Mid- and Long-Wave Infrared Optoelectronics via Intraband Transitions in PbS Colloidal Quantum Dots.

Optical sensing in the mid- and long-wave infrared (MWIR, LWIR) is of paramount importance for a large spectrum of applications including environmental monitoring, gas sensing, hazard detection, food and product manufacturing inspection, and so forth. Yet, such applications to date are served by costly and complex epitaxially grown HgCdTe quantum-well and quantum-dot infrared photodetectors. The possibility of exploiting low-energy intraband transitions make colloidal quantum dots (CQD) an attractive low-cost alternative to expensive low bandgap materials for infrared applications. Unfortunately, fabrication of quantum dots exhibiting intraband absorption is technologically constrained by the requirement of controlled heavy doping, which has limited, so far, MWIR and LWIR CQD detectors to mercury-based materials. Here, we demonstrate intraband absorption and photodetection in heavily doped PbS colloidal quantum dots in the 5-9 µm range, beyond the PbS bulk band gap, with responsivities on the order of 10-4 A/W at 80 K. We have further developed a model based on quantum transport equations to understand the impact of electron population of the conduction band in the performance of intraband photodetectors and offer guidelines toward further performance improvement.

Intraband optical activity of semiconductor nanocrystals.

Here we review our three recently developed analytical models describing the intraband optical activity of semiconductor nanocrystals, which is induced by screw dislocations, ionic impurities, or irregularities of the nanocrystal surface. The models predict that semiconductor nanocrystals can exhibit strong optical activity upon intraband transitions and have large dissymmetry of magnetic-dipole absorption. The developed models can be used to interpret experimental circular dichroism spectra of nanocrystals and to advance the existing techniques of enantioseparation, biosensing, and chiral chemistry.

Dislocation-induced chirality of semiconductor nanocrystals.

Optical activity is a common natural phenomenon, which occurs in individual molecules, biomolecules, biological species, crystalline solids, liquid crystals, and various nanosized objects, leading to numerous important applications in almost every field of modern science and technology. Because this activity can hardly be altered, creation of artificial active media with controllable optical properties is of paramount importance. Here, for the first time to the best of our knowledge, we theoretically demonstrate that optical activity can be inherent to many semiconductor nanowires, as it is induced by chiral dislocations naturally developing during their growth. By assembling such nanowires in two- or three-dimensional periodic lattices, one can create optically active quantum supercrystals whose activity can be varied in many ways owing to the size quantization of the nanowires' energy spectra. We believe that this research is of particular importance for the future development of semiconducting nanomaterials and their applications in nanotechnology, chemistry, biology, and medicine.

High-Performance Ultraviolet-to-Infrared Broadband Perovskite Photodetectors Achieved via Inter-/Intraband Transitions.

A high-performance vertically injected broadband UV-to-IR photodetector based on Gd-doped ZnO nanorods (NRs)/CH3NH3PbI3 perovskite heterojunction was fabricated on metal substrates. Our perovskite-based photodetector is sensitive to a broad spectral range, from ultraviolet to infrared light region (λ = 250-1357 nm). Such structure leads to a high photoresponsivity of 28 and 0.22 A/W, for white light and IR illumination, respectively, with high detectivity values of 1.1 × 1012 and 9.3 × 109 Jones. Optical characterizations demonstrate that the IR detection is due to intraband transition in the perovskite material. Metal substrate boosts carrier injection, resulting in higher responsivity compared to the conventional devices grown on glass, whereas the presence of Gd increases the ZnO NRs performance. For the first time, the perovskite-based photodetector is demonstrated to extend its detection capability to IR (>1000 nm) with high room temperature responsivity across the detected spectrum, leading to a high-performance ingenious cost-effective UV-to-IR broadband photodetector design for large-scale applications.

All-Optical Wavelength Conversion by Picosecond Burst Absorption in Colloidal PbS Quantum Dots.

All-optical approaches to change the wavelength of a data signal are considered more energy- and cost-effective than current wavelength conversion schemes that rely on back and forth switching between the electrical and optical domains. However, the lack of cost-effective materials with sufficiently adequate optoelectronic properties hampers the development of this so-called all-optical wavelength conversion. Here, we show that the interplay between intraband and band gap absorption in colloidal quantum dots leads to a very strong and ultrafast modulation of the light absorption after photoexcitation in which slow components linked to exciton recombination are eliminated. This approach enables all-optical wavelength conversion at rates matching state-of-the-art convertors in speed, yet with cost-effective solution-processable materials. Moreover, the stronger light-matter interaction allows for implementation in small-footprint devices with low switching energies. Being a generic property, the demonstrated effect opens a pathway toward low-power integrated photonics based on colloidal quantum dots as the enabling material.

Broadband Near-Infrared to Visible Upconversion in Quantum Dot-Quantum Well Heterostructures.

Upconversion is a nonlinear process in which two, or more, long wavelength photons are converted to a shorter wavelength photon. It holds great promise for bioimaging, enabling spatially resolved imaging in a scattering specimen and for photovoltaic devices as a means to surpass the Shockley-Queisser efficiency limit. Here, we present dual near-infrared and visible emitting PbSe/CdSe/CdS nanocrystals able to upconvert a broad range of NIR wavelengths to visible emission at room temperature. The synthesis is a three-step process, which enables versatility and tunability of both the visible emission color and the NIR absorption edge. Using this method, one can achieve a range of desired upconverted emission peak positions with a suitable NIR band gap.

Colloidal quantum dots intraband photodetectors.

Photoconductivity is demonstrated with monodispersed HgSe colloidal quantum dots that are illuminated with radiation resonant with 1S(e)-1P(e) intraband electronic absorption, between 3 and 5 µm. A doping of two electrons per dot gives the lowest dark current, and a detectivity of 8.5 × 10(8) Jones is obtained at 80 K. Photoluminescence of the intraband transition is also observed. The detector properties are discussed in terms of the measured photoluminescence quantum yield, the electron mobility in the 1P(e) state, and the responsivity. The intraband photoresponse allows to fully harness the quantum confined states in colloidal nanostructures, extending the prior limited use of interband transition.

Air-Stable n-Doped Colloidal HgS Quantum Dots.

HgS nanocrystals show a strong mid-infrared absorption and a bleach of the near-infrared band edge, both tunable in energy and reversibly controlled by exposure to solution ions under ambient conditions. The same effects are obtained by applying a reducing electrochemical potential, confirming that the mid-infrared absorption is the intraband transition of the quantum dot. This is the first time that stable carriers are present in the quantum state of strongly confined quantum dot in ambient conditions. The mechanism by which doping is achieved is attributed to the rigid shifts of the valence and conduction band with respect to the environment, similar to the sensitivity of the work function of surfaces to adsorbates.