Advantageous properties of halide perovskite quantum dots towards energy-efficient sustainable applications

As lead halide perovskite(LHP)semiconductors have shown tremendous promise in many application fields,and particularly made strong impact in the solar photovoltaic area,low dimensional quantum dot forms of these perovskites are showing the potential to make distinct marks in the fields of electronics,optoelectronics and photonics.The so-called perovskite quantum dots(PQDs)not only possess the most important features of LHP materials,i.e.,the unusual high defect tolerance,but also demonstrate clear quantum size effects,along with exhibiting desirable optoelectronic properties such as near perfect photoluminescent quantum yield,multiple exciton generation and slow hot-carrier cooling.Here,we review the advantageous properties of these nanoscale perovskites and survey the prospects for diverse applications which include lightemitting devices,solar cells,photocatalysts,lasers,detectors and memristors,emphasizing the distinct superiorities as well as the challenges.

In Situ Iodide Passivation Toward Efficient CsPbI_(3) Perovskite Quantum Dot Solar Cells

All-inorganic CsPbI_3 quantum dots(QDs) have demonstrated promising potential in photovoltaic(PV) applications. However, these colloidal perovskites are vulnerable to the deterioration of surface trap states, leading to a degradation in efficiency and stability. To address these issues, a facile yet effective strategy of introducing hydroiodic acid(HI) into the synthesis procedure is established to achieve high-quality QDs and devices. Through an in-depth experimental analysis, the introduction of HI was found to convert PbI_2 into highly coordinated [PbI_m]~(2-m), enabling control of the nucleation numbers and growth kinetics. Combined optical and structural investigations illustrate that such a synthesis technique is beneficial for achieving enhanced crystallinity and a reduced density of crystallographic defects. Finally, the effect of HI is further reflected on the PV performance. The optimal device demonstrated a significantly improved power conversion efficiency of 15.72% along with enhanced storage stability. This technique illuminates a novel and simple methodology to regulate the formed species during synthesis, shedding light on ofurther understanding solar cell performance, and aiding the design of future novel synthesis protocols for high-performance optoelectronic devices.

Electron beam pumping improves the conversion efficiency of low-frequency photons radiated by perovskite quantum dots

This research argues that using an electron beam with high kinetic energy to pump perovskite quantum dots can significantly boost the efficiency of the low-frequency photon radiation conversion.Firstly,we measure the random lasing threshold and luminescence threshold of CsPbX_(3)films pumped by an electron beam.Then,we simulate the spatial distribution of the electron beams in CsPbX_(3)films.Combined with the above data,a low-frequency photon radiation conversion model based on the electron pumped perovskite quantum dots is presented.This could be a way to create a terahertz source with a high-power output or to multiply the terahertz power.

Ligand engineering of perovskite quantum dots for efficient and stable solar cells

Lead halide perovskite quantum dots(PQDs) have recently emerged as promising light absorbers for photovoltaic application due to their extraordinary optoelectronic properties. Surface ligands are of utmost importance for the colloidal stability and property tuning of PQDs, while their highly dynamic binding nature not only impedes further efficiency improvement of PQD-based solar cells but also induces intrinsic instability. Tremendous efforts have been made in ligand engineering with good hopes to solve such challenging issues in the past few years. In this review, we first present a fundamental understanding of the role of surface ligands in PQDs, followed by a brief discussion and classification of various ligands that have the potential for improving the electronic coupling and stability of PQD solids. We then provide a critical overview of recent advances in ligand engineering including the strategies of in-situ ligand engineering, postsynthesis/-deposition ligand-exchange, and interfacial engineering, and discuss their impacts on changing the efficiency and stability of perovskite QD solar cells(QDSCs). Finally, we give our perspectives on the future directions of ligand engineering towards more efficient and stable perovskite QDSCs.

