Nanocrystal Thin Films Research Articles

Ultrabright and Efficient Green Perovskite Light-Emitting Diodes Enabled by Well-Crystallized Dense CsPbBr3 Nanocubes.

Perovskite light-emitting diodes (PeLEDs) are promising for next-generation high-definition displays. One of the keys to achieving high performance PeLEDs lies in how to fabricate crystalline and dense perovskite films. However, there exist challenges to directly grow well-crystallized CsPbBr3 nanocrystal thin films on transport layers due to low solubility in solvents and fast precipitation of all-inorganic CsPbBr3, and the corresponding bright, efficient, and stable green PeLEDs have rarely been reported. Herein, we report an efficient strategy to prepare well-crystallized and dense CsPbBr3 nanocubes for ultrabright and efficient green PeLEDs. We introduce sulfobetaine zwitterion as crystallization control agent and strontium fluoride nanocrystals as nucleation seeds to grow high-quality CsPbBr3 nanocube films. Eventually, the CsPbBr3 films enable green PeLEDs with a maximum luminance of 162 767 cd m-2 and a champion external quantum efficiency of 21.3% along with a narrow spectral line width of ∼14.7 nm, representing state-of-the-art performances in green PeLEDs.

Visible and near-infrared modulating tungsten suboxide nanorods electrochromic films in acidic aqueous electrolytes

Proton-based aqueous electrolytes can be used to achieve high performance electrochromic nanocrystal thin films due to their small ion size. However, acidic aqueous electrolyte systems have not yet been explored in near-infrared (NIR) absorbing plasmonic tungsten oxide nanocrystal films. Here, we demonstrate tungsten suboxide nanorod films with excellent visible and NIR modulation performance in the H+-based aqueous electrolytes, thanks to their mesoporous structure, nanosized domains, and open tunnel structure. Colloidally synthesized WO2.83 nanorods with an average width of 6 nm and length of 48 nm were converted to WO2.90 nanorod film via annealing in air, while still preserving open tunnels. These films exhibit fast switching speed (tc = 0.9 s, tb = 2.1 s), excellent cycling stability over 2500 cycles, wide optical modulation up to ΔT = 53.8 % in the NIR region, and a high coloration efficiency (CE) of 167 cm2 C⁻1 at 1300 nm. Additionally, introducing a thin spacer (25 μm) reduced intrinsic NIR absorption from water, thereby enhancing the NIR modulation properties. These highly performing aqueous proton-electrolytes-based electrochromic devices open new possibilities for implementing visible and NIR electrochromism.

(Invited) Redox Chemistries for Vacancy Modulation in Copper Phosphide Nanocrystals

Copper phosphide has been proposed as an anode material for lithium-ion batteries due to the ability to accommodate the electrochemical insertion of Li ions without substantial reorganization of the P-sublattice. We present three copper-coupled redox chemistries that allow post-synthetic modulation of the delocalized hole concentrations in colloidal copper phosphide nanocrystals. Changes in the structural, optical, and compositional properties are evaluated by powder X-ray diffraction, electronic absorption spectroscopy, solid-state nuclear magnetic resonance spectroscopy and elemental analysis. The redox chemistries presented herein can be used to obtain nanocrystals with Cu/P ratios of ~2.66–2.93, a larger range than has been possible through purely synthetic tuning. Importantly, oxidation with a divalent metal halide and trioctylphosphine allows access to a uniquely Cu-deficient composition. Copper phosphide nanocrystal thin-films oxidized in this way would be ideal candidates for fundamental electrochemical lithiation studies.

Synthesis of Highly Oriented Nanocrystal Thin-Films and Their Applications to Electrochemical Devices

