Doped Semiconductor Nanocrystals Research Articles

(Invited) Plasmon Induced Hot Electron Transfer from Doped Semiconductor Nanocrystals

In recent years, a new class of plasmonic materials based on doped semiconductor NCs has been developed. Similar to noble metals, localized surface plasmon resonances in doped semiconductor NCs arises from the coherent collective oscillation of free carriers within the NCs. The wide tunability of free carrier concentration results in tunable plasmon bands spanning from the visible to mid-infrared regime and these plasmonic semiconductor NCs have been reported to drive plasmonic hot carrier photocatalysis under near IR light illumination. These reports suggest that plasmonic semiconductors is an interesting material platform for efficient near IR driven hot carrier photocatalysis. So far the reported efficiencies are low and the mechanisms of hot carrier generation, transfer and recombination are unclear. There are interesting similarities and differences between metal and semiconductor plasmonics. First, plasmons in semiconductors can decay by inter- (band gap) and intra- band plasmon decay. Furthermore, charge transfer transition in semiconductor heterostructures have been extensively reported; can plasmon decay in plasmonic-semiconductor/semiconductor junctions proceed by exciting interfacial ET across the junction, similar to the PICTT pathway reported for metal/semiconductor junctions? Second, in plasmonic semiconductor materials, where there is a lack of states within the p-semiconductor bandgap, the transferred electrons in the accepting semiconductor CB can recombine only with the VB holes in the plasmonic semiconductor. This process requires dissipation of ~ >1 eV energy, which may slow down the recombination rate. In this talk, I will discuss our recent progresses in studying plasmon induced hot electron transfer and recombination in plasmonic semiconductor/semiconductor interfaces.

Colloidal‐Doped Semiconductor Nanocrystals Embedded in One‐Dimensional Photonic Crystals for Ultrafast Photonics

The optical properties of strongly doped semiconductor nanocrystals depend strongly on the carrier density of the nanocrystals. These characteristics can be exploited for the design of innovative optical devices based on ultrafast switching potentially in the THz modulation bandwidth. In this study, the optical response of one‐dimensional photonic crystals incorporating colloidal nanoparticles of a highly doped semiconductor such as indium tin oxide (ITO) is investigated, taking into consideration the angular dependence of the photonic band gap and the position dependence of the photonic band gap on the light‐induced tunability of the ITO doping.

Near-Infrared Dual-Band LSPR Coupling in Oriented Assembly of Doped Metal Oxide Nanocrystal Platelets.

Coupling effects of localized surface plasmon resonance (LSPR) represent an efficient means to tune the plasmonic modes and to enhance the near-field. While LSPR coupling in metal nanoparticles has been extensively explored, limited attention has been given to heavily doped semiconductor nanocrystals. Here, we investigate the LSPR coupling behavior of Cs-doped tungsten oxide (CsxWO3-δ) nanocrystal platelets as they undergo an oriented assembly into parallel stacks. The oriented assembly was achieved by lowering the dispersion stability of the colloidal nanoplatelets, of which the basal surface was selectively ligand-functionalized. This assembly induces simultaneous blue-shifts and red-shifts of dual-mode LSPR peaks without compromising the intensity and quality factor. This stands in contrast to the significant damping, broadening, and overall red-shift of the LSPR observed in random assemblies. Computational simulations successfully replicate the experimental observations, affirming the potential of this coupling phenomenon of near-infrared dual-mode LSPR in diverse applications including solar energy, bio-optics, imaging, and telecommunications.

Investigation of LSPR Coupling Effects toward the Rational Design of CsxWO3–δ Based Solar NIR Filtering Coatings

AbstractThe optical range of localized surface plasmon resonance (LSPR) is extended into the infrared region, thanks to the development of highly doped semiconductor nanocrystals. Particularly, the near‐infrared (NIR) range holds a significant interest in managing solar radiation. However, practical applications necessitate the arrangement of particles, which is known to possibly impact their optical properties through LSPR coupling effects. How such coupling modifies the LSPR response in semiconductor hosts remains largely unexplored. In this study, a protocol for producing composite coatings composed of cesium‐doped tungsten bronze nanocrystals embedded in a silica matrix is presented. Achieving individual dispersion of nanocrystals is made possible through careful selection of a surface polyglycerol ligand exchange. This allows to tune the interparticle distance by adjusting the nanocrystal volume fraction in the composite. The findings demonstrate that LSPR coupling effects significantly influence the LSPR intensity of nanocrystals in the composite when the nanocrystal‐to‐nanocrystal distance matches their size. Beyond elucidating the LSPR coupling effect, this study provides insights into the potential use of Cs‐HTB nanocrystals for solar control applications. Through the optimization of morphology and film structure, remarkable selectivity is obtained in terms of maintaining good transparency in the visible range while achieving high absorption in the NIR.

