Plasmonic Semiconductor Nanocrystals Research Articles

How to Quantify Electrons in Plasmonic Colloidal Metal Oxide Nanocrystals

Distinct from noble metal nanoparticles, doped metal oxide nanocrystals (NCs) exhibit localized surface plasmon resonance (LSPR) in the infrared region that can be tuned by changing the free electron concentration through both synthetic and postsynthetic doping. Redox reagents have commonly been used to postsynthetically modulate the LSPR, but to understand the relationship between the electron transfer processes and the resulting optical changes, it is imperative to quantify electrons in the NCs. Titration and LSPR peak fitting analysis are the most common methods used for quantifying electrons; however, a comparison between these methods has previously revealed discrepancies up to an order of magnitude without a clear explanation. Here, we apply these electron quantification techniques concurrently to Sn-doped In2O3 NCs with varying size, doping concentration, and extent of postsynthetic reduction. We find that oxidative titration consistently overestimates the number of electrons per NC, owing to the failure of the assumed stoichiometric equivalents between moles of oxidant added and moles of free electrons extracted from the NCs. The NC characteristics we examine strongly influence the driving force for the oxidation process, affecting the relative agreement between oxidative titration and LSPR fitting; the two methods more closely agree when the electron transfer driving force is larger. Overall, these analyses inform best practices for quantifying electrons in plasmonic semiconductor NCs and reveal how the accuracy is affected by NC characteristics.

High-performance broadband photodetector based on plasmonic semiconductor-semiconductor p-n Cu1.8S/AZO interface

Plasmonic semiconductor nanocrystals (NCs) provide intriguing optical properties which offer opportunities to extend the photo-response corresponding to photons with energies less than the semiconductor energy band gap. However, the performance of photodetectors based on individual plasmonic semiconductors is restricted due to very short-living photo-carriers, followed by carrier recombination (∼ 100 ps). Herein, a plasmonic semiconductor-semiconductor p-n interface (Cu1.8S/AZO NCs) was constructed representing 2-fold optical characteristics containing an inter-band electronic transition from the valence to conduction band in response to ultraviolet-visible (UV–vis) excitation and plasmon-induced interfacial charge-transfer transition (PICTT) in response to near infrared (NIR) excitation. We demonstrated that AZO NCs, are appropriate candidates to generate chemical interface damping (CID) of plasmons in Cu1.8S NCs as an acceptor, which is required for PICTT pathway. The device displayed outstanding broadband UV–vis–NIR photoresponsivity (R) and response-time (Trise/Tfall) as high as R = 51.48 A/W, Trise/Tfall= 130/100 ms in 390 nm, R = 37.2 A/W, Trise/Tfall= 50/60 ms in 535 nm, R = 45.6 A/W, Trise/Tfall= 400/10 ms in 750 nm and R = 38.7 A/W and Trise/Tfall= 60/50 ms in 950 nm. This study demonstrates the promising potential of plasmonic semiconductor-semiconductor p-n hybrid systems as high-performance broadband photodetectors (PDs).

Effective Mass for Holes in Paramagnetic, Plasmonic Cu5FeS4 Semiconductor Nanocrystals.

The impact of a magneto-structural phase transition on the carrier effective mass in Cu5FeS4 plasmonic semiconductor nanocrystals was examined using Magnetic Circular Dichroism (MCD). Through MCD, the sample was confirmed as p-type from variable temperature studies from 1.8 - 75 K. Magnetic field dependent behavior is observed, showing an asymptotic behavior at high field with an value 5.98 at 10 T and 2.73 at 2 T. Experimentally obtained results are holistically compared to SQUID magnetization data and DFT results, highlighting a dependency on vacancy driven polaronic coupling, magnetocrystalline anisotropy, and plasmon coupling of the magnetic field all contributing to an overall decrease in the hole mean free path dependent on the magnetic field applied to Cu5FeS4.

Properties of Free Charge Carriers Govern Exciton Polarization in Plasmonic Semiconductor Nanocrystals.

Interaction between a plasmon, as a collective property of charge carriers, and electronic or spin states in complex nanostructures has emerged as one of the fascinating topics that intertwines the fields of photonics, optoelectronics, and spintronics. Here, we investigate the magneto-optical properties of plasmonic InN and Cu2-xSe nanocrystals and show that the complete exciton polarization induced by cyclotron motion of free carriers is a universal phenomenon in semiconductor nanocrystals. The selective exciton polarization is governed by the angular momentum transfer from the carriers following cyclotron orbits to the excited electronic band states and can be controlled by carrier type (electrons or holes), mass, and velocity. The results of this work demonstrate the free-carrier-induced control of the states around the Fermi level and the exciton polarization in technologically important III-V nanocrystals, allowing for new ways of tailoring quantum states for spintronic and optoelectronic applications.

