Ligand engineering of colloid quantum dots and their application in all-inorganic tandem solar cells

How to effectively utilize the energy of the broad spectrum of sunlight is one of the basic problems in the research of tandem solar cells. Due to their size effect, quantum confinement effect and coupling effect, colloidal quantum dots(QDs) exhibit new physical properties that bulk materials don’t possess.CdX(X = Se, S, etc.) and Pb X(X = Se, S, etc.) QDs prepared by hot-injection methods have been widely studied in the areas of photovolitaic devices. However, the surfactants surrounding QDs seriously hinder the charge transport of QDs based solar cells. Therefore, how to fabricate high-performance tandem solar cells via ligands engineering has become a major challenge. In this paper, the latest progress of colloidal QDs in the research of all-inorganic tandem solar cells was summarized. Firstly, the improvement of QDs surface ligands and the optimization of ligands engineering were discussed, and the control of the physical properties of QDs films were realized. From the aspects of colloidal QDs, ligand engineering, and solar cell preparation, the future development direction of colloidal QDs solar cells was proposed, providing technical guidances for the preparation of low-cost and high-efficiency nanocrystalline solar cells.

Novel Hybrid Ligands for Passivating Pb S Colloidal Quantum Dots to Enhance the Performance of Solar Cells

We developed novel hybrid ligands to passivate Pb S colloidal quantum dots(CQDs),and two kinds of solar cells based on as-synthesized CQDs were fabricated to verify the passivation effects of the ligands.It was found that the ligands strongly affected the optical and electrical properties of CQDs,and the performances of solar cells were enhanced strongly.The optimized hybrid ligands,oleic amine/octyl-phosphine acid/Cd Cl2improved power conversion efficiency(PCE)to much higher of 3.72%for Schottky diode cell and 5.04%for p–n junction cell.These results may be beneficial to design passivation strategy for low-cost and high-performance CQDs solar cells.

Surface-Modified Graphene Oxide/Lead Sulfide Hybrid Film-Forming Ink for High-Efficiency Bulk Nano-Heterojunction Colloidal Quantum Dot Solar Cells

Solution-processed colloidal quantum dot solar cells(CQDSCs) is a promising candidate for new generation solar cells.To obtain stable and high performance lead sulfide(PbS)-based CQDSCs,high carrier mobility and low non-radiative recombination center density in the PbS CQDs active layer are required.In order to effectively improve the carrier mobility in PbS CQDs layer of CQDSCs,butylamine(BTA)-modified graphene oxide(BTA@GO) is first utilized in PbS-PbX2(X=I-,Br-) CQDs ink to deposit the active layer of CQDSCs through one-step spin-coating method.Such surface treatment of GO dramatically upholds the intrinsic superior hole transfer peculiarity of GO and attenuates the hydrophilicity of GO in order to allow for its good dispersibility in ink solvent.The introduction of B TA@GO in CQDs layer can build up a bulk nano-heterojunction architecture,which provides a smooth charge carrier transport channel in turn improves the carrier mobility and conductivity,extends the carriers lifetime and reduces the trap density of PbS-PbX2 CQDs film.Finally,the BTA@GO/PbS-PbX2 hybrid CQDs film-based relatively large-area(0.35 cm2) CQDSCs shows a champion power conversion efficiency of 11.7% which is increased by 23.1% compared with the control device.

Recent progress of colloidal quantum dot based solar cells

Colloidal quantum dot （CQD） solar cells have attracted great interest due to their low cost and superior photo-electric properties. Remarkable improvements in cell performances of both quantum dot sensitized solar cells （QDSCs） and FbX （X = S, Se） based CQD solar cells have been achieved in recent years, and the power conversion efficiencies （PCEs） ex- ceeding 12% were reported so far. In this review, we will focus on the recent progress in CQD solar cells. We firstly summarize the advance of CQD sensitizer materials and the strategies for enhancing carrier collection efficiency in QD- SCs, including developing multi-component alloyed CQDs and core-shell structured CQDs, as well as various methods to suppress interfacial carrier recombination. Then, we discuss the device architecture development of PbX CQD based solar cells and surface/interface passivation methods to increase light absorption and carrier extraction efficiencies. Finally, a short summary, challenge, and perspective are given.