High-Performance Perovskite Quantum Dot Solar Cells Enabled by Incorporation with Dimensionally Engineered Organic Semiconductor

Perovskite quantum dots(PQDs)have been considered promising and effective photovoltaic absorber due to their superior optoelectronic properties and inherent material merits combining perovskites and QDs.However,they exhibit low moisture stability at room humidity(20-30%)owing to many surface defect sites generated by inefficient ligand exchange process.These surface traps must be re-passivated to improve both charge transport ability and moisture stability.To address this issue,PQD-organic semiconductor hybrid solar cells with suitable electrical properties and functional groups might dramatically improve the charge extraction and defect passivation.Conventional organic semiconductors are typically low-dimensional(1D and 2D)and prone to excessive self-aggregation,which limits chemical interaction with PQDs.In this work,we designed a new 3D star-shaped semiconducting material(Star-TrCN)to enhance the compatibility with PQDs.The robust bonding with Star-TrCN and PQDs is demonstrated by theoretical modeling and experimental validation.The Star-TrCN-PQD hybrid films show improved cubic-phase stability of CsPbI_(3)-PQDs via reduced surface trap states and suppressed moisture penetration.As a result,the resultant devices not only achieve remarkable device stability over 1000 h at 20-30%relative humidity,but also boost power conversion efficiency up to 16.0%via forming a cascade energy band structure.

Photoresponsive characteristics of thin film transistors with perovskite quantum dots embedded amorphous InGaZnO channels

Photodetectors based on amorphous InGaZnO(a-IGZO)thin film transistor(TFT)and halide perovskites have attracted attention in recent years.However,such a stack assembly of a halide perovskite layer/an a-IGZO channel,even with an organic semiconductor film inserted between them,easily has a very limited photoresponsivity.In this article,we investigate photoresponsive characteristics of TFTs by using CsPbX3(X=Br or I)quantum dots(QDs)embedded into the a-IGZO channel,and attain a high photoresponsivity over 10^3A·W^-1,an excellent detectivity in the order of 10^16 Jones,and a light-to-dark current ratio up to 10^5 under visible lights.This should be mainly attributed to the improved transfer efficiency of photoelectrons from the QDs to the a-IGZO channel.Moreover,spectrally selective photodetection is demonstrated by introducing halide perovskite QDs with different bandgaps.Thus,this work provides a novel strategy of device structure optimization for significantly improving the photoresponsive characteristics of TFT photodetectors.

Proton‑Prompted Ligand Exchange to Achieve High‑Efficiency CsPbI_(3) Quantum Dot Light‑Emitting Diodes

CsPbI_(3)perovskite quantum dots(QDs)are ideal materials for the next generation of red light-emitting diodes.However,the low phase stability of CsPbI_(3)QDs and long-chain insulating capping ligands hinder the improvement of device performance.Traditional in-situ ligand replacement and ligand exchange after synthesis were often difficult to control.Here,we proposed a new ligand exchange strategy using a proton-prompted insitu exchange of short 5-aminopentanoic acid ligands with long-chain oleic acid and oleylamine ligands to obtain stable small-size CsPbI_(3)QDs.This exchange strategy maintained the size and morphology of CsPbI_(3)QDs and improved the optical properties and the conductivity of CsPbI_(3)QDs films.As a result,high-efficiency red QD-based light-emitting diodes with an emission wavelength of 645 nm demonstrated a record maximum external quantum efficiency of 24.45%and an operational half-life of 10.79 h.