Controlled Synthesis and Exploration of CuxFeS4 Bornite Nanocrystals.

Plasmonic semiconductor nanocrystals (NCs) are a new and exciting class of materials that enable higher control of their localized surface plasmon resonance (LSPR) than metallic counterparts. Additionally, earth-abundant and non-toxic materials such as copper iron sulfides are gaining interest as alternatives to heavy metal-based semiconductor materials. Colloidal bornite (Cu5FeS4) is an interesting but underexplored example of a heavy metal-free plasmonic semiconductor. This report details the hot-injection synthesis of bornite yielding NCs ranging from 2.7 to 6.1 nm in diameter with stoichiometric control of the copper and iron content. The absorbance spectra of bornite NCs with different Cu:Fe ratios change at different rates as the particles oxidize and develop LSPR in the near-infrared region. X-ray photoelectron spectroscopy results indicate that oxidation produces sulfates rather than metal oxides as well as a decrease in the iron content within the NCs. Additionally, increasing iron content leads to decreases in carrier density and effective mass of the carrier, as determined by the Drude model. This controlled synthesis, combined with a further understanding of the relationship between the particle structure and optical properties, will enable the continued development and application of these fascinating heavy metal-free plasmonic semiconductor nanoparticles.

Examining the Effect of Dopant Ionic Radius on Plasmonic M:ZnO Nanocrystals (M = Al3+, Ga3+, In3+)

Understanding the role of dopant deactivation on plasmon frequency and extinction is important for the rational design of plasmonic semiconductor nanocrystals (PSNCs). Aliovalent dopants do not alw...

Fe Cations Control the Plasmon Evolution in CuFeS2 Nanocrystals

Plasmonic semiconductor nanocrystals have become an appealing avenue for researching nanoscale plasmonic effects due to their wide spectral range (visible to infrared) and great tunability compared...

Carrier Density, Effective Mass, and Nuclear Relaxation Pathways in Plasmonic Sn:In2O3 Nanocrystals

Correlating changes in carrier density arising from incorporating dopant ions into the lattice of a plasmonic semiconductor nanocrystals (NCs) with the observed physical properties at the elemental...

Ultrafast and Long-Lived Transient Heating of Surface Adsorbates on Plasmonic Semiconductor Nanocrystals.

Plasmonic photocatalysts have demonstrated promising potential for enhancing the selectivity and efficiency of important chemical transformations. However, the relative contributions of nonphotothermal (i.e., hot carrier) and photothermal pathways remain a question of intense current debate, and the time scale and extent of surface adsorbate temperature change are still poorly understood. Using p-type Cu2-xSe nanocrystals as a semiconductor plasmonic platform and adsorbed Rhodamine B as a surface thermometer and hot carrier acceptor, we measure directly by transient absorption spectroscopy that the adsorbate temperature rises and decays with time constants of 1.4 ± 0.4 and 471 ± 126 ps, respectively, after the excitation of Cu2-xSe plasmon band at 800 nm. These time constants are similar to those for Cu2-xSe lattice temperature, suggesting that fast thermal equilibrium between the adsorbates and nanocrystal lattice is the main adsorbate heating pathway. This finding provides insights into the transient heating effect on surface adsorbates and their roles in plasmonic photocatalysis.

(Invited) Manipulating Carrier Polarization in Semiconductor Nanocrystals

Degenerately-doped semiconductor nanocrystals exhibiting tunable localized surface plasmon resonance (LSPR) have attracted significant attention in recent years due to their unique optoelectronic properties. Unlike noble metal nanoparticles, colloidal plasmonic semiconductor nanocrystals have LSPR frequencies tunable in the infrared region, which makes them appealing for terahertz imaging, heat-responsive devices, and surface-enhanced infrared spectroscopic measurements. Besides expanding the LSPR frequency range, plasmonic semiconductor nanocrystals could potentially bring about numerous other opportunities related to single-phase plasmon-exciton interactions. However, non-resonant nature of the LSPR and exciton in semiconductors has been a major obstacle toward realizing such opportunities. In this talk I will discuss the results of our recent work on the structure and composition dependent plasmonic properties of colloidal semiconductor nanostructures. I will particularly focus on generating robust excitonic splitting in degenerately-doped transparent metal oxide nanocrystals, enabled by non-resonant plasmon-exciton coupling in an external magnetic field. This phenomenon allows for controlling carrier polarization in semiconductor nanocrystals using circularly polarized light. Furthermore, the ability to control carrier localization and nanocrystal morphology allows for further manipulation of the excitonic splitting pattern and quantum states in these non-magnetic semiconductor nanostructures. Possible applications of this emerging class of multifunctional materials for new electronic and quantum information technologies will also be discussed.

