potential has recently emerged as a new platform for the controlled actuation of electrically active cells. In this report, we characterize the relationship between AuNP concentration and AuNP-membrane separation distance with the efficiency of photoactivated plasma membrane depolarization. We show in differentiated rat pheochromocytoma (PC-12) cells that AuNPs capped with poly(ethylene glycol) (PEG)-cholesterol ligands localize to the plasma membrane and remain resident for up to 1 h. The efficiency of AuNP-mediated depolarization is directly dependent on the concentration of the NPs on the cell surface. We further show that the efficiency of AuNP-mediated photothermal depolarization of membrane potential is directly dependent on the tethering distance between the AuNP and the plasma membrane, which we control by iteratively tuning the length of the PEG linker. Importantly, the AuNP conjugates do not adversely affect cell viability under the photoactivation conditions required for membrane depolarization. Our results demonstrate the fine control that can be elicited over AuNP bioconjugates and establishes principles for the rational design of functional nanomaterials for the control of electrically excitable cells.

4.
J Chem Phys ; 151(23): 234106, 2019 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-31864259

RESUMO

We present an analysis of quantum confinement of carriers and excitons, and exciton fine structure, in metal halide perovskite (MHP) nanocrystals (NCs). Starting with coupled-band k · P theory, we derive a nonparabolic effective mass model for the exciton energies in MHP NCs valid for the full size range from the strong to the weak confinement limits. We illustrate the application of the model to CsPbBr3 NCs and compare the theory against published absorption data, finding excellent agreement. We then apply the theory of electron-hole exchange, including both short- and long-range exchange interactions, to develop a model for the exciton fine structure. We develop an analytical quasicubic model for the effect of tetragonal and orthorhombic lattice distortions on the exchange-related exciton fine structure in CsPbBr3, as well as some hybrid organic MHPs of recent interest, including formamidinium lead bromide (FAPbBr3) and methylammonium lead iodide (MAPbI3). Testing the predictions of the quasicubic model using hybrid density functional theory (DFT) calculations, we find qualitative agreement in tetragonal MHPs but significant disagreement in the orthorhombic modifications. Moreover, the quasicubic model fails to correctly describe the exciton oscillator strength and with it the long-range exchange corrections in these systems. Introducing the effect of NC shape anisotropy and possible Rashba terms into the model, we illustrate the calculation of the exciton fine structure in CsPbBr3 NCs based on the results of the DFT calculations and examine the effect of Rashba terms and shape anisotropy on the calculated fine structure.

5.
Nature ; 575(7784): 604-605, 2019 11.
Artigo em Inglês | MEDLINE | ID: mdl-31776486
6.
Nano Lett ; 19(7): 4797-4803, 2019 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-31199150

RESUMO

Aliovalent doping of CdSe nanocrystals (NCs) via cation exchange processes has resulted in interesting and novel observations for the optical and electronic properties of the NCs. However, despite over a decade of study, these observations have largely gone unexplained, partially due to an inability to precisely characterize the physical properties of the doped NCs. Here, electrostatic force microscopy was used to determine the static charge on individual, cation-doped CdSe NCs in order to investigate their net charge as a function of added cations. While the NC charge was relatively insensitive to the relative amount of doped cation per NC, there was a remarkable and unexpected correlation between the average NC charge and PL intensity, for all dopant cations introduced. We conclude that the changes in PL intensity, as tracked also by changes in NC charge, are likely a consequence of changes in the NC radiative rate caused by symmetry breaking of the electronic states of the nominally spherical NC due to the Coulombic potential introduced by ionized cations.