In-situ synthesis of stable perovskite quantum dots in core-shell nanofibers via microfluidic electrospinning

Perovskite quantum dots(PQDs) possess remarkable optical properties, such as tunable photoluminescence(PL) emission spectra, narrow full width at half maximum(FWHM) and high PL quantum yield(QY), endowing the PQDs great application prospects. However, the inherent structural instability of PQDs has seriously hindered the application of PQDs in various photoelectric devices. In this work, a microfluidic electrospinning method was used to fabricate color-tunable fluorescent formamidinium lead halogen(FAPbX_(3), X = Cl, Br, I) PQDs/polymer core-shell nanofiber films. The core-shell spinning nanofiber not only supplies the interspace for the in-situ formation of PQDs, but also significantly reduces the permeability of moisture and oxygen in the air, which greatly improves the stability of PQDs. After adjusting the composition of precursors, the blue-emissive polystyrene(core) and polymethyl methacrylate(shell) coated FAPbCl_(3) QDs(abbreviated as PS/FAPbCl_(3)/PMMA, hereinafter), green-emissive PS/FAPbBr_(3)/PMMA and redemissive PS/FAPbI_(3)/PMMA nanofiber films were fabricated with the highest PL QY of 82.3%. Moreover,the PS/FAPbBr_(3)/PMMA nanofiber film exhibits great PL stability under blue light irradiation, long-term storage in the air and water resistance test. Finally, the green-and red-emissive nanofiber films were directly applied as light conversion films to fabricate wide-color-gamut display with the color gamut of 125%, indicating their tremendous potentials in optoelectronic applications.

Dual-stimuli responsive photonic barcodes based on perovskite quantum dots encapsulated in whispering-gallery-mode microspheres

Micro/nanoscale photonic barcodes hold great potential for broad applications in items tracking,mul-tiplexed bioassays and anti-counterfeiting.The ever-increasing demand in advanced anti-counterfeiting applications calls for micro/nanoscale barcodes with accurate recognition,large encoding capacity and high security level.Here,we proposed a strategy to construct the dual-stimuli responsive photonic barcodes based on the perovskite quantum dots(PQDs)doped polymer whispering-gallery-mode(WGM)microcavities via swelling-deswelling method.Benefiting from the well-defined spherical microcavities,the photoluminescence(PL)spectra of as-prepared composites exhibit a series of sharp peaks characteristics resulting from the effective WGM modulation,which constitutes the fingerprint of a specific resonator and thus allows a definition of photonic barcodes.On this basis,we achieved responsive photonic barcodes based on the volatile polar-solvent-controlled luminescence in the mi-crospheres benefitting from the space-confined microcavities and the ionic feature of the PQDs.More-over,the light-controlled photonic barcodes have further been acquired through reversibly regulating the inactivation and activation of the energy transfer(ET)process between the PQDs and photochromic dyes.The well-established protocols of PQDs@WGM enable the development of distinct responsive barcodes with multi-responsive features,which will pave an avenue to new types of flexible WGM-based components for optical data recording and security labels.

Passivation engineering via silica‐encapsulated quantum dots for highly sensitive photodetection

Organometal halide perovskites are promising semiconducting materials for photodetectors because of their favorable optoelectrical properties.Although nanoscale perovskite materials such as quantum dots(QDs)show novel behavior,they have intrinsic stability issues.In this study,an effectively silane barrier-capped quantum dot(QD@APDEMS)is thinly applied onto a bulk perovskite photosensitive layer for use in photodetectors.QD@APDEMS is synthesized with a silane ligand with hydrophobic CH_(3)-terminal groups,resulting in excellent dispersibility and durability to enable effective coating.The introduction of the QD@APDEMS layer results in the formation of a lowdefect perovskite film with enlarged grains.This is attributed to the grain boundary interconnection effect via interaction between the functional groups of QD@APDEMS and uncoordinated Pb^(2+)in grain boundaries.By passivating the grain boundaries,where various trap sites are distributed,hole chargecarrier injection and shunt leakage can be suppressed.Also,from the energy point of view,the deep highest occupied molecular orbital(HOMO)level of QD@APDEMS can work as a hole charge injection barrier.Improved charge dynamics(generation,transfer,and recombination properties)and reduced trap density of QD@APDEMS are demonstrated.When this perovskite film is used in a photodetector,the device performance(especially the detectivity)stands out among existing perovskites evaluated for energy sensing device applications.

