Double-crowned 2D semiconductor nanoplatelets with bicolor power-tunable emission.

Nanocrystals (NCs) are now established building blocks for optoelectronics and their use as down converters for large gamut displays has been their first mass market. NC integration relies on a combination of green and red NCs into a blend, which rises post-growth formulation issues. A careful engineering of the NCs may enable dual emissions from a single NC population which violates Kasha's rule, which stipulates that emission should occur at the band edge. Thus, in addition to an attentive control of band alignment to obtain green and red signals, non-radiative decay paths also have to be carefully slowed down to enable emission away from the ground state. Here, we demonstrate that core/crown/crown 2D nanoplatelets (NPLs), made of CdSe/CdTe/CdSe, can combine a large volume and a type-II band alignment enabling simultaneously red and narrow green emissions. Moreover, we demonstrate that the ratio of the two emissions can be tuned by the incident power, which results in a saturation of the red emission due to non-radiative Auger recombination that affects this emission much stronger than the green one. Finally, we also show that dual-color, power tunable, emission can be obtained through an electrical excitation.

Vanishing Confinement Regime in Terahertz HgTe Nanocrystals Studied under Extreme Conditions of Temperature and Pressure.

While HgTe nanocrystals (NCs) in the mid-infrared region have reached a high level of maturity, their far-infrared counterparts remain far less studied, raising the need for an in-depth investigation of the material before efficient device integration can be considered. Here, we explore the effect of temperature and pressure on the structural, spectroscopic, and transport properties of HgTe NCs displaying an intraband absorption at 10 THz. The temperature leads to a very weak modulation of the spectrum as opposed to what was observed for strongly confined HgTe NCs. HgTe NC films present ambipolar conduction with a clear prevalence of electron conduction as confirmed by transistor and thermoelectric measurements. Under the application of pressure, the material undergoes phase transitions from the zinc blende to cinnabar phase and later to the rock salt phase which we reveal using joint X-ray diffraction and infrared spectroscopy measurements. We discuss how the pressure existence domain of each phase is affected by the particle size.

Photoconductive focal plane array based on HgTe quantum dots for fast and cost-effective short-wave infrared imaging.

HgTe nanocrystals, thanks to quantum confinement, present a broadly tunable band gap all over the infrared spectral range. In addition, significant efforts have been dedicated to the design of infrared sensors with an absorbing layer made of nanocrystals. However, most efforts have been focused on single pixel sensors. Nanocrystals offer an appealing alternative to epitaxially grown semiconductors for infrared imaging by reducing the material growth cost and easing the coupling to the readout circuit. Here we propose a strategy to design an infrared focal plane array from a single fabrication step. The focal plane array (FPA) relies on a specifically designed readout circuit enabling in plane electric field application and operation in photoconductive mode. We demonstrate a VGA format focal plane array with a 15 µm pixel pitch presenting an external quantum efficiency of 4-5% (15% internal quantum efficiency) for a cut-off around 1.8 µm and operation using Peltier cooling only. The FPA is compatible with 200 fps imaging full frame and imaging up to 340 fps is demonstrated by driving a reduced area of the FPA. In the last part of the paper, we discuss the cost of such sensors and show that the latter is only driven by labor costs while we estimate the cost of the NC film to be in the 10-20 € range.

The complex optical index of PbS nanocrystal thin films and their use for short wave infrared sensor design.

As nanocrystals (NCs) gain maturity, they become central building blocks for optoelectronics in devices such as solar cells and, more recently, infrared focal plane arrays. Now that the proof of concept of these devices has been established, their optimization requires a deeper understanding of their electronic and optical features to engineer their optoelectronic properties accurately. Though PbS NCs have been extensively investigated, the complex optical index of PbS NC thin films remains mostly unknown. Some previous works have unveiled the optical index for this type of material optimized for solar cells (excitonic peak at 940 nm), but longer wavelengths remain scarce and surface chemistry effects, which are known to be of central importance for layer doping, are simply unexplored. Here, we conduct a systematic investigation of the complex optical index of PbS NC thin films using broadband spectrally resolved ellipsometry. The obtained results are then compared with simulations combining tight-binding (TB) modeling at the NC level and the Bruggeman model to expand the results to the film scale. While TB calculation gives the NC optical indices, we extract the key NC film parameters such as the NC volume fraction and ligand indices by fitting the Bruggeman formula to ellipsometry measurements. We also bring evidence that this joint modeling method can be conducted without the need for ellipsometry data while preserving the main feature of the experimental results. Finally, the unveiled optical indices are used to model the absorption of short-wave infrared diode stacks based on PbS NCs and are relevant for state-of-the-art devices. Our electromagnetic modeling shows that the absorption within the contact is now a major limitation of the current device operated at the telecom wavelength.

