Quantum Dot Films Research Articles

Fabrication of methylated carbon quantum dot-based fluorescent films for highly sensitive and stable temperature probes

Due to their distinct physicochemical characteristics and outstanding biocompatibility, carbon quantum dots have shown to offer enormous potential in the field of temperature sensing. However, there is still much to learn about the mechanism underlying carbon quantum dots' thermal sensing capabilities, and developing incredibly precise thermometers based on it is still an enormous obstacle. Herein, we successfully fabricated carbon quantum dots with variable luminescence wavelength and temperature-sensitive properties by adjusting the ingredients to modify the composition of functional groups (-NH2, -OH, -COOH and -CH2OH) on the surface of quantum dots in a simple hydrothermal synthesis process, followed by encapsulation with polyvinyl alcohol (PVA). Subsequently, structural/optical characterisation and temperature-dependent studies were utilized for investigations into the quantum dot fluorescence mechanisms as well as the thermal sensing characteristics connected to surface functional groups, respectively. Notably, the designed red-emitting methylenated carbon quantum dot film probe displayed more linear segmented temperature sensing properties (R2>0.99), a wider temperature applicability range (20–160 °C), and high temperature reversibility (20–80 °C, at least 4 cycles). Finally, the mechanism by which functional groups affect the thermal characteristics of carbon quantum dots was addressed, and we hypothesized that intramolecular and intermolecular hydrogen bonding interactions are important factors affecting the thermal properties of carbon dots. This work presents great promise and theoretical guidance for the development of highly reliable carbon quantum dot temperature sensing systems.

Long-range order enabled stability in quantum dot light-emitting diodes.

Light-emitting diodes (LEDs) based on perovskite quantum dots (QDs) have produced external quantum efficiencies (EQEs) of more than 25% with narrowband emission1,2, but these LEDs have limited operating lifetimes. We posit that poor long-range ordering in perovskite QD films-variations in dot size, surface ligand density and dot-to-dot stacking-inhibits carrier injection, resulting in inferior operating stability because of the large bias required to produce emission in these LEDs. Here we report a chemical treatment to improve the long-range order of perovskite QD films: the diffraction intensity from the repeating QD units increases three-fold compared with that of controls. We achieve this using a synergistic dual-ligand approach: an iodide-rich agent (aniline hydroiodide) for anion exchange and a chemically reactive agent (bromotrimethylsilane) that produces a strong acid that in situ dissolves smaller QDs to regulate size and more effectively removes less conductive ligands to enable compact, uniform and defect-free films. These films exhibit high conductivity (4 × 10-4 S m-1), which is 2.5-fold higher than that of the control, and represents the highest conductivity recorded so far among perovskite QDs. The high conductivity ensures efficient charge transportation, enabling red perovskite QD-LEDs that generate a luminance of 1,000 cd m-2 at a record-low voltage of 2.8 V. The EQE at this luminance is more than 20%. Furthermore, the stability of the operating device is 100 times better than previous red perovskite LEDs at EQEs of more than 20%.

Enhanced photoluminescence of a microporous quantum dot color conversion layer by inkjet printing

Owing to their high color purity, tunable bandgap, and high efficiency, quantum dots (QDs) have gained significant attention as color conversion materials for high-end display applications. Moreover, inkjet-printed QD pixels show great potential for realizing full-color mini/micro-light emitting diode (micro-LED)-based displays. As a color conversion layer, the photoluminescence intensity of QDs is limited by the insufficient absorptance of the excitation light due to the lack of scattering. Conventional scatterers, such as titanium dioxide microparticles, have been applied after additional surface engineering for sufficient dispersity to prevent nozzle clogging in inkjet printing process. In our work, as an alternative approach, we use inkjet printing for depositing a phase separating polymer ink based on polystyrene (PS) and polyethylene glycol (PEG). QD/polymer composite pixels with scattering micropores are realized. The morphology of the micropores can be tailored by the weight ratio between PS and PEG which enables the manipulation of scattering capability. With the presence of the microporous structure, the photoluminescence intensity of the QD film is enhanced by 110% in drop-cast films and by 35.3% in inkjet-printed QD pixel arrays compared to the reference samples.

