Two-Color Amplified Spontaneous Emission from Auger-Suppressed Quantum Dots in Liquids.

Colloidal quantum-dot (QD) lasing is normally achieved in close-packed solid-state films, as a high QD volume fraction is required for stimulated emission to outcompete fast Auger decay of optical-gain-active multiexciton states. Here a new type of liquid optical-gain medium is demonstrated, in which compact compositionally-graded QDs (ccg-QDs) that feature strong suppression of Auger decay are liquefied using a small amount of solvent. Transient absorption measurements of ccg-QD liquid suspensions reveal broad-band optical gain spanning a wide spectral range from 560 (green) to 675 nm (red). The gain magnitude is sufficient to realize a two-color amplified spontaneous emission (ASE) at 637 and 594 nm due to the band-edge (1S) and the excited-state (1P) transition, respectively. Importantly, the ASE regime is achieved using quasicontinuous excitation with nanosecond pulses. Furthermore, the ASE is highly stable under prolonged excitation, which stands in contrast to traditional dyes that exhibit strong degradation under identical excitation conditions. These observations point toward a considerable potential of high-density ccg-QD suspensions as liquid, dye-like optical gain media that feature readily achievable spectral tunability and stable operation under intense photoexcitation.

Spin-exchange carrier multiplication in manganese-doped colloidal quantum dots.

Carrier multiplication is a process whereby a kinetic energy of a carrier relaxes via generation of additional electron-hole pairs (excitons). This effect has been extensively studied in the context of advanced photoconversion as it could boost the yield of generated excitons. Carrier multiplication is driven by carrier-carrier interactions that lead to excitation of a valence-band electron to the conduction band. Normally, the rate of phonon-assisted relaxation exceeds that of Coulombic collisions, which limits the carrier multiplication yield. Here we show that this limitation can be overcome by exploiting not 'direct' but 'spin-exchange' Coulomb interactions in manganese-doped core/shell PbSe/CdSe quantum dots. In these structures, carrier multiplication occurs via two spin-exchange steps. First, an exciton generated in the CdSe shell is rapidly transferred to a Mn dopant. Then, the excited Mn ion undergoes spin-flip relaxation via a spin-conserving pathway, which creates two excitons in the PbSe core. Due to the extremely fast, subpicosecond timescales of spin-exchange interactions, the Mn-doped quantum dots exhibit an up-to-threefold enhancement of the multiexciton yield versus the undoped samples, which points towards the considerable potential of spin-exchange carrier multiplication in advanced photoconversion.

Colloidal Semiconductor Nanocrystal Lasers and Laser Diodes.

Lasers and optical amplifiers based on solution-processable materials have been long-desired devices for their compatibility with virtually any substrate, scalability, and ease of integration with on-chip photonics and electronics. These devices have been pursued across a wide range of materials including polymers, small molecules, perovskites, and chemically prepared colloidal semiconductor nanocrystals, also commonly referred to as colloidal quantum dots. The latter materials are especially attractive for implementing optical-gain media as in addition to being compatible with inexpensive and easily scalable chemical techniques, they offer multiple advantages derived from a zero-dimensional character of their electronic states. These include a size-tunable emission wavelength, low optical gain thresholds, and weak sensitivity of lasing characteristics to variations in temperature. Here we review the status of colloidal nanocrystal lasing devices, most recent advances in this field, outstanding challenges, and the ongoing progress toward technological viable devices including colloidal quantum dot laser diodes.

Electrically driven amplified spontaneous emission from colloidal quantum dots.

Colloidal quantum dots (QDs) are attractive materials for realizing solution-processable laser diodes that could benefit from size-controlled emission wavelengths, low optical-gain thresholds and ease of integration with photonic and electronic circuits1-7. However, the implementation of such devices has been hampered by fast Auger recombination of gain-active multicarrier states1,8, poor stability of QD films at high current densities9,10 and the difficulty to obtain net optical gain in a complex device stack wherein a thin electroluminescent QD layer is combined with optically lossy charge-conducting layers11-13. Here we resolve these challenges and achieve amplified spontaneous emission (ASE) from electrically pumped colloidal QDs. The developed devices use compact, continuously graded QDs with suppressed Auger recombination incorporated into a pulsed, high-current-density charge-injection structure supplemented by a low-loss photonic waveguide. These colloidal QD ASE diodes exhibit strong, broadband optical gain and demonstrate bright edge emission with instantaneous power of up to 170 µW.

Optically Excited Lasing in a Cavity-Based, High-Current-Density Quantum Dot Electroluminescent Device.

Laser diodes based on solution-processable materials can benefit numerous technologies including integrated electronics and photonics, telecommunications, and medical diagnostics. An attractive system for implementing these devices is colloidal semiconductor quantum dots (QDs). The progress towards a QD laser diode has been hampered by rapid nonradiative Auger decay of optical-gain-active multicarrier states, fast device degradation at high current densities required for laser action, and unfavorable competition between optical gain and optical losses in a multicomponent device stack. Here we resolve some of these challenges and demonstrate optically excited lasing from fully functional high-current density electroluminescent (EL) devices with an integrated optical resonator. This advance has become possible due to excellent optical gain properties of continuously graded QDs and a refined device architecture, which allows for highly efficient light amplification in a thin, EL-active QD layer.

