Colloidal Quantum Wells Research Articles

Light-sensitive monolayer-thick nanocrystal skins of face-down self-oriented colloidal quantum wells.

Colloidal quantum wells (CQWs), a quasi-two-dimensional, atomically-flat sub-family of semiconductor nanocrystals, are well suited to produce excellent devices for photosensing applications thanks to their extraordinarily large absorption cross-sections. In this work, we propose and demonstrate a new class of light-sensitive nanocrystal skins (LS-NS) that employ a monolayer of face-down orientation-controlled self-assembled CQWs as the active absorbing layer in the UV-visible range. This CQW LS-NS platform enables non-conventional photosensing operation that relies on the strong optical absorption of the monolayered assembly of CQWs and the subsequent photogenerated potential build-up across the device, allowing for self-powered operation. Here such self-oriented CQWs reduce the surface roughness in their monolayer-thick film, essential to high device performance. Owing to their ease of fabrication and low cost, these devices hold great promise for large-scale use in semi-transparent photosensing surfaces.

Observation of Phonon Cascades in Cu-Doped Colloidal Quantum Wells.

Electronic doping has endowed colloidal quantum wells (CQWs) with unique optical and electronic properties, holding great potential for future optoelectronic device concepts. Unfortunately, how photogenerated hot carriers interact with phonons in these doped CQWs still remains an open question. Here, through investigating the emission properties, we have observed an efficient phonon cascade process (i.e., up to 27 longitudinal optical phonon replicas are revealed in the broad Cu emission band at room temperature) and identified a giant Huang-Rhys factor (S ≈ 12.4, more than 1 order of magnitude larger than reported values of other inorganic semiconductor nanomaterials) in Cu-doped CQWs. We argue that such an ultrastrong electron-phonon coupling in Cu-doped CQWs is due to the dopant-induced lattice distortion and the dopant-enhanced density of states. These findings break the widely accepted consensus that electron-phonon coupling is typically weak in quantum-confined systems, which are crucial for optoelectronic applications of doped electronic nanomaterials.

P‐9.6: High Efficiency Deep‐Red Colloidal Quantum Well Light‐Emitting Diodes Enabled by Balanced Carrier Injection

Colloidal quantum wells (CQWs) are regarded as a frontier class of light-emitting diodes (LEDs) owing to their efficient and ultranarrow luminescence spectrum, directional emission, and high light extraction. However, CQW-LEDs with deep-red (> 660 nm) light emission, a vital part for high-definition color displays, optical medical, and horticultural lighting, remain a great challenge. Herein, high-efficiency deep-red CQW-LEDs are reported. With the enhancement of device engineering, the LED devices that based new CQW materials have shown high external quantum efficiency of 9.89%. Additionally, Mg-doped zinc oxide (ZnMgO) and In2O3 as electron transport layer (ETL) are introduced into CQW-LEDs for the first time, and the effect of different ETLs on carrier injection balance of CQW-LEDs is investigated. Furthermore, the first prototype active-matrix CQW-LED (AMCQW-LED) pixel circuit was constructed by connecting thin film transistor (TFT) source terminal with CQW-LED. The findings may not only begin the first step that TFT drives CQW-LED, but also reveal the carrier injection balance mechanism of CQW-LEDs, and can be further applied to other wavelengths of CQW-LEDs.

Efficient generation of emissive many-body correlations in copper-doped colloidal quantum wells