Light-induced photoluminescence enhancement in chiral CdSe quantum dot films.

Chiral quantum dots (QDs) are promising materials applied in many areas, such as chiral molecular recognition and spin selective filter for charge transport, and can be prepared by facile ligand exchange approaches. However, ligand exchange leads to an increase in surface defects and reduces the efficiencies of radiative recombination and charge transport, which restricts further applications. Here, we investigate the light-induced photoluminescence (PL) enhancement in chiral L- and D-cysteine CdSe QD thin films, providing a strategy to increase the PL. The PL intensity of chiral CdSe QD films can be significantly enhanced over 100 times by continuous UV laser irradiation, indicating a strong passivation of surface defects upon laser irradiation. From the comparative measurements of the PL intensity evolutions in vacuum, dry oxygen, air, and humid nitrogen atmospheres, we conclude that the mechanism of PL enhancement is photo-induced surface passivation with the assistance of water molecules.

Nanosurface-reconstructed perovskite for highly efficient and stable active-matrix light-emitting diode display.

Perovskite quantum dots (QDs) are promising for various photonic applications due to their high colour purity, tunable optoelectronic properties and excellent solution processability. Surface features impact their optoelectronic properties, and surface defects remain a major obstacle to progress. Here we develop a strategy utilizing diisooctylphosphinic acid-mediated synthesis combined with hydriodic acid-etching-driven nanosurface reconstruction to stabilize CsPbI3 QDs. Diisooctylphosphinic acid strongly adsorbs to the QDs and increases the formation energy of halide vacancies, enabling nanosurface reconstruction. The QD film with nanosurface reconstruction shows enhanced phase stability, improved photoluminescence endurance under thermal stress and electric field conditions, and a higher activation energy for ion migration. Consequently, we demonstrate perovskite light-emitting diodes (LEDs) that feature an electroluminescence peak at 644 nm. These LEDs achieve an external quantum efficiency of 28.5% and an operational half-lifetime surpassing 30 h at an initial luminance of 100 cd m-2, marking a tenfold improvement over previously published studies. The integration of these high-performance LEDs with specifically designed thin-film transistor circuits enables the demonstration of solution-processed active-matrix perovskite displays that show a peak external quantum efficiency of 23.6% at a display brightness of 300 cd m-2. This work showcases nanosurface reconstruction as a pivotal pathway towards high-performance QD-based optoelectronic devices.

Mixed quantum dot film for dual-band infrared detection

Dual-band infrared detection offers enhanced spectral information crucial for improved target identification. Traditional dual-band infrared photodetectors have often relied on expensive epitaxial growth bulk materials, limiting their widespread use in civilian applications. Colloidal quantum dots present an affordable alternative for dual-band infrared detection, owing to their spectral tunability and solution processability. In this study, we have developed an approach utilizing mixed lead sulfide quantum dot films to achieve dual-band infrared detection spanning the NIR (Near Infrared) and SWIR (Short Wave Infrared) ranges. These films exhibit a broad absorption spectrum, ranging from 400 to 1600 nm. When operating within the near-infrared band, the device based on mixed quantum dot films demonstrates an responsivity of 0.18A/W and specific detectivity of 2.38 × 109cm∙Hz1/2/W near 900 nm.While operated in the SWIR band, the detector has responsivity of 0.17A/W and specific detectivity of 2.11 × 109cm∙Hz1/2/W near 1600 nm.

Heterojunctions of Mercury Selenide Quantum Dots and Halide Perovskites with High Lattice Matching and Their Photodetection Properties.