Heavily Doped Si Nanocrystals Formed in P-(SiO/SiO2) Multilayers: A Promising Route for Si-Based Infrared Plasmonics

As building blocks of multifunctional materials involving coupling at the nanoscale, highly doped semiconductor nanocrystals are of great interest for potential applications in nanophotonics. In this work, we investigate the plasmonic properties of highly doped Si nanocrystals embedded in a silica matrix. These materials are obtained by evaporation of heavily phosphorus-doped SiO/SiO2 multilayers in an ultrahigh vacuum chamber followed by rapid thermal annealing. For P contents between 0.7 and 1.9 atom %, structural investigations at the nanoscale give clear evidence that P atoms are mainly located in the core of Si nanocrystals with concentrations reaching up to 10 atom %, i.e., well beyond the solid solubility limit of P in bulk Si. Alloying and formation of SiP nanoparticles are observed for P contents exceeding 4 atom % in the multilayer. Infrared absorption measurements give evidence of a localized surface plasmon resonance located in the 3–6 μm range. A core–shell structure was used to model Si nanocrystals embedded in a silica matrix. Based on the Mie theory and the Drude model, both the mobility and the free charge carrier density were extracted from the simulation, with values reaching 27 cm2 V–1 s–1 and 2.3 × 1020 cm–3, respectively. This results in a dopant activation rate of about 8%.

Tunable metal halide perovskite light emitting transistor based on doped semiconductor nanocrystals

Tunable metal halide perovskite light emitting transistor based on doped semiconductor nanocrystals

Tunable metal halide perovskite light emitting transistor based on doped semiconductor nanocrystals

Tunable metal halide perovskite light emitting transistor based on doped semiconductor nanocrystals

Role of Magnetic Coupling in Photoluminescence Kinetics of Mn2+-Doped ZnS Nanoplatelets.

Mn2+-doped semiconductor nanocrystals with tuned location and concentration of Mn2+ ions can yield diverse coupling regimes, which can highly influence their optical properties such as emission wavelength and photoluminescence (PL) lifetime. However, investigation on the relationship between the Mn2+ concentration and the optical properties is still challenging because of the complex interactions of Mn2+ ions and the host and between the Mn2+ ions. Here, atomically flat ZnS nanoplatelets (NPLs) with uniform thickness were chosen as matrixes for Mn2+ doping. Using time-resolved (TR) PL spectroscopy and density functional theory (DFT) calculations, a connection between coupling and PL kinetics of Mn2+ ions was established. Moreover, it is found that the Mn2+ ions residing on the surface of a nanostructure produce emissive states and interfere with the change of properties by Mn2+-Mn2+ coupling. In a configuration with suppressed surface contribution to the optical response, we show the underlying physical reasons for double and triple exponential decay by DFT methods. We believe that the presented doping strategy and simulation methodology of the Mn2+-doped ZnS (ZnS:Mn) system is a universal platform to study dopant location- and concentration-dependent properties also in other semiconductors.

Enhanced anodic electrochemiluminescence due to efficient exchange recombination and its sensing application

To obtain semiconductor nanocrystals (NCs) with strong anodic electrochemiluminescence (ECL) remains a challenge due to their insufficiency to resist following corrosion upon holes injection to the NCs. Herein, we report strong and stable anodic ECL generated from 0.8 at% Mn2+ doped CdS NC films on indium tin oxide (ITO) electrode in the presence of coreactant triethanolamine (TEOA) under potential scan to +1.5 V vs. saturated calomel electrode (SCE), which is much more negative than the valence band potential of host NCs. The Mn2+ doping leads to an 8-fold enhancement in anodic ECL intensity in comparison with undoped CdS NC films due to efficient Mn excitation via nonradiative recombination energy transfer, i.e., exchange recombination. The efficiency is dependent on Mn2+ doping amount as well as applied potential for holes injection with the maximum obtained when the charge transfer to Mn dopants is possible and the energy gap between conduction band and applied potential matches with Mn excitation. This anodic ECL was used to detect dopamine, a model analyte, showing a wide linear range from 5 nM to 1 μM with a detection limit of 1 nM at S/N=3. This work provides a new insight into ECL generation in doped semiconductor NCs. The Mn2+ doped CdS NCs passivated by carboxylic groups display great potential in future development of biosensors.

Imaging Infrared Plasmon Hybridization in Doped Semiconductor Nanocrystal Dimers.