Two-band optical gain and ultrabright electroluminescence from colloidal quantum dots at 1000 A cm-2.

Colloidal quantum dots (QDs) are attractive materials for the realization of solution-processable laser diodes. Primary challenges towards this objective are fast optical-gain relaxation due to nonradiative Auger recombination and poor stability of colloidal QD solids under high current densities required to obtain optical gain. Here we resolve these challenges and achieve broad-band optical gain spanning the band-edge (1S) and the higher-energy (1P) transitions. This demonstration is enabled by continuously graded QDs with strongly suppressed Auger recombination and a current-focusing device design, combined with short-pulse pumping. Using this approach, we achieve ultra-high current densities (~1000 A cm-2) and brightness (~10 million cd m-2), and demonstrate an unusual two-band electroluminescence regime for which the 1P band is more intense than the 1S feature. This implies the realization of extremely large QD occupancies of up to ~8 excitons per-dot, which corresponds to complete filling of the 1S and 1P electron shells.

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.

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.

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.

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.

Doping as a Strategy to Tune Color of 2D Colloidal Nanoplatelets.

Among colloidal nanocrystals, 2D nanoplatelets (NPLs) made of II-VI compounds appear as a special class of emitters with an especially narrow photoluminescence signal. However, the PL signal in the case of NPLs is only tunable by a discrete step. Here, we demonstrate that doping is a viable path to finely tune the color of these NPLs from green to red, making them extremely interesting as phosphors for wide-gamut display. In addition, using a combination of luminescence spectroscopy, tight-binding simulation, transport, and photoemission, we provide a consistent picture for the Ag+-doped CdSe NPLs. The Ag-activated state is strongly bound and located 340 meV above the valence band of the bulk material. The Ag dopant induces a relative shift of the Fermi level toward the valence band by up to 400 meV but preserves the n-type nature of the material.

Road Map for Nanocrystal Based Infrared Photodetectors.

Infrared (IR) sensors based on epitaxially grown semiconductors face two main challenges which are their prohibitive cost and the difficulty to rise the operating temperature. The quest for alternative technologies which will tackle these two difficulties requires the development of new IR active materials. Over the past decade, significant progresses have been achieved. In this perspective, we summarize the current state of the art relative to nanocrystal based IR sensing and stress the main materials, devices and industrial challenges which will have to be addressed over the 5 next years.

Millijoule femtosecond pulses at 1937 nm from a diode-pumped ring cavity Tm:YAP regenerative amplifier.

We present an infrared source operating at 1937 nm center wavelength capable of generating 1.35 mJ pulse energies with 1 kHz repetition rate and 2 GW peak power based on a diode-pumped Tm:YAP regenerative amplifier. The obtained pulses after 45 round trips have been compressed down to 360 fs. Using only a small portion (15 µJ) of the output of the system we managed to generate a white light continuum in a 3 mm YAG window that exhibits the viability of the system as a suitable candidate for a pumping source of a mid-infrared optical parametric amplifier.

Wave-Function Engineering in HgSe/HgTe Colloidal Heterostructures To Enhance Mid-infrared Photoconductive Properties.

The use of intraband transition is an interesting alternative path for the design of optically active complex colloidal materials in the mid-infrared range. However, so far, the performance obtained for photodetection based on intraband transition remains much smaller than the one relying on interband transition in narrow-band-gap materials operating at the same wavelength. New strategies have to be developed to make intraband materials more effective. Here, we propose growing a heterostructure of HgSe/HgTe as a means of achieving enhanced intraband-based photoconduction. We first tackle the synthetic challenge of growing a heterostructure on soft (Hg-based) material. The electronic spectrum of the grown heterostructure is then investigated using a combination of numerical simulation, infrared spectroscopy, transport measurement, and photoemission. We report a type-II band alignment with reduced doping compared with a core-only object and boosted hole conduction. Finally, we probe the photoconductive properties of the heterostructure while resonantly exciting the intraband transition by using a high-power-density quantum cascade laser. Compared to the previous generation of material based on core-only HgSe, the heterostructures have a lower dark current, stronger temperature dependence, faster photoresponse (with a time response below 50 µs), and detectivity increased by a factor of 30.

Terahertz HgTe Nanocrystals: Beyond Confinement.

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.

Band Edge Dynamics and Multiexciton Generation in Narrow Band Gap HgTe Nanocrystals.

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.

HgSe Self-Doped Nanocrystals as a Platform to Investigate the Effects of Vanishing Confinement.

Self-doped colloidal quantum dots (CQDs) attract a strong interest for the design of a new generation of low-cost infrared (IR) optoelectronic devices because of their tunable intraband absorption feature in the mid-IR region. However, very little remains known about their electronic structure which combines confinement and an inverted band structure, complicating the design of optimized devices. We use a combination of IR spectroscopy and photoemission to determine the absolute energy levels of HgSe CQDs with various sizes and surface chemistries. We demonstrate that the filling of the CQD states ranges from 2 electrons per CQD at small sizes (<5 nm) to more than 18 electrons per CQD at large sizes (≈20 nm). HgSe CQDs are also an interesting platform to observe vanishing confinement in colloidal nanoparticles. We present lines of evidence for a semiconductor-to-metal transition at the CQD level, through temperature-dependent absorption and transport measurements. In contrast with bulk systems, the transition is the result of the vanishing confinement rather than the increase of the doping level.