Heterojunction semiconductors have been extensively applied in various optoelectronic devices due to their unique carrier transport characteristics. However, it is still a challenge to construct heterojunctions based on colloidal quantum dots (CQDs) due to stress and lattice mismatch. Herein, HgSe/CsPbBrxI3-x heterojunctions with type I band alignment are acquired that are derived from minor lattice mismatch (~1.5%) via tuning the ratio of Br and I in halide perovskite. Meanwhile, HgSe CQDs with oleylamine ligands can been exchanged with a halide perovskite precursor, acquiring a smooth and compact quantum dot film. The photoconductive detector based on HgSe/CsPbBrxI3-x heterojunction presents a distinct photoelectric response under an incident light of 630 nm. The work provides a promising strategy to construct CQD-based heterojunctions, simultaneously achieving inorganic ligand exchange, which paves the way to obtain high-performance photodetectors based on CQD heterojunction films.

High Mobility HgTe Quantum Dot Films with Small Energy and Dynamic Disorder

High Mobility HgTe Quantum Dot Films with Small Energy and Dynamic Disorder

Stronger Coupling of Quantum Dots in Hole Transport Layer Through Intermediate Ligand Exchange to Enhance the Efficiency of PbS Quantum Dot Solar Cells.

Nowadays, the extensively used lead sulfide (PbS) quantum dot (QD) hole transport layer (HTL) relies on layer-by-layer method to replace long chain oleic acid (OA) ligands with short 1,2-ethanedithiol (EDT) ligands for preparation. However, the inevitable significant volume shrinkage caused by this traditional method will result in undesired cracks and disordered QD arrangement in the film, along with adverse increased defect density and inhomogeneous energy landscape. To solve the problem, a novel method for EDT passivated PbS QD (PbS-EDT) HTL preparation using small-sized benzoic acid (BA) as intermediate ligands is proposed in this work. BA is substituted for OA ligands in solution followed by ligand exchange with EDT layer by layer. With the new method, smoother PbS-EDT films with more ordered and closer QD packing are gained. It is demonstrated stronger coupling between QDs and reduced defects in the QD HTL owing to the intermediate BA ligand exchange. As a result, the suppressed nonradiative recombination and enhanced carrier mobility are achieved, contributing to ≈20% growth in short circuit current density (Jsc) and a 23.4% higher power conversion efficiency (PCE) of 13.2%. This work provides a general framework for layer-by-layer QD film manufacturing optimization.

Surface-Originated Weak Confinement in Tetrahedral Indium Arsenide Quantum Dots.

While the shape-dependent quantum confinement (QC) effect in anisotropic semiconductor nanocrystals has been extensively studied, the QC in facet-specified polyhedral quantum dots (QDs) remains underexplored. Recently, tetrahedral nanocrystals have gained prominence in III-V nanocrystal synthesis. In our study, we successfully synthesized well-faceted tetrahedral InAs QDs with a first excitonic absorption extending up to 1700 nm. We observed an unconventional sizing curve, indicating weaker confinement than for equivalently volumed spherical QDs. The (111) surface states of InAs QDs persist at the conduction band minimum state even after ligand passivation with a significantly reduced band gap, which places tetrahedral QDs at lower energies in the sizing curve. Consequently, films composed of tetrahedral QDs demonstrate an extended photoresponse into the short-wave infrared region, compared to isovolume spherical QD films.