Carrier-doped semiconductor nanocrystals (NCs) offer strong plasmonic responses at frequencies beyond those accessible by conventional plasmonic nanoparticles. Like their noble metal analogues, these emerging materials can harness free space radiation and confine it to the nanoscale but at resonance frequencies that are natively infrared and spectrally tunable by carrier concentration. In this work we combine monochromated STEM-EELS and theoretical modeling to investigate the capability of colloidal indium tin oxide (ITO) NC pairs to form hybridized plasmon modes, providing an additional route to influence the IR plasmon spectrum. These results demonstrate that ITO NCs may have greater coupling strength than expected, emphasizing their potential for near-field enhancement and resonant energy transfer in the IR region.

Intrinsic Optical and Electronic Properties from Quantitative Analysis of Plasmonic Semiconductor Nanocrystal Ensemble Optical Extinction

The optical extinction spectra arising from localized surface plasmon resonance in doped semiconductor nanocrystals (NCs) have intensities and lineshapes determined by free charge carrier concentrations and the various mechanisms for damping the oscillation of those free carriers. However, these intrinsic properties are convoluted by heterogeneous broadening when measuring spectra of ensembles. We reveal that the traditional Drude approximation is not equipped to fit spectra from a heterogeneous ensemble of doped semiconductor NCs and produces fit results that violate Mie scattering theory. The heterogeneous ensemble Drude approximation (HEDA) model rectifies this issue by accounting for ensemble heterogeneity and near-surface depletion. The HEDA model is applied to tin-doped indium oxide NCs for a range of sizes and doping levels but we expect it can be employed for any isotropic plasmonic particles in the quasistatic regime. It captures individual NC optical properties and their contributions to the ensemble spectra thereby enabling the analysis of intrinsic NC properties from an ensemble measurement. Quality factors for the average NC in each ensemble are quantified and found to be notably higher than those of the ensemble. Carrier mobility and conductivity derived from HEDA fits matches that measured in the bulk thin film literature.

Influence of Crystalline and Shape Anisotropy on Electrochromic Modulation in Doped Semiconductor Nanocrystals

Localized surface plasmon resonance (LSPR) modulation appearing in the near-infrared range in doped semiconductor nanocrystals improves electrochromic performance. Although crystalline and shape an...

Antimony-Doped Tin Oxide Nanocrystals for Enhanced Photothermal Theragnosis Therapy of Cancers.

The doped semiconductor nanocrystal with free holes in valence band exhibits strong near-infrared (NIR) local surface plasmon resonance effects, which is essential for photothermal agents. Herein, the hydrophilic Sb doped SnO2 nanocrystals were successfully prepared by a simple hydrothermal synthesis method. The doping makes the Sb doped SnO2 nanocrystals possessing defect structures. Compared with the un-doped SnO2 nanocrystals, Sb doped SnO2 nanocrystals exhibit stronger absorption in the NIR region from 500 to 1,100 nm and higher photothermal conversion efficiency (up to 73.6%) which makes the synthesized Sb doped SnO2 nanocrystals be used as excellent photothermal agents. Importantly, Sb doped SnO2 nanocrystals can efficiently kill cancer cells both in vitro and in vivo under the irradiation of a 980 nm laser with a power density of 0.6 W cm–2. In addition, Sb doped SnO2 nanocrystals can also be served as efficient CT imaging agents owing to the large X-ray attenuation coefficient of tin.

Infrared driven hot electron generation and transfer from non-noble metal plasmonic nanocrystals

Non-noble metal plasmonic materials, e.g. doped semiconductor nanocrystals, compared to their noble metal counterparts, have shown unique advantages, including broadly tunable plasmon frequency (from visible to infrared) and rich surface chemistry. However, the fate and harvesting of hot electrons from these non-noble metal plasmons have been much less explored. Here we report plasmon driven hot electron generation and transfer from plasmonic metal oxide nanocrystals to surface adsorbed molecules by ultrafast transient absorption spectroscopy. We show unambiguously that under infrared light excitation, hot electron transfers in ultrafast timescale (<50 fs) with an efficiency of 1.4%. The excitation wavelength and fluence dependent study indicates that hot electron transfers right after Landau damping before electron thermalization. We revealed the efficiency-limiting factors and provided improvement strategies. This study paves the way for designing efficient infrared light absorption and photochemical conversion applications based on non-noble metal plasmonic materials.