Bias Tunable Spectral Response of Nanocrystal Array in a Plasmonic Cavity.

Nanocrystals (NCs) have gained considerable attention for their broadly tunable absorption from the UV to the THz range. Nevertheless, their optical features suffer from a lack of tunability once integrated into optoelectronic devices. Here, we show that bias tunable aspectral response is obtained by coupling a HgTe NC array with a plasmonic resonator. Up to 15 meV blueshift can be achieved from a 3 µm absorbing wavelength structure under a 3 V bias voltage when the NC exciton is coupled with a mode of the resonator. We demonstrate that the blueshift arises from the interplay between hopping transport and inhomogeneous absorption due to the presence of the photonic structure. The observed tunable spectral response is qualitatively reproduced in simulation by introducing a bias-dependent diffusion length in the charge transport. This work expands the realm of existing NC-based devices and paves the way toward light modulators.

Correlating Structure and Detection Properties in HgTe Nanocrystal Films.

HgTe nanocrystals (NCs) enable broadly tunable infrared absorption, now commonly used to design light sensors. This material tends to grow under multipodic shapes and does not present well-defined size distributions. Such point generates traps and reduces the particle packing, leading to a reduced mobility. It is thus highly desirable to comprehensively explore the effect of the shape on their performance. Here, we show, using a combination of electron tomography and tight binding simulations, that the charge dissociation is strong within HgTe NCs, but poorly shape dependent. Then, we design a dual-gate field-effect-transistor made of tripod HgTe NCs and use it to generate a planar p-n junction, offering more tunability than its vertical geometry counterpart. Interestingly, the performance of the tripods is higher than sphere ones, and this can be correlated with a stronger Te excess in the case of sphere shapes which is responsible for a higher hole trap density.

Mercury Chalcogenide Quantum Dots: Material Perspective for Device Integration.

Nanocrystals (NCs) are one of the few nanotechnologies to have attained mass market applications with their use as light sources for displays. This success relies on Cd- and In-based wide bandgap materials. NCs are likely to be employed in more applications as they provide a versatile platform for optoelectronics, specifically, infrared optoelectronics. The existing material technologies in this range of wavelengths are generally not cost-effective, which limits the spread of technologies beyond a few niche domains, such as defense and astronomy. Among the potential candidates to address the infrared window, mercury chalcogenide (HgX) NCs exhibit the highest potential in terms of performance. In this review, we discuss how material developments have facilitated device enhancements. Because these materials are mainly used for their infrared optical features, we first review the strategies for their colloidal growth and their specific electronic structure. The review is organized considering three main device-related applications: light emission, electronic transport, and infrared photodetection.

Infrared photoconduction at the diffusion length limit in HgTe nanocrystal arrays.

Narrow band gap nanocrystals offer an interesting platform for alternative design of low-cost infrared sensors. It has been demonstrated that transport in HgTe nanocrystal arrays occurs between strongly-coupled islands of nanocrystals in which charges are partly delocalized. This, combined with the scaling of the noise with the active volume of the film, make case for device size reduction. Here, with two steps of optical lithography we design a nanotrench which effective channel length corresponds to 5-10 nanocrystals, matching the carrier diffusion length. We demonstrate responsivity as high as 1 kA W-1, which is 105 times higher than for conventional µm-scale channel length. In this work the associated specific detectivity exceeds 1012 Jones for 2.5 µm peak detection under 1 V at 200 K and 1 kHz, while the time response is as short as 20 µs, making this performance the highest reported for HgTe NC-based extended short-wave infrared detection.

Electroluminescence from HgTe Nanocrystals and Its Use for Active Imaging.

Mercury telluride (HgTe) nanocrystals are among the most versatile infrared (IR) materials with the absorption of lowest energy optical absorption which can be tuned from the visible to the terahertz range. Therefore, they have been extensively considered as near IR emitters and as absorbers for low-cost IR detectors. However, the electroluminescence of HgTe remains poorly investigated despite its ability to go toward longer wavelengths compared to traditional lead sulfide (PbS). Here, we demonstrate a light-emitting diode (LED) based on an indium tin oxide (ITO)/zinc oxide (ZnO)/ZnO-HgTe/PbS/gold-stacked structure, where the emitting layer consists of a ZnO/HgTe bulk heterojunction which drives the charge balance in the system. This LED has low turn-on voltage, long lifetime, and high brightness. Finally, we conduct short wavelength infrared (SWIR) active imaging, where illumination is obtained from a HgTe NC-based LED, and demonstrate moisture detection.

Nanoplatelet-Based Light-Emitting Diode and Its Use in All-Nanocrystal LiFi-like Communication.