The precisely defined particle assembly at the nanoscale with simultaneously scalable patterning at the microscale is indispensable for enabling functionality and improving the performance of devices. While synthetic advances in the past decades now allow precise control of their size, shape, and composition, they must be processed from dispersion into functional films for many applications, which presents additional challenges. In this work, we introduce the self-assembly of inorganic nanoubes (Co3O4 NCs) and we also describe the fabrication of centimeter-scale NC superlattice thin-films on silicone substrate with anisotropic NC building blocks, thin-film patterning, and the supercrystal formation of superlattice structures. As a result, the Raman spectra of Co3O4 NC thin-films clearly exhibits the distinct feature of vibration modes of Co3O4 and synchrotron-based X-ray diffraction techniques showed the Co3O4 NCs order into [100] aligned arrays. Also, the uniformly prepared Co3O4 NC building blocks and thin-films were examined by field-emission scanning electron microscopy analysis and it shows well-defined nanostructures with ~13nm-side of NCs and ~3nm space between self-assembled NCs. To investigate the distinct feature of functional films, we prepared various type of device structures (memory, electrode, gas sensor) and examined the performances. In case of memristor, the device exhibits excellent bipolar resistance switching characteristics with better reliability and stability over various polycrystalline metal oxide nanostructures. Utilizing our approach enables the creation of miniaturized devices, followed by the transfer of NC thin-films onto TEM grids. Subsequent in-situ TEM analysis offers the potential to observe unique phenomena at the nano-scale, unveiling phase transitions in nanocrystalline materials or electrochemical reaction mechanisms previously unexplored by researchers.

Probing the cw-Laser-Induced Fluorescence Enhancement in CsPbBr3 Nanocrystal Thin Films: An Interplay between Photo and Thermal Activation.

Perovskite nanocrystals hold significant promise for a wide range of applications, including solar cells, LEDs, photocatalysts, humidity and temperature sensors, memory devices, and low-cost photodetectors. Such technological potential stems from their exceptional quantum efficiency and charge carrier conduction capability. Nevertheless, the underlying mechanisms of photoexcitation, such as phase segregation, annealing, and ionic diffusion, remain insufficiently understood. In this context, we harnessed hyperspectral fluorescence microspectroscopy to advance our comprehension of fluorescence enhancement triggered by UV continuous-wave (cw) laser irradiation of CsPbBr3 colloidal nanocrystal thin films. Initially, we explored the kinetics of fluorescence enhancement and observed that its efficiency (φph) correlates with the laser power (P), following the relationship φph = 7.7⟨P⟩0.47±0.02. Subsequently, we estimated the local temperature induced by the laser, utilizing the finite-difference method framework, and calculated the activation energy (Ea) required for fluorescence enhancement to occur. Our findings revealed a very low activation energy, Ea ∼ 9 kJ/mol. Moreover, we mapped the fluorescence photoenhancement by spatial scanning and real-time static mode to determine its microscale length. Below a laser power of 60 μW, the photothermal diffusion length exhibited nearly constant values of approximately (22 ± 5) μm, while a significant increase was observed at higher laser power levels. These results were ascribed to the formation of nanocrystal superclusters within the film, which involves the interparticle spacing reduction, creating the so-called quantum dot solid configuration along with laser-induced annealing for higher laser powers.

Superfluorescence in Metal Halide Perovskites

AbstractSuperfluorescence (SF) is a unique quantum optical phenomenon where an ensemble of atoms or molecules exhibit coherent emission of an intense burst of light of high directionality, with temporal coherence. SF exhibits ultrafast optical characteristics and is considerably explored in diverse inorganic and hybrid semiconductor materials at cryogenic temperatures, including inorganic and hybrid metal halide perovskites. Notably, SF is reported in different perovskites’ nanocrystal superlattices, alongside two examples in thin films, impressively achieving SF at room temperature. The density of quantum emitters, excited state characteristics, interaction strengths, and temperature all affect the SF threshold. Although significant progress is reported in the observance of SF phenomena, a full interpretation of the relationship between the factors that determine the SF threshold and the intrinsic material properties remains unclear. This review addresses the current state‐of‐the‐art observations of SF in perovskite systems, such as nanocrystal superlattices and thin films, elucidating the optical properties, ultrafast dynamics, and the proposed mechanisms for room‐temperature SF. The review concludes with a discussion on the existing challenges, unresolved questions, and future perspectives for advancing perovskite SF research

Elucidating the Role of Ligand Engineering on Local and Macroscopic Charge‐Carrier Transport in NaBiS2 Nanocrystal Thin Films