PbS quantum dot thin film dry etching

Many consumer products used daily contain sensors and image sensors (smartphones, cars, automated tools, etc.). There is a growing demand to enhance the capabilities of industrial products to probe their environment more efficiently, i.e., under difficult conditions (smoke, darkness, etc.). One solution is to extend the capabilities of image sensors to detect light toward the near-infrared and short-wave infrared (SWIR) regions. Because silicon has weak absorption properties in the infrared, especially in the SWIR region, manufacturers are investigating the use of new materials to build these sensors. To this end, colloidal quantum dot (QD) thin films made from the assembly of PbS nanoparticles have emerged as promising materials. They offer tunable bandgaps, favorable absorption properties, and scalability in production. However, patterning the active parts of photodiodes by plasma etching of this new material presents challenges. The etching chemistry must be selected to volatilize Pb and S without modifying the unetched active part of the PbS QD photodiode, and the etching profile should be anisotropic. In this study, we have screened several plasma operating conditions (power, pressure, and temperature) in various chemistries (H2, Cl2, HBr, and N2). To understand the etch mechanisms and profiles, ToF-SIMS and TEM/energy dispersive x-ray were employed. Our findings reveal that halogen-based plasmas cause QD material deterioration through Cl or Br diffusion deep in the film. While H2 plasmas are efficient to etch PbS QD films, they result in high roughness due to the removal of the carbonated ligands that separate PbS QDs. This ligand etching is followed by QD coalescence leading to significant roughness. However, the addition of N2 to H2 can prevent this phenomenon by forming a diffusion barrier at the surface, resulting in favorable etching characteristics.

Suppression of Thermally Induced Surface Traps in Colloidal Quantum Dot Solids via Ultrafast Pulsed Light.

Thermal annealing (TA) of colloidal quantum dot (CQD) films is considered an important process for recent high-performing CQD solar cells (SCs) due to its beneficial effects on CQD solids, including enhanced electrical conductivity, denser packing of CQD films, and the removal of organic residues and solvents. However, the conventional TA for CQDs, which requires several minutes, leads to hydroxylation and oxidation on the CQD surface, resulting in the formation of trap states and a subsequent decline in SC performance. To address these challenges, this study introduces a flashlight annealing (FLA) technique that significantly reduces the annealing time to the millisecond scale. Through the FLA approach, it successfully suppressed hydroxylation and oxidation, resulting in decreased trap states within the CQD solids while simultaneously preserving their charge transport properties. As a result, CQD SCs treated with FLA exhibited a notable improvement, achieving an open-circuit voltage of 0.66V compared to 0.63V in TA-treated devices, leading to an increase in power conversion efficiency from 12.71% to 13.50%.

Incorporation of carbon quantum-dot films with silicon substrates for improved photovoltaic performances

Employment of fluorine-ion doped carbon quantum dot (FCQD) films with silicon (Si) substrates is realized via the facile solution process that exhibits the remarkable photovoltaic characterizations. In-depth materials and cell characterizations are performed, and the improvement of charge separation at FCQD/Si interfaces compared with undoped CQD/Si cases are experimentally elucidated, showing the conversion efficiency of 13.6 %, approximately 2 times higher than undoped CQD-based solar cells with conversion efficiency of 6.8%. The results are of great importance for QD-based light-harvesting and optoelectronic applications.

Lensless opto-electronic neural network with quantum dot nonlinear activation

With the swift advancement of neural networks and their expanding applications in many fields, optical neural networks have gradually become a feasible alternative to electrical neural networks due to their parallelism, high speed, low latency, and power consumption. Nonetheless, optical nonlinearity is hard to realize in free-space optics, which restricts the potential of the architecture. To harness the benefits of optical parallelism while ensuring compatibility with natural light scenes, it becomes essential to implement two-dimensional spatial nonlinearity within an incoherent light environment. Here, we demonstrate a lensless opto-electrical neural network that incorporates optical nonlinearity, capable of performing convolution calculations and achieving nonlinear activation via a quantum dot film, all without an external power supply. Through simulation and experiments, the proposed nonlinear system can enhance the accuracy of image classification tasks, yielding a maximum improvement of 5.88% over linear models. The scheme shows a facile implementation of passive incoherent two-dimensional nonlinearities, paving the way for the applications of multilayer incoherent optical neural networks in the future.