Now that colloidal nanocrystals (NCs) have been integrated as green and red sources for liquid crystal displays, the next challenge for quantum dots is their use in electrically driven light-emitting diodes (LEDs). Among various colloidal NCs, nanoplatelets (NPLs) have appeared as promising candidates for light-emitting devices because their two-dimensional shape allows a narrow luminescence spectrum, directional emission, and high light extraction. To reach high quantum efficiency, it is critical to grow core/shell structures. High temperature growth of the shells seems to be a better strategy than previously reported low-temperature approaches to obtain bright NPLs. Here, we synthesize CdSe/CdZnS core/shell NPLs whose shell alloy content is tuned to optimize the charge injection in the LED structure. The obtained LED has exceptionally low turn-on voltage, long-term stability (>3100 h at 100 cd m-2), external quantum efficiency above 5%, and luminance up to 35,000 cd m-2. We study the low-temperature performance of the LED and find that there is a delay of droop in terms of current density as temperature decreases. In the last part of the paper, we design a large LED (56 mm2 emitting area) and test its potential for LiFi-like communication. In such an approach, the LED is not only a lightning source but also used to transmit a communication signal to a PbS quantum dot solar cell used as a broadband photodetector. Operating conditions compatible with both lighting and information transfer have been identified. This work paves the way toward an all NC-based communication setup.

Pushing Absorption of Perovskite Nanocrystals into the Infrared.

To date, defect-tolerance electronic structure of lead halide perovskite nanocrystals is limited to an optical feature in the visible range. Here, we demonstrate that IR sensitization of formamidinium lead iodine (FAPI) nanocrystal array can be obtained by its doping with PbS nanocrystals. In this hybrid array, absorption comes from the PbS nanocrystals while transport is driven by the perovskite which reduces the dark current compared to pristine PbS. In addition, we fabricate a field-effect transistor using a high capacitance ionic glass made of hybrid FAPI/PbS nanocrystal arrays. We show that the hybrid material has an n-type nature with an electron mobility of 2 × 10-3 cm2 V-1 s-1. However, the dark current reduction is mostly balanced by a loss of absorption. To overcome this limitation, we couple the FAPI/PbS hybrid to a guided mode resonator that can enhance the infrared light absorption.

Reconfigurable 2D/0D p-n Graphene/HgTe Nanocrystal Heterostructure for Infrared Detection.

Nanocrystals are promising building blocks for the development of low-cost infrared optoelectronics. Gating a nanocrystal film in a phototransistor geometry is commonly proposed as a strategy to tune the signal-to-noise ratio by carefully controlling the carrier density within the semiconductor. However, the performance improvement has so far been quite marginal. With metallic electrodes, the gate dependence of the photocurrent follows the gate-induced change of the dark current. Graphene presents key advantages: (i) infrared transparency that allows back-side illumination, (ii) vertical electric field transparency, and (iii) carrier selectivity under gate bias. Here, we investigate a configuration of 2D/0D infrared photodetectors taking advantage of a high capacitance ionic glass gate, large-scale graphene electrodes, and a HgTe nanocrystals layer of high carrier mobility. The introduction of graphene electrodes combined with ionic glass enables one to reconfigure selectively the HgTe nanocrystals and the graphene electrodes between electron-doped (n) and hole-doped (p) states. We unveil that this functionality enables the design a 2D/0D p-n junction that expands throughout the device, with a built-in electric field that assists charge dissociation. We demonstrate that, in this specific configuration, the signal-to-noise ratio for infrared photodetection can be enhanced by 2 orders of magnitude, and that photovoltaic operation can be achieved. The detectivity now reaches 109 Jones, whereas the device only absorbs 8% of the incident light. Additionally, the time response of the device is fast (<10 µs), which strongly contrasts with the slow response commonly observed for 2D/0D mixed-dimensional heterostructures, where larger photoconduction gains come at the cost of slower response.

HgTe Nanocrystals for SWIR Detection and Their Integration up to the Focal Plane Array.

Infrared applications remain too often a niche market due to their prohibitive cost. Nanocrystals offer an interesting alternative to reach cost disruption especially in the short-wave infrared (SWIR, λ < 1.7 µm) where material maturity is now high. Two families of materials are candidate for SWIR photoconduction: lead and mercury chalcogenides. Lead sulfide typically benefits from all the development made for a wider band gap such as the one made for solar cells, while HgTe takes advantage of the development relative to mid-wave infrared detectors. Here, we make a fair comparison of the two material detection properties in the SWIR and discuss the material stability. At such wavelengths, studies have been mostly focused on PbS rather than on HgTe, therefore we focus in the last part of the discussion on the effect of surface chemistry on the electronic spectrum of HgTe nanocrystals. We unveil that tuning the capping ligands is a viable strategy to adjust the material from the p-type to ambipolar. Finally, HgTe nanocrystals are integrated into multipixel devices to quantize spatial homogeneity and onto read-out circuits to obtain a fast and sensitive infrared laser beam profile.