AbstractTernary chalcogenides have emerged as potential candidates for ultrathin photovoltaics, and NaBiS2 nanocrystals (NCs) have gained appeal because of their months‐long phase‐stability in air, high absorption coefficients >105 cm−1, and a pseudo‐direct bandgap of 1.4 eV. However, previous investigations into NaBiS2 NCs used long‐chain organic ligands separating individual NCs during synthesis, which severely limits macroscopic charge‐carrier transport. In this work, these long‐chain ligands are exchanged for short iodide‐based ligands, allowing to understand the macroscopic charge‐carrier transport properties of NaBiS2 and evaluate its photovoltaic potential in more depth. It is found that ligand exchange results in simultaneous improvements in intra‐NC (microscopic) and inter‐NC (macroscopic) mobilities, while charge‐carrier localization still takes place, which places a fundamental limit on the transport lengths achievable. Despite this limitation, the high absorption coefficients enable ultrathin (55 nm thick) solar absorbers to be used in photovoltaic devices, which have peak external quantum efficiencies > 50%. In addition, temperature‐dependent transient current measurements uncover a small activation energy barrier of 88 meV for ion migration, which accounts for the strongly hysteretic behavior of NaBiS2 photovoltaic devices. This work not only reveals how the charge‐carrier transport properties of NaBiS2 NCs over several length and time scales are influenced by ligand engineering, but also unveils the facile ionic transport in this material, which limits the potential of NaBiS2 in photovoltaics. On the other hand, the discovery shows that there are opportunities to use this material in memristors, electrolytes, and other applications requiring ionic conduction.

Enhancement of light emission of a low-resistivity silicon nanocrystal thin film: A simulational and experimental study

A silicon nanocrystal (Si NC) white light-emitting (λ = ∼400–900 nm) thin film with a relatively low resistivity of 1.6 × 104 Ω m has been prepared as an active medium for electrically driven Si light sources. The average size of Si NC is 2.4 ± 0.4 nm. To enhance the light emission efficiency of this low-resistivity Si NC thin film, approach of hydrogen passivation suitable for the traditional high-resistivity (1.2 × 107 Ω m in this work for example) red light-emitting Si NC thin film has been tried and found unavailable unfortunately. Our first principles simulation shows that Si NCs bonded to −O, −NH2, −OH, and −H ligands are responsible for red, green, and blue (RGB) primary color emissions in this white light-emitting sample, respectively. Passivation of the sample in NH3 and H2O atmosphere is then conducted, aiming to increase the number of the RGB light emitters. The light emission is significantly enhanced, with photoluminescence intensity, photoluminescence quantum yield, electroluminescence intensity, and net optical gains increased by factors of 4.6, 4.2, 4.0, and ∼3.0, respectively, after 10-day passivation. Further enhancements are expected for longer passivation.

Probing compositional engineering effects on lead-free perovskite-inspired nanocrystal thin films using correlative nonlinear optical microscopy.

We introduce the use of correlative third-harmonic generation and multiphoton-induced luminescence microscopy to investigate the impact of manganese (Mn) doping on bismuth (Bi)-based perovskite-inspired nanocrystal thin films. The technique was found to be extremely sensitive to the microscopic features of the perovskite film and its structural compositions, allowing the unambiguous detection of compositionally different emitters in the perovskite film and manipulation of their nonlinear optical responses. Our work unveils a new way to investigate, manipulate, and exploit perovskite-inspired functional materials for nonlinear optical conversion at the nanoscale.

Elucidating the photophysics behind the stimulated emission processes in CsPbBr3 nanocrystals films

Thanks to their excellent photoluminescence quantum yields, their facile and low-cost production, and their processing versatility, CsPbBr3 perovskite nanocrystals (NCs) stand out as excellent candidates to implement light-emitting devices. Elucidating their stimulated emission mechanisms is fundamental to achieve much more efficient and versatile perovskite lasers. In particular, two questions remain open: why the Amplified Spontaneous Emission (ASE) band is significantly shifted from the fluorescence one, and why the former seems to suddenly emerge from, and coexist with, the latter. These characteristic features have led to a debate, which is not settled yet, on which is the mechanism behind the ASE band shift. In this communication, we try to settle this debate and address these questions through experimental ASE measurements combined with numerical simulations. We show that the ASE behaviour in CsPbBr3 NCs thin films stems from a combination of reabsorption, excited state absorption, excitation of differently polarized waveguide modes, and the coexistence of short- and long-lived localized single excitons. The results in this work help understanding the stimulated emission mechanisms in perovskites and provide insightful information on research avenues to increase the efficiency of the light-emitting devices based on these materials.