7.
Nano Lett ; 19(6): 4068-4077, 2019 06 12.
Artigo em Inglês | MEDLINE | ID: mdl-31088061

RESUMO

The bright emission observed in cesium lead halide perovskite nanocrystals (NCs) has recently been explained in terms of a bright exciton ground state [ Becker et al. Nature 2018 , 553 , 189 - 193 ], a claim that would make these materials the first known examples in which the exciton ground state is not an optically forbidden dark exciton. This unprecedented claim has been the subject of intense experimental investigation that has so far failed to detect the dark ground-state exciton. Here, we review the effective-mass/electron-hole exchange theory for the exciton fine structure in cubic and tetragonal CsPbBr3 NCs. In our calculations, the crystal field and the short-range electron-hole exchange constant were calculated using density functional theory together with hybrid functionals and spin-orbit coupling. Corrections associated with long-range exchange and surface image charges were calculated using measured bulk effective mass and dielectric parameters. As expected, within the context of the exchange model, we find an optically inactive ground exciton level. However, in this model, the level order for the optically active excitons in tetragonal CsPbBr3 NCs is opposite to what has been observed experimentally. An alternate explanation for the observed bright exciton level order in CsPbBr3 NCs is offered in terms of the Rashba effect, which supports the existence of a bright ground-state exciton in these NCs. The size dependence of the exciton fine structure calculated for perovskite NCs shows that the bright-dark level inversion caused by the Rashba effect is suppressed by the enhanced electron-hole exchange interaction in small NCs.

8.
Nano Lett ; 18(10): 6353-6359, 2018 10 10.
Artigo em Inglês | MEDLINE | ID: mdl-30193071

RESUMO

CuInS2 (CIS) quantum dots (QDs) have emerged as one of the most promising candidates for application in a number of new technologies, mostly due to their heavy-metal-free composition and their unique optical properties. Among those, the large Stokes shift and the long-lived excited state are the most striking ones. Although these properties are important, the physical mechanism that originates them is still under debate. Here, we use two-photon absorption spectroscopy and ultrafast dynamics studies to investigate the physical origin of those phenomena. From the two-photon absorption spectroscopy, we observe yet another unique property of CIS QDs, a two-photon absorption transition below the one-photon absorption band edge, which has never been observed before for any other semiconductor nanostructure. This originates from the inversion of the 1S and 1P hole level order at the top of the valence band and results in a blue-shift of the experimentally measured one photon absorption edge by nearly 100 to 200 meV. However, this shift is not large enough to account for the Stokes shift observed, 200-500 meV. Consequently, despite the existence of the below band gap optical transition, photoluminescence in CIS QDs must originate from trap sites. These conclusions are reinforced by the multiexciton dynamics studies. From those, we demonstrate that biexciton Auger recombination behaves similarly to negative trion dynamics on these nanomaterials, which suggests that the trap state is an electron donating site.

9.
J Am Chem Soc ; 140(42): 13753-13763, 2018 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-30255707

RESUMO

We developed a postsynthetic treatment to produce impurity n-type doped PbSe QDs with In3+ as the substitutional dopant. Increasing the incorporated In content is accompanied by a gradual bleaching of the interband first-exciton transition and concurrently the appearance of a size-dependent, intraband absorption, suggesting the controlled introduction of delocalized electrons into the QD band edge states under equilibrium conditions. We compare the optical properties of our In-doped PbSe QDs to cobaltocene treated QDs, where the n-type dopant arises from remote reduction of the PbSe QDs and observe similar behavior. Spectroelectrochemical measurements also demonstrate characteristic n-type signatures, including both an induced absorption within the electrochemical bandgap and a shift of the Fermi-level toward the conduction band. Finally, we demonstrate that the In3+ dopants can be reversibly removed from the PbSe QDs, whereupon the first exciton bleach is recovered. Our results demonstrate that PbSe QDs can be controllably n-type doped via impurity aliovalent substitutional doping.

10.
Nano Lett ; 18(7): 4061-4068, 2018 07 11.
Artigo em Inglês | MEDLINE | ID: mdl-29927610

RESUMO

In this Mini Review, we summarize major corrections to the dark-bright exciton theory [ Efros et al. Phys. Rev B 1996 , 54 , 4843 - 4856 ], which should be used for quantitative description of the band edge exciton in II-VI and III-V compound quantum-dot nanocrystals (NCs). The theory previously did not take into account the long-range exchange interaction, resulting in the under-estimation of the splitting between the upper bright and lower dark or quasi-dark exciton, as reported by several experimental groups. Another type of correction originates from the closeness in energy of the ground, 1S3/2, and the first excited, 1P3/2, hole levels in a spherical NC, resulting in significant energetic overlap of the levels from the 1S3/21Se and 1P3/21Se exciton manifolds connected with the ground 1Se electron level. The thermal occupation of the optically forbidden 1P3/21Se exciton levels changes the radiative decay time of the NCs at both helium and room temperatures. We demonstrate the role of both effects in CdSe NCs and compare our predictions with available experimental data.