Field-Effect Transistor and Photo-Transistor of Narrow-Band-Gap Nanocrystal Arrays Using Ionic Glasses.

The gating of nanocrystal films is currently driven by two approaches: either the use of a dielectric such as SiO2 or the use of electrolyte. SiO2 allows fast bias sweeping over a broad range of temperatures but requires a large operating bias. Electrolytes, thanks to large capacitances, lead to the significant reduction of operating bias but are limited to slow and quasi-room-temperature operation. None of these operating conditions are optimal for narrow-band-gap nanocrystal-based phototransistors, for which the necessary large-capacitance gate has to be combined with low-temperature operation. Here, we explore the use of a LaF3 ionic glass as a high-capacitance gating alternative. We demonstrate for the first time the use of such ionic glasses to gate thin films made of HgTe and PbS nanocrystals. This gating strategy allows operation in the 180 to 300 K range of temperatures with capacitance as high as 1 µF·cm-2. We unveil the unique property of ionic glass gate to enable the unprecedented tunability of both magnitude and dynamics of the photocurrent thanks to high charge-doping capability within an operating temperature window relevant for infrared photodetection. We demonstrate that by carefully choosing the operating gate bias, the signal-to-noise ratio can be improved by a factor of 100 and the time response accelerated by a factor of 6. Moreover, the good transparency of LaF3 substrate allows back-side illumination in the infrared range, which is highly valuable for the design of phototransistors.

A colloidal quantum dot infrared photodetector and its use for intraband detection.

Wavefunction engineering using intraband transition is the most versatile strategy for the design of infrared devices. To date, this strategy is nevertheless limited to epitaxially grown semiconductors, which lead to prohibitive costs for many applications. Meanwhile, colloidal nanocrystals have gained a high level of maturity from a material perspective and now achieve a broad spectral tunability. Here, we demonstrate that the energy landscape of quantum well and quantum dot infrared photodetectors can be mimicked from a mixture of mercury selenide and mercury telluride nanocrystals. This metamaterial combines intraband absorption with enhanced transport properties (i.e. low dark current, fast time response and large thermal activation energy). We also integrate this material into a photodiode with the highest infrared detection performances reported for an intraband-based nanocrystal device. This work demonstrates that the concept of wavefunction engineering at the device scale can now be applied for the design of complex colloidal nanocrystal-based devices.

Halide Ligands To Release Strain in Cadmium Chalcogenide Nanoplatelets and Achieve High Brightness.

Zinc blende II-VI semiconductor nanoplatelets (NPLs) are defined at the atomic scale along the thickness of the nanoparticle and are initially capped with carboxylates on the top and bottom [001] facets. These ligands are exchanged on CdSe NPLs with halides that act as X-L-type ligands. These CdSe NPLs are costabilized by amines to provide colloidal stability in nonpolar solvents. The hydrogen from the amine can participate in a hydrogen bond with the lone pair electrons of surface halides. After ligand exchange, the optical features are red-shifted. Thus, ligand tuning is another way, in addition to confinement, to tune the optical features of NPLs. The improved surface passivation leads to an increase in the fluorescence quantum efficiency of up to 70% in the case of bromide. However, for chloride and iodide, the surface coverage is incomplete, and thus, the fluorescence quantum efficiency is lower. This ligand exchange is associated with a decrease in stress that leads to unfolding of the NPLs, which is particularly noticeable for iodide-capped NPLs.

Impact of dimensionality and confinement on the electronic properties of mercury chalcogenide nanocrystals.

We demonstrate the growth of 2D nanoplatelets (NPLs) made of a HgTe/CdS heterostructure, with an optical absorption reaching the shortwave infrared range. The material is an interesting platform to investigate the effect of dimensionality (0D vs. 2D) and confinement on the electronic spectrum and carrier dynamics in colloidal materials. We bring consistent evidence for the p-type nature of this material from transport and photoemission measurements. The majority carrier dynamics probed using pump-probe photoemission is found to be mostly dependent on the presence of a confinement barrier at the surface rather than on the material dimensionality. The minority carrier, on the other hand, is strongly affected by the material shape showing a longer lived minority carrier in 2D NPLs compared to their 0D equivalent with a similar band gap. Finally, we test the potential of this material for photodetection in the short-wave infrared range (SWIR) and show that fast photoresponse and detectivity reaching 109 Jones at room temperature can be achieved.