Cation-Disorder Engineering Promotes Efficient Charge-Carrier Transport in AgBiS2 Nanocrystal Films.

Efficient charge-carrier transport is critical to the success of emergent semiconductors in photovoltaic applications. So far, disorder has been considered detrimental for charge-carrier transport, lowering mobilities, and causing fast recombination. This work demonstrates that, when properly engineered, cation disorder in a multinary chalcogenide semiconductor can considerably enhance the charge-carrier mobility and extend the charge-carrier lifetime. Here, the properties of AgBiS2 nanocrystals (NCs) are explored as a function of Ag and Bi cation-ordering, which can be modified via thermal-annealing. Local Ag-rich and Bi-rich domains formed during hot-injection synthesis are transformed to induce homogeneous disorder (random Ag-Bi distribution). Such cation-disorder engineering results in a sixfold increase in the charge-carrier mobility, reaching ≈2.7 cm2 V-1 s-1 in AgBiS2 NC thin films. It is further demonstrated that homogeneous cation disorder reduces charge-carrier localization, a hallmark of charge-carrier transport recently observed in silver-bismuth semiconductors. This work proposes that cation-disorder engineering flattens the disordered electronic landscape, removing tail states that would otherwise exacerbate Anderson localization of small polaronic states. Together, these findings unravel how cation-disorder engineering in multinary semiconductors can enhance the efficiency of renewable energy applications.

Ultrafast Carrier Drift Transport Dynamics in CsPbI3 Perovskite Nanocrystalline Thin Films.

We study the early time carrier drift dynamics in CsPbI3 nanocrystal thin films with a sub 25 ps time resolution. Prior to trapping, carriers exhibit band-like transport characteristics, which is similar to those of traditional semiconductor solar absorbers including Si and GaAs due to optical phonon and carrier scattering at high temperatures. In contrast to the popular polaron scattering mechanism, the CsPbI3 nanocrystal thin film demonstrates the strongest optical phonon scattering mechanism among other inorganic-organic hybrid perovskites, Si, and GaAs. This ultrafast dynamics study establishes a foundation for understanding the fundamental carrier drift properties that drive perovskite nanocrystal optoelectronics.

Understanding optical and structural properties of the CH3NH3PbI3 nanocrystal thin films under humidity conditions

Low-dimensional organic-inorganic hybrid perovskite materials have drawn a lot of interest in optoelectronic applications because of their unique optoelectronic performance in comparison to their bulk counterparts. There is an influence of humidity conditions on the stability of perovskite in both positive and negative ways. The passivation of surface and bulk defects in the thin film of perovskite by the H2O molecules is a positive way. The negative way is that the material's stability will hinder the commercialization of perovskite-based devices. Herein, CH3NH3PbI3 nanocrystals are synthesized by the hot-injection method. The optical and structural properties of the thin film of the synthesized nanocrystals under different humidity conditions are studied through photoluminescence (PL), TRPL, Raman, X-ray diffraction (XRD), UV–Vis, spectroscopic ellipsometry, and FTIR techniques for 4 weeks. The redshift in the PL spectra of the thin film with an increase in PL intensity and carrier lifetime is caused by the shallow trap-assisted radiative recombination and localization of the charge carriers at the interface of the CH3NH3PbI3/water. The XRD, Raman, and FTIR peaks of the thin film are also shifted due to defect formation and structure distortion of the CH3NH3PbI3 crystal lattice. The thin films of these nanocrystals exhibit very high PLQY of 56% and 60% after 5 h and 1 week respectively. The results pave the way to analyse the stability of CH3NH3PbI3 nanocrystals through their optical and structural behaviour under different humidity conditions. The results also reflect that the photoemission of the synthesized material can be tuned by regulating the defect density and the structural deformation of the nanocrystals under controlled humidity conditions.