Samarium doping improves luminescence efficiency of Cs_(3)Bi_(2)Br_(g)perovskite quantum dots enabling efficient white light-emitting diodes

Considering the toxicity problem of lead-based perovskite quantum dots(PQDs),the lead-free Cs_(3)Bi_(2)Br_(g)PQDs has been recognized as one of the promising candidates.However,the low photoluminescence quantum yields(PLQYs)hinder its practical application in optoelectronic devices.Here,w e successfully prepared Sm^(3+)ions doped Cs_(3)Bi_(2)Br_(g)PQDs with effective white light-emission by modified ligandassisted recrystallization method.The realization of white light-emission is attributed to the broadband blue emission of excitons and the red emission(^(4)G_(5/2)-^(6)HJ(J=5/2,7/2,9/2))of Sm^(3+)ions for Sm^(3+)ions doped Cs_(3)Bi_(2)Br_(g)PQDs.More importantly,compared with the undoped Cs_(3)Bi_(2)Br_(g)PQDs,the PLQYs of Sm^(3+)ions doped Cs_(3)Bi_(2)Br_(g)PQDs are improved from 10.9%to 20.8%,and the anti-water stability is also obviously improved.Finally,the Sm^(3+)ions doped PQDs based white light-emitting diodes(LEDs)with luminous efficiency of 12.6 lm/W were explored,which indicates that there is a potential prospect of lead-free PQDs in white light lighting application.

Nanocomposites of CsPbBr_(3) perovskite quantum dots embedded in Gd_(2)O_(3):Eu^(3+) hollow spheres for LEDs application

Gd_(2)O_(3):Eu^(3+)@CsPbBr_(3) quantum dots(QDs)mesoporous hollow nanocomposites with good luminescent properties and high stability were built.Among which,the hollow Gd_(2)O_(3):Eu^(3+)spheres and CsPbBr_(3) QDs were prepared by urea homogeneous precipitation and hot-injection method,respectively.Finally,the Gd_(2)O_(3):Eu^(3+)@CsPbBr_(3) QDs shell-core compounds were constructed through mechanical stirring.The structure,morphology,stability and luminescent properties were studied by Fourier transform infrared spectroscopy(FT-IR),differential scanning calorimetry/thermogravity(DSC/TG),X-ray diffraction(XRD),field-emission scanning electron microscopy(FE-SEM),transmission electron microscopy(TEM),photoluminescence excitation/photoluminescence(PLE/PL)and life decay tools.Compared to the original CsPbBr_(3) QDs,Gd_(2)O_(3):Eu^(3+)@CsPbBr_(3) QDs display better photostability,thermal stability and current stability.The resulting Gd_(2)O_(3):Eu^(3+)@CsPbBr_(3) QDs composite exhibits good yellow emission.The Gd_(2)O_(3):Eu^(3+)@CsPbBr_(3) QDs mixed silicone resin was directly coated on the blue LED chip,then the w-LED device with the color coordinate of(0.31,0.32)was successfully assembled.The Gd_(2) O_(3):Eu^(3+)@CsPbBr_(3) QDs compounds with excellent luminescent properties and stability are expected to be widely used in lighting and display areas.

Embedding lead halide perovskite quantum dots in carboxybenzene microcrystals improves stability

The stability of lead halide perovskite quantum dots （PQDs） was improved by embedding them in carboxybenzene microcrystals. The resulting needle-shaped mixed microcrystals preserved the strong photoluminescence of the PQDs. Compared with previously reported polystyrene-encapsulated PQDs, the carboxybenzene crystals were robust and protected the dots from moisture and photodegradation. The enhanced stability was attributed to the tight matrix of carboxybenzene microcrystals, which protected the PQDs from moisture. This versatile strategy protected various QDs, including all-inorganic PQDs and chalcogenide QDs （e.g., CdSe/ZnS QDs and CuInS/ZnS QDs）. It provides a facile and versatile method of protecting PQDs and may enable applications in solid-state systems with high color quality requirements such as displays, lasers, and light emitting diodes.