11.
Nat Nanotechnol ; 13(4): 278-288, 2018 04.
Artigo em Inglês | MEDLINE | ID: mdl-29636589

RESUMO

Success in the projects aimed at providing an advanced understanding of the brain is directly predicated on making critical advances in nanotechnology. This Perspective addresses the unique interface of neuroscience and nanomaterials by considering the foundational problem of sensing neuron membrane voltage and offers a potential solution that may be facilitated by a prototypical nanomaterial. Despite substantial improvements, the visualization of instantaneous voltage changes within individual neurons, whether in cell culture or in vivo, at both the single-cell and network level at high speed remains complex and problematic. The unique properties of semiconductor quantum dots (QDs) have made them powerful fluorophores for bioimaging. What is not widely appreciated, however, is that QD photoluminescence is exquisitely sensitive to proximal electric fields. This property should be suitable for sensing voltage changes that occur in the active neuronal membrane. Here, we examine the potential role of QDs in addressing the important challenge of real-time optical voltage imaging.


Assuntos
Corantes Fluorescentes/análise , Neurônios/metabolismo , Imagem Óptica/métodos , Pontos Quânticos/análise , Animais , Sinalização do Cálcio , Eletricidade , Transferência Ressonante de Energia de Fluorescência/métodos , Humanos , Luminescência , Potenciais da Membrana , Neurônios/citologia
12.
PLoS Comput Biol ; 14(3): e1006032, 2018 03.
Artigo em Inglês | MEDLINE | ID: mdl-29584719

RESUMO

Vibrations are important cues for tactile perception across species. Whisker-based sensation in mice is a powerful model system for investigating mechanisms of tactile perception. However, the role vibration plays in whisker-based sensation remains unsettled, in part due to difficulties in modeling the vibration of whiskers. Here, we develop an analytical approach to calculate the vibrations of whiskers striking objects. We use this approach to quantify vibration forces during active whisker touch at a range of locations along the whisker. The frequency and amplitude of vibrations evoked by contact are strongly dependent on the position of contact along the whisker. The magnitude of vibrational shear force and bending moment is comparable to quasi-static forces. The fundamental vibration frequencies are in a detectable range for mechanoreceptor properties and below the maximum spike rates of primary sensory afferents. These results suggest two dynamic cues exist that rodents can use for object localization: vibration frequency and comparison of vibrational to quasi-static force magnitude. These complement the use of quasi-static force angle as a distance cue, particularly for touches close to the follicle, where whiskers are stiff and force angles hardly change during touch. Our approach also provides a general solution to calculation of whisker vibrations in other sensing tasks.


Assuntos
Tato/fisiologia , Vibrissas/fisiologia , Potenciais de Ação/fisiologia , Animais , Fenômenos Biomecânicos/fisiologia , Simulação por Computador , Mecanorreceptores/fisiologia , Camundongos , Neurônios/fisiologia , Estimulação Física/métodos , Percepção do Tato/fisiologia , Vibração
13.
Nature ; 553(7687): 189-193, 2018 01 10.
Artigo em Inglês | MEDLINE | ID: mdl-29323292

RESUMO

Nanostructured semiconductors emit light from electronic states known as excitons. For organic materials, Hund's rules state that the lowest-energy exciton is a poorly emitting triplet state. For inorganic semiconductors, similar rules predict an analogue of this triplet state known as the 'dark exciton'. Because dark excitons release photons slowly, hindering emission from inorganic nanostructures, materials that disobey these rules have been sought. However, despite considerable experimental and theoretical efforts, no inorganic semiconductors have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in caesium lead halide perovskites (CsPbX3, with X = Cl, Br or I) involves a highly emissive triplet state. We first use an effective-mass model and group theory to demonstrate the possibility of such a state existing, which can occur when the strong spin-orbit coupling in the conduction band of a perovskite is combined with the Rashba effect. We then apply our model to CsPbX3 nanocrystals, and measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright triplet character of the lowest exciton explains the anomalous photon-emission rates of these materials, which emit about 20 and 1,000 times faster than any other semiconductor nanocrystal at room and cryogenic temperatures, respectively. The existence of this bright triplet exciton is further confirmed by analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals, which are already used in lighting, lasers and displays, these excitons could lead to materials with brighter emission. More generally, our results provide criteria for identifying other semiconductors that exhibit bright excitons, with potential implications for optoelectronic devices.