A Furan-Substituted Polymeric Hole-Transporting Material for Energy Level Regulation and Less Planarity in Colloidal Quantum Dot Solar Cells

For efficient colloidal quantum dot(CQD)solar cells(CQD-SCs),thiol-passivated p-type CQDs are generally used as a hole-transporting material(HTM);however,there are issues with the control of optoelectrical properties,low thiol passivation rate,and poor morphology with a power conversion efficiency(PCE)of approximately 11%.Although polymeric HTMs have been introduced to address these issues,maximizing efficiency and achieving green-solvent processability and thermal stability for commercialization is necessary.Here,we synthesize a novel benzodifuran(BDF)-based HTM(asy-ranPBTBDF)showing an electron-deficient state,low steric hindrance,and low planarity compared to those of a typical benzodithiophene(BDT)-based HTM(asy-ranPBTBDT).BDF properties lead to deep high occupied molecular orbital(HOMO)levels,closeπ-πstacking,excellent solubility,and amorphous properties related to efficiency,green-solvent processability,and thermal stability.With these benefits,the asy-ranPBTBDF-based CQD-SC showed enhanced open-circuit voltage(Voc)(0.65 V)and PCE(13.29%)compared to those of the asy-ranPBTBDT-based device(0.63 V and 12.22%)in toxic processes with chlorobenzene.The asy-ranPBTBDF-based CQD-SC showed a PCE of 12.51%in a green-solvent process with 2-methylanisole and improved thermal stability at 80℃(83.8%retaining after 24 h)owing to less lateral crystallization than the asy-ranPBTBDT-based device(60.8%retaining after 24 h).

Tuning energy transfer efficiency in quantum dots mixture by controling donor/acceptor ratio

Improving the emission performance of colloidal quantum dots(QDs)is of paramount importance for their applications on light-emitting diodes(LEDs),displays and lasers.A highly promising approach is to tune the carrier recombination channels and lifetime by exploiting the energy transfer process.However,to achieve this precise emission optimization,quantitative modulation on energy transfer efficiency is highly desirable but still challenging.Here,we demonstrate a convenient approach to realize tunable energy transfer efficiency by forming QDs mixture with controllable donor/acceptor(D/A)ratio.With the mixing ratio ranging from 16/1 to 1/16,the energy transfer efficiency could be effectively tuned from near zero to~70%.For the high mixing ratio of 16/1,acceptors obtain adequate energy supplied by closely surrounding donors,leading to~2.4-fold PL enhancement.While for the low mixing ratio,the ultrafast and efficient energy extraction process directly suppresses the multi-exciton and Auger recombination in the donor,bringing about a higher threshold.The facile modulation of emission performance by controllably designed mixing ratio and quantitatively tunable energy transfer efficiency will facilitate QD-based optoelectronic and photovoltaic applications.

Review of roll-to-roll fabrication techniques for colloidal quantum dot solar cells

Colloidal quantum dots(CQDs)are of great interest to photovoltaic(PV)technologies as they possess the benefits of solution-processability,size-tunability,and roll-to-roll manufacturability,as well as unique capabilities to harvest near-infrared(NIR)radiation.During the last decade,lab-scale CQD solar cells have achieved rapid improvement in the power conversion efficiency(PCE)from~1%to 18%,which will potentially exceed 20%in the next few years and approach the performance of other PV technologies,such as perovskite solar cells and organic solar cells.In the meanwhile,CQD solar cells exhibit long lifetimes either under shelf storage or continuous operation,making them highly attractive to industry.However,in order to meet the industrial requirements,mass production techniques are necessary to scale up the fabrication of those lab devices into large-area PV modules,such as roll-to-toll coating.This paper reviews the recent developments of large-area CQD solar cells with a focus on various fabrication methods and their principles.It covers the progress of typical large-area coating techniques,including spray coating,blade coating,dip coating,and slot-die coating.It also discusses next steps and new strategies to accomplish the ultimate goal of the low-cost large-area fabrication of CQD solar cells and emphasizes how artificial intelligence or machine learning could facilitate the developments of CQD solar cell research.

Photostability of colloidal single photon emitter in near-infrared regime at room temperature

The photostability of a colloidal single photon emitter in near-infrared regime at room temperature is investigated.The fluorescence lifetime,blinking phenomenon,and anti-bunching effect of a single CdTeSe/ZnS quantum dot with an emission wavelength of 800 nm at room temperature are studied.The second-order correlation function at zero delay time is much smaller than 0.1,which proves that the emission from single quantum dots at 800 nm is a highly pure single-photon source.The effects of the irradiation duration on the fluorescence from single quantum dots are analyzed.The experimental results can be explained by a recombination model including a multi-nonradiative recombination center model and a multi-charged model.

Unraveling the efficiency losses and improving methods in quantum dot-based infrared up-conversion photodetectors

Quantum dot-based up-conversion photodetector,in which an infrared photodiode(PD)and a quantum dot light-emitting diode(QLED)are back-to-back connected,is a promising candidate for low-cost infrared imaging.However,the huge efficiency losses caused by integrating the PD and QLED together hasn’t been studied sufficiently.This work revealed at least three origins for the efficiency losses.First,the PD unit and QLED unit usually didn’t work under optimal conditions at the same time.Second,the potential barriers and traps at the interconnection between PD and QLED units induced unfavorable carrier recombination.Third,much emitted visible light was lost due to the strong visible absorption in the PD unit.Based on the understandings on the loss mechanisms,the infrared up-conversion photodetectors were optimized and achieved a breakthrough photon-to-photon conversion efficiency of 6.9%.This study provided valuable guidance on how to optimize the way of integration for up-conversion photodetectors.

