We report the synthesis of nanocrystals with an optical feature in the THz range. To do so, we develop a new synthetic procedure for the growth of HgTe, HgSe, and HgS nanocrystals, with strong size tunability from 5 to 200 nm. This is used to tune the absorption of the nanocrystals all over the infrared range up to terahertz (from 2 to 65 μm for absorption peak and even 200 μm for cutoff wavelength). The interest for this procedure is not limited to large sizes since for small objects we demonstrate low aggregation and good shape control (i.e., spherical object) while using nonexpansive and simple mercury halogenide precursors. By integrating these nanocrystals into an electrolyte-gated transistor, we evidence a change of carrier density from p-doped to n-doped as the confinement is vanishing.

Nanocrystals are promising materials for the design of low cost infrared detectors. Here we focus on HgTe colloidal quantum dots (CQDs) as an active material for detection in the extended shortwave infrared (2.5 µm as cutoff wavelength). In this paper, we propose a strategy to enhance the performances of previously reported photodiodes. In particular we integrate in this diode an unipolar barrier which role is to prevent the dark current injection to enhance the signal to noise ratio. We demonstrate that such unipolar barrier can be designed from another layer of HgTe CQDs with a wider band gap. Using a combination of IR spectroscopy and photoemission, we show that the barrier is resonant with the absorbing layer valence band, while presenting a clear offset with the conduction band. The combination of contacts with improved design and use of unipolar barrier allows us to reach a detectivity as high as 3•10 8 Jones at room temperature with 3 dB cut off frequency above 10 kHz.

Colloidal quantum dots (CQDs) are candidates of interest for the design of low cost IR detector especially in the short wave infrared (SWIR; 0.8-3 µm), where the vicinity of the visible range makes the high cost of available technologies even more striking. HgTe nanocrystals are among the most promising candidates to address SWIR since their spectrum can be tuned all over this range while demonstrating photoconductive properties. However, several main issues have been kept under the rug, which prevents further development of active materials and devices.Here we address two central questions, which are (i) the stability of the device under ambient air condition and (ii) the reduction of dark current. Encapsulation of HgTe CQDs is difficult because of their extreme sensitivity to annealing, we nevertheless demonstrate an efficient encapsulation method based on a combination of O2 and H2O repellant layers leading to stability over >100 days. Finally, we demonstrate that the dark current reduction can be obtained by switching from a photoconductive geometry to a photovoltaic (PV) device, which is fabricated using solution and low temperature based approach. We demonstrate fast photoresponse (>10 kHz) and detectivity enhancement by 1 order of magnitude in the PV configuration at room temperature. These results pave the way for narrow bandgap CQD based cost-effective optoelectronic devices in developing next generation SWIR photonic systems.

Abstract:Colloidal nanocrystals are an interesting platform for the design of low cost optoelectronic devices especially in the infrared range of wavelengths. Mercury chalcogenides have reached high maturity to address wavelengths above the telecom range (1.5 µm). However, no screening of the surface chemistry influence has been conducted yet. In this paper, we systematically probe the influence of a series of ligands: Cl -, SCN -, 1,2 ethanedithiol, 1,4 benzenedithiol, 1 octanethiol, 1 butanethiol, As 2 S 3 , S 2-on the photoconductive properties of HgTe nanocrystal thin films. A high bandwidth, large dynamic transient photocurrent setup is used to determine the photocarrier dynamics. Two regimes are clearly identified. At early stage (few ns) a fast decay of the photocurrent is resulting from recombination and trapping. Then transport enters in a multiple trapping regime where carriers present a continuously decreasing effective value of their mobility. The power law dependence of the conductance can be used to estimate the trap carrier density and determine the value of the Urbach energy (35 to 50 meV). We demonstrate that a proper choice of ligand is necessary for a trade-off between the material performance (µτ product) and the quality of the surface passivation (to keep a low Urbach energy).