Silicon solar cell efficiency improvement employing electrostatically assembled polyelectrolyte–quantum dot multilayers

Down-shifting (DS) has proven to be an effective technique to address thermalization losses in photovoltaic devices. It involves the modification of the incident solar spectrum by luminescent species to better suit solar cell’s optimal absorption regions. Despite the number of favorable characteristics of quantum dots (QDs) as DS materials, their incorporation into highly ordered close-packed films remains the major drawback of QD-based DS applications. This limitation can be overcome by the sequential integration of QDs into a multilayered film via the layer-by-layer assembly technique, that allows the precise control of composition and thickness. The experimental results discussed herein indicate that upon optimization employing a model-assisted design approach, the spectral response of a silicon solar cell benefits from the down-shifting and antireflection capabilities of the QD film, as evinced by their quantum efficiency. For the optimum design, the incorporation of QDs triggered an increment of 26.1% in the power conversion efficiency driven by an increase of 29.2% in the short circuit current density. The controlled assembly of QD multilayers offers unique opportunities in light harvesting for new hybrid photovoltaic technologies.

Homogeneous mono-layer mixed-halide perovskite quantum dots towards blue light-emitting diodes with stable spectra under continuous driving

Mixed-halide perovskite quantum dots (QDs) light-emitting diodes (QLEDs) with blue emission still suffer from low efficiency due to surface defects and halide migration. The issue of halide migration in the mixed-halide perovskite QLEDs under increasing biases have been basically solved. However, under continuous driving, the QLEDs still face the problem of halide migration or electroluminescence (EL) peak shift. In this work, we found that when ligand passivation effects on mixed-halide perovskite QDs are similar, the homogeneity of a mono-layer QDs film plays a decisive role in suppressing halide migration and improving the EL spectral stability of the QLEDs under continuous driving. Moreover, 4 and 64 mm2 QLEDs with emission peaks from pure-blue to deep-blue and low efficiency roll-off were fabricated and the analysis results show that factors, such as chlorine content or defects in the QDs, driving bias, operation time at the driving bias and current density, also matter in the EL spectral stability of the QLEDs. In addition, we found that the devices exhibit similar performance after being stored for a year, demonstrating high stability of the devices with homogeneous mono-layer QDs structure. Our work provides a timely and systematic guide on achieving spectrally stable and efficient blue QLEDs with high color purity based on mixed-halide perovskite QDs.

Uncooled High Detectivity Mid-Infrared Photoconductor Using HgTe Quantum Dots and Nanoantennas.

Using a metal/insulator/metal (MIM) structure with a gold nanoantenna array made by electron beam lithography, the responsivity of a HgTe colloidal quantum dot film is enhanced in the mid-infrared. Simulations indicate that the spatially averaged peak spectral absorption of an 80 nm film is 60%, enhanced 23-fold compared to that of the same film on a bare sapphire substrate. The field intensity enhancement is focused near the antenna tips, being 20-fold 100 nm away, which represents only 1% of the total area and up to 1000-fold at the tips. The simulated polarized absorption spectra are in good agreement with the experiments, with a strong resonance around 4 μm. A responsivity of 0.6 A/W is obtained at a 1 V bias. Noise measurements separate the 1/f noise from the generation-recombination white noise and give a spatially averaged photoconductive gain of 0.3 at 1 V bias. The spatially averaged peak detectivity is improved 15-fold compared to the same film on a sapphire substrate without an MIM structure. The experimental peak detectivity reaches 9 × 109 Jones at 2650 cm-1 and 80 kHz, decreasing at lower frequencies. The MIM structure also enhances the spatially averaged peak photoluminescence of the CQD film by 16-fold, which is a potential Purcell enhancement. The good agreement between simulations and measurements confirms the viability of lithographically designed nanoantenna structures for vastly improving the performance of mid-IR colloidal quantum dot photoconductors. Further improvements will be possible by matching the optically enhanced and current collection areas.