A perspective on functionalizing colloidal quantum dots with DNA

This perspective provides an overview of the techniques that have been developed for the conjugation of DNA to colloidal quantum dots （QDs）, or semiconductor nanocrystals. Methods described include： ligand exchange at the QD surface, covalent conjugation of DNA to the QD surface ligands, and one-step DNA functionalization on core QDs or during core/shell QD synthesis in aqueous solution, with an emphasis on tile most recent progress in our lab. We will also discuss emerging trends in DNA-functionalized QDs for potential applications.

Mechanisms for electric field induced color change in coupled colloidal quantum dot molecules revealed by low temperatures single particle spectroscopy

Colloidal quantum dots(QDs),the building blocks of modern displays and optoelectronic devices,have reached the highest level of size and shape control,and stability during the last 30 years.However,full utilization of their potential requires integration or assembly of more than one nanocrystal as in the case of coupled quantum dots molecules(CQDM),where two core–shell QDs are fused to form two emission centers in close proximity.These CQDMs were recently shown to switch color under an applied electric field at room temperature.Here we use cryogenic single particle spectroscopy of single CQDMs under an electric field to show that various mechanisms can contribute to the spectrum change under an applied electric field at cryogenic temperatures.The first mechanism is the control of the delocalized electron wave function when the electric field is applied along the dimer axis.The electric field bends the conduction band and forces the electron wave function to localize in one of the QDs yielding preferential emission of that particular center.In addition,we found that QDs and CQDMs could become sensitive to surface traps under an electric field.In the case of CQDMs,that can result in decreasing the intensity of one of the QDs while increasing the other QD’s intensity.Moreover,we show that there are surface charges which screen the applied electric field in some of the QDs.This as well can result in electric field-induced color-tuning of CQDMs.Understanding the underlying mechanisms responsible for spectral shifts under applied electric fields is critical for the development of color-tunable devices utilizing CQDMs,including efficient displays and single photon sources.

Double-ended passivator enables dark-current-suppressed colloidal quantum dot photodiodes for CMOS-integrated infrared imagers

Lead sulfide(PbS)colloidal quantum dot(CQD)photodiodes integrated with silicon-based readout integrated circuits(ROICs)offer a promising solution for the next-generation short-wave infrared(SWIR)imaging technology.Despite their potential,large-size CQD photodiodes pose a challenge due to high dark currents resulting from surface states on nonpassivated(100)facets and trap states generated by CQD fusion.In this work,we present a novel approach to address this issue by introducing double-ended ligands that supplementally passivate(100)facets of halidecapped large-size CQDs,leading to suppressed bandtail states and reduced defect concentration.Our results demonstrate that the dark current density is highly suppressed by about an order of magnitude to 9.6 nA cm^(2) at -10 mV,which is among the lowest reported for PbS CQD photodiodes.Furthermore,the performance of the photodiodes is exemplary,yielding an external quantum efficiency of 50.8%(which corresponds to a responsivity of 0.532 A W^(-1))and a specific detectivity of 2.5×10^(12) Jones at 1300 nm.By integrating CQD photodiodes with CMOS ROICs,the CQD imager provides high-resolution(640×512)SWIR imaging for infrared penetration and material discrimination.

Highly-efficient thermoelectric-driven light-emitting diodes based on colloidal quantum dots

Driven by sub-bandgap electric work and Peltier heat,thermoelectric-driven light-emitting diodes(TED-LEDs)not only offer much enhanced power-conversion-efficiency but also eliminate the waste heat generated during the operation of LEDs.However,costeffective and high-efficiency TED-LEDs are not readily accessible for the epitaxially grown III-V LEDs due to the high chip cost and efficiency droop at low-medium brightness(current densities).Here we show that electroluminescence of colloidal quantum dots(QDs)LEDs(QLEDs)circumvents the deficiencies faced by conventional LEDs.The optimal red-emitting device fabricated by cost-effective solution processing technics exhibits external-and internal-power-conversion-efficiency of 21.5%and 93.5%at 100 cd/m^(2),suited for high-efficiency solid-state lighting and high-resolution display.At this brightness,the electric driving voltage(V)of 1.89 V is lower than the photon voltage(Vp=hv/q=1.96 V,q being the elemental charge).With typical Vp=1.96 V,electroluminescence can be detected with the driving voltage as low as 1.0-1.2 V.Luminance of the thermoelectric-driven QLEDs(TED-QLEDs)remains ideally diffusion-dominated with the driving voltage lower than~1.5 V,and further improvement on charge transport is expected to extend the linear ideality to all practical driving voltages.