Colloidal quantum wells (CQWs) provide an appealing platform to achieve emissive many-body correlations for novel optoelectronic devices, given that they act as hosts for strong carrier Coulomb interactions and present suppressed Auger recombination. However, the demonstrated high-order excitonic emission in CQWs requires ultrafast pumping with high excitation levels and can only be spectrally resolved at the single-particle level under cryogenic conditions. Here, through systematic investigation using static power-dependent emission spectroscopy and transient carrier dynamics, we show that Cu-doped CdSe CQWs exhibit continuous-wave-pumped high-order excitonic emission at room temperature with a large binding energy of ∼64 meV. We attribute this unique behavior to dopant excitons in which the ultralong lifetime and the highly localized wavefunction facilitate the formation of many-body correlations. The spectrally resolved high-order excitonic emission generated at power levels compatible with solar irradiation and electrical injection might pave the way for novel solution-processed solid-state devices. • Continuous-wave-pumped high-order excitonic emission at room temperature is shown • The excitation level is compatible with solar irradiation and electrical injection • 64 meV binding energy enables spectrally resolved high-order excitonic emission Yu et al. demonstrate continuous-wave-pumped high-order excitonic emission at room temperature in Cu-doped CdSe colloidal quantum wells. The properties of dopant excitons enable an ultra-low excitation level compatible with solar irradiation or electrical injection and a binding energy of ∼64 meV, which makes the high-order excitonic emission spectrally resolvable at room temperature.

High-Performance Deep Red Colloidal Quantum Well Light-Emitting Diodes Enabled by the Understanding of Charge Dynamics.

Colloidal quantum wells (CQWs) have emerged as a promising family of two-dimensional (2D) optoelectronic materials with outstanding properties, including ultranarrow luminescence emission, nearly unity quantum yield, and large extinction coefficient. However, the performance of CQWs-based light-emitting diodes (CQW-LEDs) is far from satisfactory, particularly for deep red emissions (≥660 nm). Herein, high efficiency, ultra-low-efficiency roll-off, high luminance, and extremely saturated deep red CQW-LEDs are reported. A key feature for the high performance is the understanding of charge dynamics achieved by introducing an efficient electron transport layer, ZnMgO, which enables balanced charge injection, reduced nonradiative channels, and smooth films. The CQW-LEDs based on (CdSe/CdS)@(CdS/CdZnS) ((core/crown)@(colloidal atomic layer deposition shell/hot injection shell)) show an external quantum efficiency of 9.89%, which is a record value for 2D nanocrystal LEDs with deep red emissions. The device also exhibits an ultra-low-efficiency roll-off and a high luminance of 3853 cd m-2. Additionally, an exceptional color purity with the CIE coordinates of (0.719, 0.278) is obtained, indicating that the color gamut covers 102% of the International Telecommunication Union Recommendation BT 2020 (Rec. 2020) standard in the CIE 1931 color space, which is the best for CQW-LEDs. Furthermore, an active-matrix CQW-LED pixel circuit is demonstrated. The findings imply that the understanding of charge dynamics not only enables high-performance CQW-LEDs and can be further applied to other kinds of nanocrystal LEDs but also is beneficial to the development of CQW-LEDs-based display technology and related integrated optoelectronics.

Color Enrichment Solids of Spectrally Pure Colloidal Quantum Wells for Wide Color Span in Displays

AbstractColloidal quantum wells (CQWs) are excellent candidates for lighting and display applications owing to their narrow emission linewidths (<30 nm). However, realizing their efficient and stable light‐emitting solids remains a challenge. To address this problem, stable, efficient solids of CQWs incorporated into crystal matrices are shown. Green‐emitting CdSe/CdS core/crown and red‐emitting CdSe/CdS core/shell CQWs wrapped into these crystal solids are employed as proof‐of‐concept demonstrations of light‐emitting diode (LED) integration targeting a wide color span in display backlighting. The quantum yield of the green‐ and red‐emitting CQW‐containing solids of sucrose reach ≈20% and ≈55%, respectively, while emission linewidths and peak wavelengths remain almost unaltered. Furthermore, sucrose matrix preserves ≈70% and ≈45% of the initial emission intensity of the green‐ and red‐emitting CQWs after >60 h, respectively, which is ≈4× and ≈2× better than the drop‐casted CQW films and reference (KCl) host. Color‐converting LEDs of these green‐ and red‐emitting CQWs in sucrose possess luminous efficiencies 122 and 189 lm W−1elect, respectively. With the liquid crystal display filters, this becomes 39 and 86 lm W−1elect, respectively, providing with a color gamut 25% broader than the National Television Standards Committee standard. These results prove that CQW solids enable efficient and stable color converters for display and lighting applications.