Efficient multiphoton absorption of near-infrared emitting Cu-doped ZnInS/ZnS nanocrystals

Due to their unique optoelectronic properties, doped semiconductor nanocrystals (NCs) are promising fluorescent probes for deep-tissue bioimaging applications. However, studies on the photophysical properties of cadmium-free doped NCs are scarce. In this study, we synthesized and studied the photophysical properties of one type of cadmium-free doped NCs (Cu: ZnInS/ZnS NCs), which exhibit near infrared-I (NIR-I) emission at 730 nm and long emission lifetime up to 1.38 μs. Femtosecond transient absorption spectra revealed a strong exciton coupling effect between the Cu2+ ions and the ZnInS/ZnS host, with a fast energy transfer time of ≈100 ps. More importantly, Cu: ZnInS/ZnS NCs exhibit efficient volume-normalized two- and three-photon absorption cross-sections in NIR-I (800–900 nm) and NIR-III regions (1600–1990 nm), with maximum values up to 6.9 GM nm−3 at 800 nm and 1.1 × 10−80 cm6 s2 photon−2 nm−3 at 1600 nm, respectively. This study can shed light on the exploration of novel environmentally friendly doped NCs for deep-tissue bioimaging applications.

Dependence of Quantum Yield for Periodic Array of Doped Semiconductor Nanocrystals

Dependence of Quantum Yield for Periodic Array of Doped Semiconductor Nanocrystals

Facile synthesis of manganese (II)-doped ZnSe nanocrystals with controlled dimensionality.

Doping is one of the key technologies in modern semiconductor science and industry. However, the synthetic control of doped nanocrystals is difficult to achieve. Here, we report the facile synthesis of manganese (II) doped ZnSe nanocrystals with controlled dimensionality. A strong Lewis acid-base reaction using air-stable and environmentally friendly metal chlorides as precursors can readily produce a large amount of quantum-confined ZnSe:Mn2+ nanocrystals. A combination of primary and secondary amines is used to control the synthetic chemistry, which enables the shape of the doped nanocrystals to be controlled. The final doping concentration of the products can be finely tunable, which is critical for carrier relaxation dynamics. It turns out that the threshold doping level for the maximum photoluminescence intensity of doped nanocrystals highly depends on their shape. Furthermore, this simple synthetic method is extendable to obtain various Mn2+-doped II-VI semiconductor nanocrystals such as CdS:Mn2+ and ZnS:Mn2+. Our study will facilitate the fundamental understanding of the doped semiconductor nanocrystals with different shapes, which is potentially useful for a wide range of applications such as lighting, photocatalysis, and bioimaging.

Effect of Dopant Activation and Plasmon Damping on Carrier Polarization in In2O3 Nanocrystals

Expanding the range of available aliovalently doped semiconductor nanocrystals has largely been motivated by the potential for realizing and controlling plasmon-exciton coupling in a single phase. ...

Quantitative Analysis of Extinction Coefficients of Tin-Doped Indium Oxide Nanocrystal Ensembles.

The optical extinction coefficients of localized surface plasmon resonance (LSPR) in doped semiconductor nanocrystals (NCs) have intensities determined by the density and damping mechanisms of free charge carriers. We investigate the dependence of the extinction coefficient of tin-doped indium oxide (ITO) NCs on size and dopant concentration and find extinction coefficients as high as 56.6 μm-1 in the near-infrared for 20 nm diameter ITO NCs with 7.5 atomic% Sn. We find ITO NCs to be more efficient infrared light absorbers than metal nanoparticles or molecular dyes. We also find the intensive, volume-normalized extinction coefficient increases significantly with NC doping and NC diameter, but only up to the point of saturation in both cases. We qualitatively analyze trends in LSPR peak position and width to explain the effect of doping and size on extinction.

Wide Dynamic Range in Tunable Electrochromic Bragg Stacks from Doped Semiconductor Nanocrystals

AbstractElectrochromic properties can be enhanced by constructing photonic architectures, in which the reflectance contributes to optical modulation along with the intrinsic dynamic absorptivity of the material. However, optimization of reflectance is challenging without a rational design approach. Here, electrochemically tunable Bragg reflectors are demonstrated that are tuned to be highly transparent in the “off” state, achieving synergistic dynamic optical modulation of absorption and reflection in the visible and near‐infrared range. These Bragg stacks are composed of alternating doped semiconductor nanocrystal (NC) layers of 5 nm sized oxygen vacancy‐doped WO3−x and 15 nm sized 0.4 at% Sn:In2O3 NCs. Combining judicious NC selection and processing optimization with guidance from optical simulations, optimized Bragg stacks are implemented for electrochromic window applications. NCs with high absorption coefficients are essential for strong transmission modulation, though this characteristic limits the dynamic range of the Bragg reflectance. Optimal reflectance modulation including a highly transparent “off” state is confirmed with in situ reflectance and transmittance measurement. More broadly, ligand‐stripped NCs can enable fabrication of complex device architectures on low‐cost flexible substrates. These results guide the design rules for accessing different types of doped semiconductor NC‐based tunable Bragg stacks, an exemplary photonic structure, over a broad wavelength range.