Mercury chalcogenide nanocrystals and especially HgTe appear as an interesting platform for the design of low cost mid-infrared (mid-IR) detectors. Nevertheless, their electronic structure and transport properties remain poorly understood, and some critical aspects such as the carrier relaxation dynamics at the band edge have been pushed under the rug. Some of the previous reports on dynamics are setup-limited, and all of them have been obtained using photon energy far above the band edge. These observations raise two main questions: (i) what are the carrier dynamics at the band edge and (ii) should we expect some additional effect (multiexciton generation (MEG)) as such narrow band gap materials are excited far above the band edge? To answer these questions, we developed a high-bandwidth setup that allows us to understand and compare the carrier dynamics resonantly pumped at the band edge in the mid-IR and far above the band edge. We demonstrate that fast (>50 MHz) photoresponse can be obtained even in the mid-IR and that MEG is occurring in HgTe nanocrystal arrays with a threshold around 3 times the band edge energy. Furthermore, the photoresponse can be effectively tuned in magnitude and sign using a phototransistor configuration.

The chemistry of nanocrystals enables the receipt of semiconductor nanoparticles with tunable optical properties. So far most scientific efforts have been focused on wide band gap materials to achieve a bright luminescence and a higher solar power conversion efficiency. Their properties in the infrared range of wavelengths are interesting as well. Two strategies can be used to achieve mid-infrared (mid-IR) transition, either interband transition in narrow band gap material or intraband transition in doped material. In this review, we discuss recent progress to achieve stable doped nanocrystals. We focus on mercury chalcogenide compounds since they are so far the only materials that combine mid-IR absorption with photoconductive properties in this range of energies. We discuss the origin of the doping and its tunability as well as how the doping impacts the optical, transport, and photodetection properties. Finally, we discuss Hg-free alternative materials, and present mid-IR transitions.

We discuss the transport properties of CsPbBrxI3−x perovskite nanocrystal arrays as a model ensemble system of caesium lead halide-based perovskite nanocrystal arrays. While this material is very promising for the design of light emitting diodes, laser, and solar cells, very little work has been devoted to the basic understanding of their (photo)conductive properties in an ensemble system. By combining DC and time-resolved photocurrent measurements, we demonstrate fast photodetection with time response below 2 ns. The photocurrent generation in perovskite nanocrystal-based arrays is limited by fast bimolecular recombination of the material, which limits the lifetime of the photogenerated electron-hole pairs. We propose to use nanotrench electrodes as a strategy to ensure that the device size fits within the obtained diffusion length of the material in order to boost the transport efficiency and thus observe an enhancement of the photoresponse by a factor of 1000.

Naturally formed CdTe/CdS core/shell quantum dot (QD) structures in the presence of surface stabilizing agents have been synthesized by a hydrothermal method. Size and temperature dependent photoluminescence (PL) spectra have been investigated to understand the exciton-phonon interaction, and radiative and nonradiative relaxation of carriers in these QDs. The PL of these aqueous CdTe QDs (3.0-4.8 nm) has been studied in the temperature range 15-300 K. The strength of the exciton-LO-phonon coupling, as reflected in the Huang-Rhys parameter 'S' is found to increase from 1.13 to 1.51 with the QD size varying from 4.8 to 3.0 nm. The PL linewidth (FWHM) increases with increase in temperature and is found to have a maximum in the case of QDs of 3.0 nm in size, where the exciton-acoustic phonon coupling coefficient is enhanced to 51 μeV K(-1), compared to the bulk value of 0.72 μeV K(-1). To understand the nonradiative processes, which affect the relaxation of carriers, the integrated PL intensity is observed as a function of temperature. The integrated PL intensity remains constant until 50 K for relatively large QDs (3.9-4.8 nm) beyond which a thermally activated process takes over. Below 150 K, a small activation energy, 45-19 meV, is found to be responsible for the quenching of the PL. Above 150 K, the thermal escape from the dot assisted by scattering with multiple longitudinal optical (LO) phonons is the main mechanism for the fast quenching of the PL. Besides this high temperature quenching, interestingly for relatively smaller size QDs (3.4-3.0 nm), the PL intensity enhances as the temperature increases up to 90-130 K, which is attributed to the emission of carriers from interface/trap states having an activation energy in the range of 6-13 meV.