14.
ACS Nano ; 11(6): 5598-5613, 2017 06 27.
Artigo em Inglês | MEDLINE | ID: mdl-28514167

RESUMO

We report the development of a quantum dot (QD)-peptide-fullerene (C60) electron transfer (ET)-based nanobioconjugate for the visualization of membrane potential in living cells. The bioconjugate is composed of (1) a central QD electron donor, (2) a membrane-inserting peptidyl linker, and (3) a C60 electron acceptor. The photoexcited QD donor engages in ET with the C60 acceptor, resulting in quenching of QD photoluminescence (PL) that tracks positively with the number of C60 moieties arrayed around the QD. The nature of the QD-capping ligand also modulates the quenching efficiency; a neutral ligand coating facilitates greater QD quenching than a negatively charged carboxylated ligand. Steady-state photophysical characterization confirms an ET-driven process between the donor-acceptor pair. When introduced to cells, the amphiphilic QD-peptide-C60 bioconjugate labels the plasma membrane by insertion of the peptide-C60 portion into the hydrophobic bilayer, while the hydrophilic QD sits on the exofacial side of the membrane. Depolarization of cellular membrane potential augments the ET process, which is manifested as further quenching of QD PL. We demonstrate in HeLa cells, PC12 cells, and primary cortical neurons significant QD PL quenching (ΔF/F0 of 2-20% depending on the QD-C60 separation distance) in response to membrane depolarization with KCl. Further, we show the ability to use the QD-peptide-C60 probe in combination with conventional voltage-sensitive dyes (VSDs) for simultaneous two-channel imaging of membrane potential. In in vivo imaging of cortical electrical stimulation, the optical response of the optimal QD-peptide-C60 configuration exhibits temporal responsivity to electrical stimulation similar to that of VSDs. Notably, however, the QD-peptide-C60 construct displays 20- to 40-fold greater ΔF/F0 than VSDs. The tractable nature of the QD-peptide-C60 system offers the advantages of ease of assembly, large ΔF/F0, enhanced photostability, and high throughput without the need for complicated organic synthesis or genetic engineering, respectively, that is required of traditional VSDs and fluorescent protein constructs.


Assuntos
Fulerenos/química , Potenciais da Membrana , Imagem Óptica/métodos , Peptídeos/química , Pontos Quânticos/química , Sequência de Aminoácidos , Animais , Encéfalo/citologia , Encéfalo/fisiologia , Feminino , Células HeLa , Humanos , Masculino , Camundongos , Microscopia de Fluorescência/métodos , Células PC12 , Ratos , Espectrometria de Fluorescência/métodos
15.
Nat Nanotechnol ; 12(6): 569-574, 2017 07.
Artigo em Inglês | MEDLINE | ID: mdl-28288118

RESUMO

Non-magnetic colloidal nanostructures can demonstrate magnetic properties typical for diluted magnetic semiconductors because the spins of dangling bonds at their surface can act as the localized spins of magnetic ions. Here we report the observation of dangling-bond magnetic polarons (DBMPs) in 2.8-nm diameter CdSe colloidal nanocrystals (NCs). The DBMP binding energy of 7 meV is measured from the spectral shift of the emission lines under selective laser excitation. The polaron formation at low temperatures occurs by optical orientation of the dangling-bond spins (DBSs) that result from dangling-bond-assisted radiative recombination of spin-forbidden dark excitons. Modelling of the temperature dependence of the DBMP-binding energy and emission intensity shows that the DBMP is composed of a dark exciton and about 60 DBSs. The exchange integral of one DBS with the electron confined in the NC is ∼0.12 meV.