Gain roll-off in cadmium selenide colloidal quantum wells under intense optical excitation

Colloidal quantum wells, or nanoplatelets, show among the lowest thresholds for amplified spontaneous emission and lasing among solution-cast materials and among the highest modal gains of any known materials. Using solution measurements of colloidal quantum wells, this work shows that under photoexcitation, optical gain increases with pump fluence before rolling off due to broad photoinduced absorption at energies lower than the band gap. Despite the common occurrence of gain induced by an electron–hole plasma found in bulk materials and epitaxial quantum wells, under no measurement conditions was the excitonic absorption of the colloidal quantum wells extinguished and gain arising from a plasma observed. Instead, like gain, excitonic absorption reaches a minimum intensity near a photoinduced carrier sheet density of 2 × 1013 cm−2 above which the absorption peak begins to recover. To understand the origins of these saturation and reversal effects, measurements were performed with different excitation energies, which deposit differing amounts of excess energy above the band gap. Across many samples, it was consistently observed that less energetic excitation results in stronger excitonic bleaching and gain for a given carrier density. Transient and static optical measurements at elevated temperatures, as well as transient X-ray diffraction of the samples, suggest that the origin of gain saturation and reversal is a heating and disordering of the colloidal quantum wells which produces sub-gap photoinduced absorption.

Management of electroluminescence from silver-doped colloidal quantum well light-emitting diodes

Impurity doping is a promising strategy to afford colloidal nanocrystals exhibiting novel optical, catalytic, and electronic characteristics. However, some significant properties of noble metal-doped nanocrystals (NMD-NCs) remain unknown. Here, we report the electroluminescence (EL) from NMD-NCs. By doping silver impurity into cadmium selenide colloidal quantum wells (CQWs), dual-emission emitters are achieved and a light-emitting diode (LED) with a luminance of 1,339 cd m −2 is reported. In addition, the proposed energy gap engineering to manage exciton recombination is a feasible scheme for tunable EL emissions (e.g., the dopant emission is tuned from 606 to 761 nm). Furthermore, an organic-inorganic hybrid white LED based on CQWs is realized, reaching a color rendering index of 82. Moreover, flexible CQW-LEDs are reported. The findings present a step to unveil the EL property of NMD-NCs, which can be extended to other noble metal impurities, and pave the pathway for NMD-NCs as a class of electronic materials for EL applications. • Electroluminescence from noble metal-doped nanocrystals • Energy gap engineering to manage exciton recombination and tune emission • Organic-inorganic hybrid white LEDs based on colloidal quantum wells • Flexible colloidal quantum well LEDs Liu et al. report on electroluminescence from Ag-doped CdSe colloidal quantum wells. Energy gap engineering to manage exciton recombination is a feasible strategy for tunable electroluminescence emission of light-emitting diodes. Organic-inorganic hybrid white light-emitting diodes based on colloidal quantum wells and flexible colloidal quantum well light-emitting diodes are reported.

Observation of optical gain from aqueous quantum well heterostructures in water.

Although achieving optical gain using aqueous solutions of colloidal nanocrystals as a gain medium is exceptionally beneficial for bio-optoelectronic applications, the realization of optical gain in an aqueous medium using solution-processed nanocrystals has been extremely challenging because of the need for surface modification to make nanocrystals water dispersible while still maintaining their gain. Here, we present the achievement of optical gain in an aqueous medium using an advanced architecture of CdSe/CdS@CdxZn1-xS core/crown@gradient-alloyed shell colloidal quantum wells (CQWs) with an ultralow threshold of ∼3.4 μJ cm-2 and an ultralong gain lifetime of ∼2.6 ns. This demonstration of optical gain in an aqueous medium is a result of the carefully heterostructured CQWs having large absorption cross-section and gain cross-section in addition to inherently slow Auger recombination in these CQWs. Furthermore, we show low-threshold in-water amplified spontaneous emission (ASE) from these aqueous CQWs with a threshold of 120 μJ cm-2. In addition, we demonstrate a whispering gallery mode laser with a low threshold of ∼30 μJ cm-2 obtained by incorporating films of CQWs by exploiting layer-by-layer approach on a fiber. The observation of low-threshold optical gain with ultralong gain lifetime presents a significant step toward the realization of advanced optofluidic colloidal lasers and their continuous-wave pumping.