Self-Standing Thin Films of Cellulose Nanocrystals and Graphene Quantum Dots for Detection of Trace Iron(III)

Cellulose nanocrystal (CNC) thin films have gained attention for application in green optoelectronics devices. However, the dependence on plasticizers, external cross-linkers, or auxiliary polymers can impair the full exploration of the nanomaterials’ properties. Herein, we report on the evaluation of a surface-oxidized CNCs ultrathin film, made from a formulation that excludes the use of auxiliary compounds, to be used as a sensing platform. The physicochemical characterizations using UV–vis, Fourier transform infrared , and Raman spectroscopies, nuclear magnetic resonance, zeta potential, transmission electron and field emission scanning electron microscopies, X-ray diffraction, thermogravimetric analysis, and contact angle measurement showed that the adopted procedure led to (i) the modification of the CNC surface and (ii) the formation of smaller CNCs. The production of casting films from highly diluted CNC-modified aqueous suspensions showed that a very thin, transparent, self-supporting, and manipulable film could be obtained, which was not the case for diluted unmodified CNC suspension. Additionally, the CNC thin film has been demonstrated to be a suitable platform for hosting graphene quantum dots, based on which an optochemical sensor was successfully employed to detect iron(III) in a dynamic range from 1 fM to 2 pM, yielding a limit of detection of 0.8 fM.

Surface Engineering of Metal and Semiconductor Nanocrystal Assemblies and Their Optical and Electronic Devices.

ConspectusColloidal nanocrystals (NCs) are composed of inorganic cores and organic or inorganic ligand shells and serve as building blocks of NC assemblies. Metal and semiconductor NCs are well known for the size-dependent physical properties of their cores. The large NC surface-to-volume ratio and the space between NCs in assemblies places significant importance on the composition of the NC surface and ligand shell. Nonaqueous colloidal NC syntheses use relatively long organic ligands to control NC size and uniformity during growth and to prepare stable NC dispersions. However, these ligands create large interparticle distances that dilute the metal and semiconductor NC properties of their assemblies. In this Account, we describe postsynthesis chemical treatments to engineer the NC surface and design the optical and electronic properties of NC assemblies. In metal NC assemblies, compact ligand exchange reduces the interparticle distance and drives an insulator-to-metal transition tuning the dc resistivity over a 1010 range and the real part of the optical dielectric function from positive to negative across the visible-to-IR region. Juxtaposing NC and bulk metal thin films in bilayers allows the differential chemical and thermal addressability of the NC surface to be exploited in device fabrication. Ligand exchange and thermal annealing densifies the NC layer, creating interfacial misfit strain that triggers folding of the bilayers and is used to fabricate, with only one lithography step, large-area 3D chiral metamaterials. In semiconductor NC assemblies, chemical treatments such as ligand exchange, doping, and cation exchange control the interparticle distance and composition to add impurities, tailor stoichiometry, or make entirely new compounds. These treatments are employed in longer studied II-VI and IV-VI materials and are being developed as interest in III-V and I-III-VI2 NC materials grows. NC surface engineering is used to design NC assemblies with tailored carrier energy, type, concentration, mobility, and lifetime. Compact ligand exchange increases the coupling between NCs but can introduce intragap states that scatter and reduce the lifetime of carriers. Hybrid ligand exchange with two different chemistries can enhance the mobility-lifetime product. Doping increases carrier concentration, shifts the Fermi energy, and increases carrier mobility, creating n- and p-type building blocks for optoelectronic and electronic devices and circuits. Surface engineering of semiconductor NC assemblies is also important to modify device interfaces to allow the stacking and patterning of NC layers and to realize excellent device performance. It is used to construct NC-integrated circuits, exploiting the library of metal, semiconductor, and insulator NCs, to achieve all-NC, solution-fabricated transistors.