Highly Luminescent and Stable Perovskite Quantum Dots Films for Light‐Emitting Devices and Information Encryption

AbstractThe inherent flexibility and excellent mechanical strength of lead halide perovskite quantum dots (LHP‐QDs) films have attracted much attention in the fields of flexible lighting, displays, non‐planar x‐ray imaging, and wearable optoelectronics. Unfortunately, the complicated synthesis process and poor stability limit its practical applications, hence there is an urgent need to develop a feasible fabrication process for films to attain high device performance. Herein, a molecular level hybridization of bridged polysilsesquioxane (BPSQ) is designed as matrix to harvest both flexibility of organics and stability of inorganics, resulting in improved interfacial compatibility between the CsPbBr3 QDs and the matrix through chemical bond anchoring. The CsPbBr3@3‐aminopropyl‐triethoxysilane (APTES)@BPSQ films showcase bright narrow‐band photoluminescence, with a photoluminescence quantum yield of 61% and a half‐peak full width at half maximum of <17 nm. Notably, these films demonstrate excellent environmental stability, UV resistance, water stability (experiencing only an 18% decrease in luminescence intensity after 168 h of water immersion), and high‐temperature stability (withstanding temperatures up to 500 K). Furthermore, white light‐emitting diodes (WLEDs) and anti‐counterfeiting patterns have been fabricated using CsPbBr3@APTES@BPSQ, highlighting their wide application potential in flexible light‐emitting devices and information encryption.

Monolithic Two-Terminal Tandem Solar Cells Using Sb2S3 and Solution-Processed PbS Quantum Dots Achieving an Open-Circuit Potential beyond 1.1 V.

Multijunction solar cells have the prospect of a greater theoretical efficiency limit than single-junction solar cells by minimizing the transmissive and thermalization losses a single absorber material has. In solar cell applications, Sb2S3 is considered an attractive absorber due to its elemental abundance, stability, and high absorption coefficient in the visible range of the solar spectrum, yet with a band gap of 1.7 eV, it is transmissive for near-IR and IR photons. Using it as the top cell (the cell where light is first incident) in a two-terminal tandem architecture in combination with a bottom cell (the cell where light arrives second) of PbS quantum dots (QDs), which have an adjustable band gap suitable for absorbing longer wavelengths, is a promising approach to harvest the solar spectrum more effectively. In this work, these two subcells are monolithically fabricated and connected in series by a poly(3,4-ethylene-dioxythiophene) polystyrene sulfonate (PEDOT:PSS)-ZnO tunnel junction as the recombination layer. We explore the surface morphology of ZnO QD films with different spin-coating conditions, which serve as the PbS QD cell's electron transport material. Furthermore, we examine the differences in photogenerated current upon varying the PbS QD absorber layer thickness and the electrical and optical characteristics of the tandem with respect to the stand-alone reference cells. This tandem architecture demonstrates an extended spectral response into the IR with an open-circuit potential exceeding 1.1 V and a power conversion efficiency of 5.6%, which is greater than that of each single-junction cell.

One-pot heat-up synthesis of short-wavelength infrared, colloidal InAs quantum dots.

III-V colloidal quantum dots (QDs) promise Pb and Hg-free QD compositions with which to build short-wavelength infrared (SWIR) optoelectronic devices. However, their synthesis is limited by the availability of group-V precursors with controllable reactivities to prepare monodisperse, SWIR-absorbing III-V QDs. Here, we report a one-pot heat-up method to synthesize ∼8nm edge length (∼6.5nm in height) tetrahedral, SWIR-absorbing InAs QDs by increasing the [In3+]:[As3+] ratio introduced using commercially available InCl3 and AsCl3 precursors and by decreasing the concentration and optimizing the volume of the reducing reagent superhydride to control the concentration of In(0) and As(0) intermediates through QD nucleation and growth. InAs QDs are treated with NOBF4, and their deposited films are exchanged with Na2S to yield n-type InAs QD films. We realize the only colloidal InAs QD photoconductors with responsivity at the technologically important wavelength of 1.55μm.