All-colloidal parity-time-symmetric microfiber lasers balanced between the gain of colloidal quantum wells and the loss of colloidal metal nanoparticles.

Lasers based on semiconductor colloidal quantum wells (CQWs) have attracted wide attention, thanks to their facile solution-processability, low threshold and wide range spectral tunability. Colloidal microlasers based on whispering-gallery-mode (WGM) resonators have already been widely demonstrated. However, due to their microscale size typically supporting multiple modes, they suffer from multimode competition and higher threshold. The ability to control the multiplicity of modes oscillating within colloidal laser resonators and achieving single-mode lasers is of fundamental importance in many photonic applications. Here we show that as a unique, simple and versatile architecture of all-colloidal lasers intrinsically enabled by balanced gain/loss segments, the lasing threshold reduction and spectral purification can be readily achieved in a system of a WGM-supported microfiber cavity by harnessing the notions of parity-time symmetry (PT). In particular, we demonstrate a proof-of-concept PT-symmetric microfiber laser employing CQWs as the colloidal gain medium along with a carefully tuned nanocomposite of Ag nanoparticles (Ag NPs) incorporated into a PMMA matrix altogether and conveniently coated around a coreless microfiber as a rigorously tailored colloidal loss medium to balance the gain. The realization of gain/loss segments in our PT-symmetric all-colloidal arrangement is independent of selected pumping, reducing the complexity of the system and making compact device applications feasible, where control over the pumping is not possible. We observed a reduction in the number of modes, resulting in a reduced threshold and enhanced output power of the PT-symmetric laser. The PT-symmetric CQW-WGM microcavity architecture offers new opportunities towards simple implementation of high-performance optical resonators for colloidal lasers.

Transient reshaping of intraband transitions by hot electrons.

Hot electrons, far above the lattice temperature of a material, present opportunities for enhanced solar energy harvesting or performance of otherwise unfavorable chemistry. The spectroscopic signatures and dynamics of hot carrier absorption and emission have been extensively studied in bulk and nanoscopic semiconductors, but the effects on intraband transitions are largely unexplored. Here, the effect of hot electrons on the properties of colloidal quantum wells made of cadmium selenide is examined using ultrafast spectroscopy. Similar to expitaxial quantum wells, these atomically precise materials support intersubband transitions (a class of intraband transitions in 1D and 2D materials) in the near-infrared spectral window. Using energy-dependent photoexcitation, it is shown that electrons reach effective temperatures of 2000 K or greater. This results in a substantial transient shift in the oscillator strength of the instersubband transition to lower energies on a sub-picosecond time-scale. Similar heating of electrons is achieved under mid-infrared re-excitation, which permits ultrafast transmittance modulation throughout the near-infrared.

Broadband Optical Phase Modulation by Colloidal CdSe Quantum Wells.

Two-dimensional (2D) semiconductors are primed to realize a variety of photonic devices that rely on the transient properties of photogenerated charges, yet little is known on the change of the refractive index. The associated optical phase changes can be beneficial or undesired depending on the application, but require proper quantification. Measuring optical phase modulation of dilute 2D materials is, however, not trivial with common methods. Here, we demonstrate that 2D colloidal CdSe quantum wells, a useful model system, can modulate the phase of light across a broad spectrum using a femtosecond interferometry method. Next, we develop a toolbox to calculate the time-dependent refractive index of colloidal 2D materials from widely available transient absorption experiments using a modified effective medium algorithm. Our results show that the excitonic features of 2D materials result in broadband, ultrafast, and sizable phase modulation, even extending to the near infrared because of intraband transitions.