Dual-Mode Infrared Absorption by Segregating Dopants within Plasmonic Semiconductor Nanocrystals

When aliovalent dopants are sufficiently segregated to the core or near the surface of semiconductor nanocrystals, charge carriers donated by the dopants are also segregated to the core or near the surface, respectively. In Sn-doped indium oxide nanocrystals, we find that this contrast in free charge carrier concentration creates a core and shell with differing dielectric properties and results in two distinctly observable plasmonic extinction peaks. The trends in this dual-mode optical response with shell growth differ from core/shell nanoparticles composed of traditional plasmonic metals such as Au and Ag. We developed a model employing a core/shell effective medium approximation that can fit the dual-mode spectra and explain the trends in the extinction response. Lastly, we show that dopant segregation can improve sensitivity of plasmon spectra to changes in refractive index of the surrounding environment.

Photochemically Derived Plasmonic Semiconductor Nanocrystals as an Optical Switch for Ultrafast Photonics

Establishing a new photonic material with large optical nonlinearity in the near-infrared regime is significant for ultrafast optical science and devices. In this paper, we developed a facile photo...

Properties, fabrication and applications of plasmonic semiconductor nanocrystals

We highlight three widely explored oxide-based plasmonic materials, including HxMoO3−y, HxWO3−y, and MoxW1−xO3−y, and their applications in catalysis.

Localized Surface Plasmon Resonance in Semiconductor Nanocrystals.

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals (NCs) that results in resonant absorption, scattering, and near field enhancement around the NC can be tuned across a wide optical spectral range from visible to far-infrared by synthetically varying doping level, and post synthetically via chemical oxidation and reduction, photochemical control, and electrochemical control. In this review, we will discuss the fundamental electromagnetic dynamics governing light matter interaction in plasmonic semiconductor NCs and the realization of various distinctive physical properties made possible by the advancement of colloidal synthesis routes to such NCs. Here, we will illustrate how free carrier dielectric properties are induced in various semiconductor materials including metal oxides, metal chalcogenides, metal nitrides, silicon, and other materials. We will highlight the applicability and limitations of the Drude model as applied to semiconductors considering the complex band structures and crystal structures that predominate and quantum effects that emerge at nonclassical sizes. We will also emphasize the impact of dopant hybridization with bands of the host lattice as well as the interplay of shape and crystal structure in determining the LSPR characteristics of semiconductor NCs. To illustrate the discussion regarding both physical and synthetic aspects of LSPR-active NCs, we will focus on metal oxides with substantial consideration also of copper chalcogenide NCs, with select examples drawn from the literature on other doped semiconductor materials. Furthermore, we will discuss the promise that LSPR in doped semiconductor NCs holds for a wide range of applications such as infrared spectroscopy, energy-saving technologies like smart windows and waste heat management, biomedical applications including therapy and imaging, and optical applications like two photon upconversion, enhanced luminesence, and infrared metasurfaces.

3D-printed millifluidic chip for synthesising plasmonic semiconductor nanocrystals as sensors substrate

ABSTRACTIn the past, plasmonics were always referred to as the collective oscillation of free electrons on metal surfaces such as gold (Au) and silver (Ag). This changed when plasmonic behaviour was experimentally demonstrated in semiconductors, i.e. self-doped copper sulfur, nanocrystals (Cu2−xS NCs) in 2009. In fact, Cu2−xS NC possesses different plasmonic behaviour than Au and Ag, in which the resonant condition is governed by another regime (free holes as the carriers) and its sensing capability has not yet been fully explored. In this contribution, the as-prepared (organic phase) Cu2−xS NCs were transferred in water and were tested with glycerin-water mixtures and anions. The results showed that Cu2−xS NC is very sensitive to the variation of refractive index in the surrounding environment. Furthermore, it was found that the plasmonic properties of these NCs are also very sensitive to the presence of anions. By taking the advantages of this “additional” effect, Cu2−xS NC can be used as a potential su...

Universal Near-Infrared and Mid-Infrared Optical Modulation for Ultrafast Pulse Generation Enabled by Colloidal Plasmonic Semiconductor Nanocrystals.

Field effect relies on the nonlinear current-voltage relation in semiconductors; analogously, materials that respond nonlinearly to an optical field can be utilized for optical modulation. For instance, nonlinear optical (NLO) materials bearing a saturable absorption (SA) feature an on-off switching behavior at the critical pumping power, thus enabling ultrafast laser pulse generation with high peak power. SA has been observed in diverse materials preferably in its nanoscale form, including both gaped semiconductor nanostructures and gapless materials like graphene; while the presence of optical bandgap and small carrier density have limited the active spectral range and intensity. We show here that solution-processed plasmonic semiconductor nanocrystals exhibit superbroadband (over 400 THz) SA, meanwhile with large modulation depth (∼7 dB) and ultrafast recovery (∼315 fs). Optical modulators fabricated using these plasmonic nanocrystals enable mode-locking and Q-switching operation across the near-infrared and mid-infrared spectral region, as exemplified here by the pulsed lasers realized at 1.0, 1.5, and 2.8 μm bands with minimal pulse duration down to a few hundreds of femtoseconds. The facile accessibility and superbroadband optical nonlinearity offered by these nonconventional plasmonic nanocrystals may stimulate a growing interest in the exploiting of relevant NLO and photonic applications.