Ink-Based CuIn0.3Ga0.7S2 Nanocrystal Thin Films as Photocathodes for Photoelectrochemical CO2 Reduction Reaction

One of the promising methods to solve the current energy and environment issues is photoelectrochemical (PEC) water splitting and CO2 reduction reaction. Chalcopyrite copper indium gallium sulfide (CIGS) and CuIn0.3Ga0.7S2 nanocrystal thin films have been considered photovoltaic materials, and here, we demonstrated their potential to reduce CO2 into CO. A modified solution process affords to decrease the number of surface ligands, which triggers an increase in the crystal size and an improved reproducibility in performance and output current. After depositing gold nanoparticles on the surface of CIGS, the Faradic efficiency related to the CO2-to-CO conversion can reach 12.93% in aqueous electrolytes and 25% in nonaqueous electrolytes. Further investigation points out that in the range of applied potential between −0.1 and −0.2 V vs a reversible hydrogen electrode (RHE), the CIGS photocathode appears to display a stable photocurrent density for 1 h, but when applying a higher applied bias, such as of −0.3 V vs RHE, the degradation of the current is significant. Additionally, we found that coupling catalysts to the CIGS increases the selectivity toward CO and minimizes the competitive hydrogen evolution reaction.

Air-sensitive amplified spontaneous emission in lecithin-capped CsPbBr3 nanocrystals thin films

Fully inorganic lead halide perovskite nanocrystals (NCs) are receiving great attention as active materials for photonic and optoelectronic devices. While the lack of long-term stability, due to their sensitivity to ambient air exposure, currently prevents their application to commercial devices, the presence of reversible environmental effects opens the way for possible applications of lead halide perovskites in resistive or optical sensors. In this work we investigate the Amplified Spontaneous Emission (ASE) properties and their dependence on the surrounding environment of lecithin-capped CsPbBr3 NCs thin films. We demonstrate low ASE threshold under nanosecond pumping, both in air and in vacuum, with emission intensity lower in air than in vacuum. We also show that the emission quenching induced by ambient air exposure, ascribed to moisture-induced surface solvation, is reversible and it is fully restored by a suited vacuum stint application. The ASE sensitivity is up to 6.5 larger than the spontaneous emission one, making lecithin-capped CsPbBr3 NCs thin films promising systems for the development of optical humidity sensors with high sensitivity.

Effect of Heating and Citric Acid on the Performance of Cellulose Nanocrystal Thin Films

Cellulose nanocrystals (CNCs) were extracted from bleached cotton by sulfuric acid hydrolysis. Thin films were prepared from the aqueous suspension of CNCs by casting and evaporation with 15% glycerol as a plasticizer. Our research aimed to create stable films resistant to water. The structure and the interactions of the films were modified by short (10 min) heating at different temperatures (100, 140, and 160 °C) and by adding different amounts of citric acid (0, 10, 20, and 30%). Various analytical methods were used to determine the structure, surface properties, and mechanical properties. The interaction of composite films with water and water vapor was also investigated. Heat treatment did not significantly affect the film properties. Citric acid, without heat treatment, acted as a plasticizer. It promoted the disintegration of films in water, increased water vapor sorption, and reduced tensile strength, resulting in flexible and easy-to-handle films. The combination of heat treatment and citric acid resulted in stable liquid-water-resistant films with excellent mechanical properties. A minimum heating temperature of 120 °C and a citric acid concentration of 20% were required to obtain a stable CNC film structure resistant to liquid water.

Directional emissions from perovskite nanocrystals thin film enabled by metasurface integration through one step spin-coating process

Directional emissions from perovskite nanocrystals thin film enabled by metasurface integration through one step spin-coating process

Deciphering the Role of Water in Promoting the Optoelectronic Performance of Surface-Engineered Lead Halide Perovskite Nanocrystals.

Lead halide perovskites are promising candidates for high-performance light-emitting diodes (LEDs); however, their applicability is limited by their structural instability toward moisture. Although a deliberate addition of water to the precursor solution has recently been shown to improve the crystallinity and optical properties of perovskites, the corresponding thin films still do not exhibit a near-unity quantum yield. Herein, we report that the direct addition of a minute amount of water to post-treated formamidinium lead bromide (FAPbBr3) nanocrystals (NCs) substantially enhances the stability while achieving a 95% photoluminescence quantum yield in a NC thin film. We unveil the mechanism of how moisture assists in the formation of an additional NH4Br component. Alongside, we demonstrate the crucial role of moisture in assisting localized etching of the perovskite crystal, facilitating the partial incorporation of NH4+, which is key for improved performance under ambient conditions. Finally, as a proof-of-concept, the application of post-treated and water-treated perovskites is tested in LEDs, with the latter exhibiting a superior performance, offering opportunities toward commercial application in moisture-stable optoelectronics.