Fluorescent aptasensor for detection of live foodborne pathogens based on multicolor perovskite-quantum-dot-encoded DNA probes and dual-stirring-bar-assisted signal amplification

In this study,a fluorescent(FL)aptasensor was developed for on-site detection of live Salmonella typhimurium(S.T.)and Vibrio parahaemolyticus(V.P.).Complementary DNA(cDNA)of aptamer(Apt)-functionalized multicolor polyhedral oligomeric silsesquioxane-perovskite quantum dots(cDNA-POSSPQDs)were used as encoded probes and combined with dual-stirring-bar-assisted signal amplification for pathogen quantification.In this system,bar 1 was labeled with the S.T.and V.P.Apts,and then bar 2 was functionalized with cDNA-POSS-PQDs.When S.T.and V.P.were introduced,pathogen-Apt complexes would form and be released into the supernatant from bar 1.Under agitation,the two complexes reached bar 2 and subsequently reacted with cDNA-POSS-PQDs,which were immobilized on MXene.Then,the encoded probes would be detached from bar 2 to generate FL signals in the supernatant.Notably,the pathogens can resume their free state and initiate next cycle.They swim between the two bars,and the FL signals can be gradually enhanced to maximum after several cycles.The FL signals from released encoded probes can be used to detect the analytes.In particular,live pathogens can be distinguished from dead ones by using an assay.The detection limits and linear range for S.T.and V.P.were 30 and 10 CFU/mL and 10^(2) -10^(6) CFU/mL,respectively.Therefore,this assay has broad application potential for simultaneous on-site detection of various live pathogenic bacteria in water.

A corona modulation device structure and mechanism based on perovskite quantum dots random laser pumped using an electron beam

Although laser pumping using electron beam(EB)has high transient power output and easy modulation based on perovskite quantum dot(PQD)film,its lasing emitting direction is the same as the pumped EB's direction.Thus,realizing the conventional direct device structure through the film lasing mechanism is extremely difficult.Therefore,using the random lasing principle,herein,we proposed a corona modulation device structure based on PQDs random laser pumped using an EB.We discussed and stimulated the optimized designed method of the device in terms of parameters of the electronic optical device and the utilization ratio of output power and its modulation extinction ratio,respectively.According to the simulation results,this type of device structure can effectively satisfy the new random lasing mechanism in terms of high-speed and high-power modulation.

Coarse and fine-tuning of lasing transverse electromagnetic modes in coupled all-inorganic perovskite quantum dots

Inorganic perovskite lasers are of particular interest,with much recent work focusing on Fabry-P6rot cavity-forming nanowires.We demonstrate the direct observation of lasing from transverse electromagnetic(TEM)modes with a long coherence time-9.5ps in coupled CsPbBr_(3) quantum dots,which dispense with an external cavity resonator and show how the wavelength of the modes can be controlled via two independent tuning-mechanisms.Controlling the pump power allowed us tofine-tune the TEM mode structure to the emission wavelength,thus providing a degree of control over the properties of the lasing signal.The temperature-tuning provided an additional degree of control over the wavelength of the lasing peak,importantly,maintained a constant full width at half maximum(FWHM)over the entire tuning range without mode-hopping.

Microfluidic generation of barcodes with in situ synthesized perovskite quantum dot encapsulation

Perovskite quantum dots(PQDs)are new class of optoelectronic materials,which have been widely studied for their extraordinary physical properties.Attempts to develop these materials are tending to make their fabrication much controllable and extend their values in different areas.Here,we present a novel strategy for one-step in situ synthesis of PQD-encapsulated barcode particles with the assistance of microfluidic technique.By changing the halide ratio in perovskite precursor solutions that emulsified in microfluidic devices,a series of PQDs with different colors have been successfully fabricated,which made them ideal materials as barcodes.Because of the stable encapsulation of ethyleneglycol dimethacrylate(EGDMA)resin,the PQD-encapsulated barcode particles were with no cytotoxicity and could be anti-quenched.It was demonstrated for the first time that the PQD-encapsutated barcode particles by microfluidics were valuable for multiplex biomolecular encoding and assays.These features indicate that the PQD-encapsutated barcode particles by microfluidics are ideal for many practical applications and have a broad prospect in biomedical field.