Shape-Dependent Field Enhancement and Plasmon Resonance of Oxide Nanocrystals

Metallic nanostructures can manipulate light-matter interactions to induce absorption, scattering, and local heating through their localized surface plasmon resonances. Recently, plasmonic behavior of semiconductor nanocrystals has been investigated to stretch the boundaries of plasmonics farther into the infrared spectral range and to introduce unprecedented tunability. However, many fundamental questions remain regarding characteristics of plasmons in doped semiconductor nanocrystals. Field enhancement, especially near features with high curvature, is essential in many applications of plasmonic metal nanostructures, yet the potential for plasmonic field enhancement by semiconductor nanocrystals remains unknown. Here, we use the discrete dipole approximation (DDA) to understand the dependence of field enhancement on size, shape, and doping level of plasmonic semiconductor nanocrystals. Indium-doped cadmium oxide is considered as a prototypical material for which faceted cube-octohedral nanocrystals have been experimentally realized; their optical spectra are compared to our computational results. The computed extinction spectra are sensitive to changes in doping level, dielectric environment, and shape and size of the nanocrystals, providing insight for materials design. High-scattering efficiencies and efficient local heat production make 100 nm particles suitable for photothermal therapies and simultaneous bioimaging. Meanwhile, single particles and dimers of nanocrystals demonstrate strong, shape- and wavelength-dependent near-field enhancement, highlighting their potential for applications in infrared sensing, imaging, spectroscopy, and solar conversion.

Plasmonic Semiconductor Nanocrystals as Chemical Sensors: Pb2+ Quantitation via Aggregation-Induced Plasmon Resonance Shift

We demonstrate, for the first time, the use of plasmonic semiconductor nanocrystals for the analysis of heavy metal ions in water. This highly sensitive localized surface plasmon resonance (LSPR)-based platform is built on glutathione (GSH) capped Cu2−xS nanocrystals, which exhibit LSPR at near infrared (NIR) wavelengths. Aggregation of GSH-capped Cu2−x S occurs specifically in the presence of lead ions, Pb2+, producing a shift in the LSPR absorbance peak. Under optimal assay conditions, the detection limit was as low as 0.25 μM (52.5 ppb) of Pb2+. This provides a new plasmonic semiconductor nanocrystal-based assay for the detection of environmentally hazardous materials. The assay employs non-toxic and earth-abundant elements and could potentially be produced at much lower cost than similar gold nanoparticle-based assays.

Controllable conversion of plasmonic Cu2−xS nanoparticles to Au2S by cation exchange and electron beam induced transformation of Cu2−xS–Au2S core/shell nanostructures

Self-doped Cu2-xS nanocrystals (NCs) were converted into monodisperse Cu2-xS-Au2S NCs of tunable composition, including pure Au2S, by cation exchange. The near-infrared (NIR) localized surface plasmon resonance (LSPR) was dampened and red-shifted with increasing Au content. Cation exchange was accompanied by elimination of cation vacancies and a change in crystal structure. Partially exchanged Cu2-xS-Au2S core/shell structures evolved to dumbbell-like structures under electron irradiation in the transmission electron microscope (TEM).

Shape-Dependent Plasmonic Response and Directed Self-Assembly in a New Semiconductor Building Block, Indium-Doped Cadmium Oxide (ICO)

The influence of particle shape on plasmonic response and local electric field strength is well-documented in metallic nanoparticles. Morphologies such as rods, plates, and octahedra are readily synthesized and exhibit drastically different extinction spectra than spherical particles. Despite this fact, the influence of composition and shape on the optical properties of plasmonic semiconductor nanocrystals, in which free electrons result from heavy doping, has not been well-studied. Here, we report the first observation of plasmonic resonance in indium-doped cadmium oxide (ICO) nanocrystals, which exhibit the highest quality factors reported for semiconductor nanocrystals. Furthermore, we are able to independently control the shape and free electron concentration in ICO nanocrystals, allowing for the influence of shape on the optical response of a plasmonic semiconductor to be conclusively demonstrated. The highly uniform particles may be self-assembled into ordered single component and binary nanocrystal superlattices, and in thin films, exhibit negative permittivity in the near infrared (NIR) region, validating their use as a new class of tunable low-loss plasmonic building blocks for 3-D optical metamaterials.