Deep‐Red‐Emitting Colloidal Quantum Well Light‐Emitting Diodes Enabled through a Complex Design of Core/Crown/Double Shell Heterostructure

AbstractExtending the emission peak wavelength of quasi‐2D colloidal quantum wells has been an important quest to fully exploit the potential of these materials, which has not been possible due to the complications arising from the partial dissolution and recrystallization during growth to date. Here, the synthetic pathway of (CdSe/CdS)@(1‐4 CdS/CdZnS) (core/crown)@(colloidal atomic layer deposition shell/hot injection shell) hetero‐nanoplatelets (NPLs) using multiple techniques, which together enable highly efficient emission beyond 700 nm in the deep‐red region, is proposed and demonstrated. Given the challenges of using conventional hot injection procedure, a method that allows to obtain sufficiently thick and passivated NPLs as the seeds is developed. Consequently, through the final hot injection shell coating, thick NPLs with superior optical properties including a high photoluminescence quantum yield of 88% are achieved. These NPLs emitting at 701 nm exhibit a full‐width‐at‐half‐maximum of 26 nm, enabled by the successfully maintained quasi‐2D shape and minimum defects of the resulting heterostructure. The deep‐red light‐emitting diode (LED) device fabricated with these NPLs has shown to yield a high external quantum efficiency of 6.8% at 701 nm, which is on par with other types of LEDs in this spectral range.

High Efficiency and Narrow Emission Band Pure-Red Perovskite Colloidal Quantum Wells.

Colloidal quantum wells (CQWs) have excellent optical performance, such as ultranarrow emission, due to strong quantum confinement in the vertical direction. However, there are few reports on metal halide perovskite CQWs with high-purity red emission (∼630 nm) for the display application, owing to the broadened photoluminescence spectrum and beyond the red emission range. Herein, we successfully synthesize high-quality CsPbI3 CQWs in a strong electronegative solvent (mesitylene), which cut the chemical reaction rate of the precursor system to slow down the crystal nuclei growth. The number of PbI64- octahedral layers (n) of CQWs can be regulated to achieve the emission of the CQW shift from orange (596 nm, n = 3) to red (626 nm, n = 4). The pure-red-emitting CQWs have a high photoluminescence quantum yield of 99% and a narrow emission bandwidth (28 nm). The Commission Internationale de l'Eclairage coordinates (0.69, 0.31) meet the requirement of the Rec. 2020 standard.

51.2: Invited Paper: Approaches to achieve high‐performance colloidal quantum wells light‐emitting diodes

51.2: <i>Invited Paper:</i> Approaches to achieve high‐performance colloidal quantum wells light‐emitting diodes

(Invited) Conduction Band Structure of Colloidal Quantum Wells

Similar to epitaxial quantum wells, colloidal quantum wells display electron intersubband transitions when photoexcited or electrochemically charged. Compared to epitaxial quantum wells, the strong confinement effect of thin, monodisperse colloidal quantum wells results in narrow intersubband transitions which reach high energies spanning the near-infrared spectral range. The composition of surface ligand chemistry subtly tunes the strain of the colloidal quantum wells to generate intersubband transitions over nearly continuously tunable energies. The divergent behavior of the band gap energy and intersubband transition energy implicates a substantial role of biaxial (in-plane) strain on the valence band structure. Multiple pump transient spectroscopy was furthermore employed to examine the lifetime of intersubband transitions, which is critical to their implementation in quantum cascade lasers or infrared detectors. In all cases, including core/shell samples, the lifetime of intersubband transitions is limited by surface or LO phonons to 1 ps or less, much shorter than comparable intraband transitions in quantum dots.

Self-Resonant Microlasers of Colloidal Quantum Wells Constructed by Direct Deep Patterning.