Ligand exchange engineering of FAPbI_(3) perovskite quantum dots for solar cells

Formamidinium lead triiodide(FAPbI_(3))perovskite quantum dots(PQDs)show great advantages in photovoltaic applications due to their ideal bandgap energy,high stability and solution processability.The anti-solvent used for the post-treatment of FAPbI_(3) PQD solid flms signifcantly afects the surface chemistry of the PQDs,and thus the vacancies caused by surface ligand removal inhibit the optoelectronic properties and stability of PQDs.Here,we study the efects of diferent anti-solvents with diferent polarities on FAPbI_(3) PQDs and select a series of organic molecules for surface passivation of PQDs.The results show that methyl acetate could efectively remove surface ligands from the PQD surface without destroying its crystal structure during the post-treatment.The benzamidine hydrochloride(PhFACl)applied as short ligands of PQDs during the post-treatment could fll the A-site and X-site vacancies of PQDs and thus improve the electronic coupling of PQDs.Finally,the PhFACl-based PQD solar cell(PQDSC)achieves a power conversion efciency of 6.4%,compared to that of 4.63%for the conventional PQDSC.This work provides a reference for insights into the surface passivation of PQDs and the improvement in device performance of PQDSCs.

Solution processed high performance perovskite quantum dots/ZnO phototransistors

Phototransistors that can detect visible light have been fabricated using solution processed zinc oxide channel/zirconium oxide gate insulator thin film transistors(TFTs)and room temperature synthesized perovskite quantum dots(PeQDs)as active layer.Typical ZnO thin film transistors did not show a photocurrent under visible light illumination.However,ZnO TFTs decorated with PeQDs exhibited enhanced photocurrent upon exposure to visible light.The device had a responsivity of 567 A/W(617 A/W),a high detectivity of 6.59×10^(13)Jones(1.85×10^(14)J)and a high sensitivity of 10^(7)(10^(8))under green(blue)light at a low drain voltage of 0.1 V.The high photo-responsivity and detectivity under green light resulted from the combination of short ligands in the QDs films and the high mobility of the spray coated ZnO films.Those results are relevant for the development of low cost and low energy consumption phototransistors working in the visible range.

Efficient red perovskite quantum dot light-emitting diode fabricated by inkjet printing

Perovskite quantum dots(PeQDs)are considered potential display materials due to their high color purity,high photoluminescence quantum yield(PLQY),low cost and easy film casting.In this work,a novel electroluminescence(EL)device consisting of the interface layer of long alkyl-based oleylammonium bromide(OAmBr),which passivates the surface defects of PeQDs and adjusts the carrier transport properties,was designed.The PLQY of the OAmBr/PeQD bilayer was significantly improved.A high-performance EL device with the structure of indium tin oxide/poly(3,4-ethylenedioxythiophene)polystyrene sulfonate/poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine)/OAmBr/PeQDs/2,2′,2′′-(1,3,5-benzinetriyl)-tris(1-phenyl-1H benzimidazole)/LiF/Al was constructed using a spin-coating method.A peak external quantum efficiency(EQE)of 16.5%at the emission wavelength of 646 nm was obtained.Furthermore,an efficient matrix EL device was fabricated using an inkjet printing method.A high-quality PeQD matrix film was obtained by introducing small amounts of polybutene into the PeQDs to improve the printing process.The EQE reached 9.6%for the matrix device with 120 pixels per inch and the same device structure as that of the spin-coating one.