16.
Nat Nanotechnol ; 11(8): 661-71, 2016 08 03.
Artigo em Inglês | MEDLINE | ID: mdl-27485584

RESUMO

Semiconductor nanocrystals offer an enormous diversity of potential device applications, based on their size-tunable photoluminescence, high optical stability and 'bottom-up' chemical approaches to self-assembly. However, the promise of such applications can be seriously limited by photoluminescence intermittency in nanocrystal emission, that is, 'blinking', arising from the escape of either one or both of the photoexcited carriers to the nanocrystal surface. In the first scenario, the remaining nanocrystal charge quenches photoluminescence via non-radiative Auger recombination, whereas for the other, the exciton is thought to be intercepted before thermalization and does not contribute to the photoluminescence. This Review summarizes the current understanding of the mechanisms responsible for nanocrystal blinking kinetics as well as core-shell engineering efforts to control such phenomena. In particular, 'softening' of the core-shell confinement potential strongly suppresses non-radiative Auger processes in charged nanocrystals, with successful non-blinking implementations demonstrated in CdSe-CdS core-thick-shell nanocrystals and their modifications.

17.
Nano Lett ; 15(10): 6848-54, 2015 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-26414396

RESUMO

The intrinsic properties of quantum dots (QDs) and the growing ability to interface them controllably with living cells has far-reaching potential applications in probing cellular processes such as membrane action potential. We demonstrate that an electric field typical of those found in neuronal membranes results in suppression of the QD photoluminescence (PL) and, for the first time, that QD PL is able to track the action potential profile of a firing neuron with millisecond time resolution. This effect is shown to be connected with electric-field-driven QD ionization and consequent QD PL quenching, in contradiction with conventional wisdom that suppression of the QD PL is attributable to the quantum confined Stark effect.


Assuntos
Sondas Moleculares , Pontos Quânticos , Semicondutores , Luminescência
18.
Nano Lett ; 15(6): 4214-22, 2015 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-25919576

RESUMO

We predict theoretically that nonmagnetic CdSe nanocrystals may possess macroscopic magnetic moments due to the formation of dangling-bond magnetic polarons (DBMPs). A DBMP is created in optically pumped nanocrystals by dynamic polarization of dangling bond spins (DBSs) at the nanocrystal surface during radiative recombination of the ground state "dark" exciton assisted by a spin-flip of the DBS. The formation of DBMPs suppresses the radiative recombination of the dark exciton and leads to a temperature-dependent contribution to the Stokes shift of the photoluminescence. This model consistently explains the experimentally observed low-temperature photoluminescence features of nonmagnetic CdSe nanocrystals as manifestations of their spin-related magnetic properties.

19.
Nano Lett ; 15(3): 2092-8, 2015 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-25693512

RESUMO

We calculate the rate of nonradiative Auger recombination in negatively charged CdSe nanocrystals (NCs). The rate is nonmonotonic, strongly oscillating with NC size, and sensitive to the NC surface. The oscillations result in nonexponential decay of carriers in NC ensembles. Using a standard single-exponential approximation of the decay dynamics, we determine the apparent size dependence of the Auger rate in an ensemble and derive CdSe surface parameters consistent with the experimental dependence on size.

20.
ACS Nano ; 9(1): 725-32, 2015 Jan 27.
Artigo em Inglês | MEDLINE | ID: mdl-25531244

RESUMO

The electronic structure of single InSb quantum dots (QDs) with diameters between 3 and 7 nm was investigated using atomic force microscopy (AFM) and scanning tunneling spectroscopy (STS). In this size regime, InSb QDs show strong quantum confinement effects which lead to discrete energy levels on both valence and conduction band states. Decrease of the QD size increases the measured band gap and the spacing between energy levels. Multiplets of equally spaced resonance peaks are observed in the tunneling spectra. There, multiplets originate from degeneracy lifting induced by QD charging. The tunneling spectra of InSb QDs are qualitatively different from those observed in the STS of other III-V materials, for example, InAs QDs, with similar band gap energy. Theoretical calculations suggest the electron tunneling occurs through the states connected with L-valley of InSb QDs rather than through states of the Γ-valley. This observation calls for better understanding of the role of indirect valleys in strongly quantum-confined III-V nanomaterials.

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