Here, the first account of self-resonant fully colloidal μ-lasers made from colloidal quantum well (CQW) solution is reported. A deep patterning technique is developed to fabricate well-defined high aspect-ratio on-chip CQW resonators made of grating waveguides and in-plane reflectors. The fabricated waveguide-coupled laser, enabling tight optical confinement, assures in-plane lasing. CQWs of the patterned layers are closed-packed with sharp edges and residual-free lifted-off surfaces. Additionally, the method is successfully applied to various nanoparticles including colloidal quantum dots and metal nanoparticles. It is observed that the patterning process does not affect the nanocrystals (NCs) immobilized in the attained patterns and the different physical and chemical properties of the NCs remain pristine. Thanks to the deep patterning capability of the proposed method, patterns of NCs with subwavelength lateral feature sizes and micron-scale heights can possibly be fabricated in high aspect ratios.

Low‐Threshold Lasing from Copper‐Doped CdSe Colloidal Quantum Wells

AbstractTransition metal doped colloidal nanomaterials (TMDCNMs) have recently attracted attention as promising nano‐emitters due to dopant‐induced properties. However, despite ample investigations on the steady‐state and dynamic spectroscopy of TMDCNMs, experimental understandings of their performance in stimulated emission regimes are still elusive. Here, the optical gain properties of copper‐doped CdSe colloidal quantum wells (CQWs) are systemically studied with a wide range of dopant concentration for the first time. This work demonstrates that the amplified spontaneous emission (ASE) threshold in copper‐doped CQWs is a competing result between the biexciton formation, which is preferred to achieve population inversion, and the hole trapping which stymies the population inversion. An optimum amount of copper dopants enables the lowest ASE threshold of ≈7 µJ cm−2, about 8‐fold reduction from that in undoped CQWs (≈58 µJ cm−2) under sub‐nanosecond pulse excitation. Finally, a copper‐doped CQW film embedded in a vertical cavity surface‐emitting laser (VCSEL) structure yields an ultralow lasing threshold of 4.1 µJ cm−2. Exploiting optical gain from TMDCNMs may help to further boost the performance of colloidal‐based lasers.

Colloidal Gain Media: Single‐Mode Lasing from a Single 7 nm Thick Monolayer of Colloidal Quantum Wells in a Monolithic Microcavity (Laser Photonics Rev. 15(4)/2021)

In article number 2000479, Hilmi Volkan Demir and co-workers demonstrate single-mode lasing from an ultrathin self-assembled monolayer of colloidal quantum wells (CQWs) with a record thickness of 7 nm. The CQWs are integrated into a high-quality-factor microcavity with accurate spectral/spatial alignment of the cavity mode. By overcoming the long-pending problem of limited electrical conductivity in thicker colloidal films, such ultrathin colloidal gain media may enable electrically-driven colloidal lasers.

Single‐Mode Lasing from a Single 7 nm Thick Monolayer of Colloidal Quantum Wells in a Monolithic Microcavity

AbstractIn this work, monolithically‐fabricated vertical cavity surface emitting lasers (VCSELs) of densely‐packed, orientation‐controlled, atomically flat colloidal quantum wells (CQWs) using a self‐assembly method is reported and single‐mode lasing from a record thin colloidal gain medium with a film thickness of 7 nm under femtosecond optical excitation is demonstrated. Specially engineered CQWs are used to demonstrate these hybrid CQW‐VCSELs consisting of only a few layers to a single monolayer of CQWs and are achieved the lasing from these thin gain media by thoroughly modeling and implementing a vertical cavity consisting of distributed Bragg reflectors with an additional dielectric layer for mode tuning. Accurate spectral and spatial alignment of the cavity mode with the CQW films is secured with the help of full electromagnetic computations. While overcoming the long‐pending problem of limited electrical conductivity in thicker colloidal films, such ultrathin colloidal gain media can be helpful to enable fully electrically‐driven colloidal lasers.