Colloidal quantum dot for infrared-absorbing solar cells:State-oftheart and prospects

Colloidal quantum dot(CQD)shows great potential for application in infrared solar cells due to the simple synthesis techniques,tunable infrared absorption spectrum,and high stability and solution-processability.Thanks to significant efforts made on the surface chemistry of CQDs,device structure optimization,and device physics of CQD solar cells(CQDSCs),remarkable breakthroughs are achieved to boost the infrared photovoltaic performance and stability of CQDSCs.In particular,the CQDSC with a high power conversion efficiency of~14%and good stability is reported,which is very promising for infrared-absorbing solar cells.In this review,we highlight the unique optoelectronic properties of CQDs for the development of infrared-absorbing solar cells.Meanwhile,the latest advances in finely controlling surface properties of CQDs are comprehensively summarized and discussed.Moreover,the device operation of CQDSCs is discussed in-depth to highlight the impact of the device structure optimization of CQDSCs on their photovoltaic performance,and the emerging novel types of CQDSCs,such as semitransparent,flexible,and lightweight CQDSCs,are also demonstrated.The device stability of CQDSCs is also highlighted from the viewpoint of practical applications.Finally,the conclusions and possible challenges and opportunities are presented to promote the development steps of the CQDSCs with higher infrared photovoltaic performance and robust stability.

Recent development in colloidal quantum dots photovoltaics

The increasing demand for sustainable and green energy supply spurred the surging research on high- efficiency, low-cost photovoltaics. Colloidal quantum dot solar cell （CQDSC） is a new type of photovoltaic device using lead chalcogenide quantum dot film as absorber materials. It not only has a potential to break the 33% Shockley-Queisser efficiency limit for single junction solar cell, but also possesses low-temperature, high-throughput solution processing. Since its first report in 2005, CQDSCs experienced rapid progress achieving a certified 7% efficiency in 2012, an averaged 1% efficiency gain per year. In this paper, we reviewed the research progress reported in the last two years. We started with background introduction and motivation for CQDSC research. We then briefly introduced the evolution history of CQDSC development as well as multiple exciton generation effect. We further focused on the latest efforts in improving the light absorption and carrier collection efficiency, including the bulk-heterojunction structure, quantum funnel concept, band alignment optimization and quantum dot passivation. Afterwards, we discussed the tandem solar cell and device stability, and concluded this article with a perspective. Hopefully, this review paper covers the major achievement in this field in year 2011-2012 and provides readers with a concise and clear understanding of recent CQDSC development.

Electrochemical biosensor employing PbS colloidal quantum dots/Au nanospheres-modified electrode for ultrasensitive glucose detection

Rapid and accurate detection of glucose is of great significance for diabetic management.Highly sensitive glucose sensors promise to achieve noninvasive detection technology,enabling more convenient and efficient means for large-scale screening and long-term dynamic monitoring of diabetes patients.In this work,we demonstrate a sensitive glucose electrochemical biosensor through the synergetic labelling strategy utilizing PbS colloidal quantum dots(CQDs)and Au nanospheres(AuNSs).The PbS CQDs/AuNSs/glucose oxidase(GOx)mixture could be stably immobilized on the carbon electrode surface via the onestep dip-coating method.The electrochemical biosensor employing PbS CQDs/AuNSs/GOx-modified electrode integrates the functions of specific molecule recognition,signal transduction as well as signal amplification.The sensor is capable of transducing the glucose enzyme-catalyzed reaction into significant current signals,exhibiting a good linear response in the glucose concentration range of 0.1μM-10 mM with the limit of detection being 1.432 nM.

Broadband, sensitive and spectrally distinctive SnS_(2) nanosheet/PbS colloidal quantum dot hybrid photodetector

Photodetectors convert photons into current or voltage outputs and are thus widely used for spectroscopy,imaging and sensing.Traditional photodetectors generally show a consistent-polarity response to incident photons within their broadband responsive spectrum.Here we introduced a new type of photodetector employing SnS_(2) nanosheets sensitized with PbS colloidal quantum dots(CQDs)that are not only sensitive(~105AW−1)and broadband(300–1000 nm)but also spectrally distinctive,that is,show distinctive(positive or negative)photoresponse toward incident photons of different wavelengths.A careful mechanism study revealed illumination-modulated Schottky contacts between SnS_(2) nanosheets and Au electrodes,altering the photoresponse polarity toward incident photons of different wavelengths.Finally,we applied our SnS_(2) nanosheet/PbS CQDs hybrid photodetector to differentiate the color temperature of emission from a series of white light-emitting diodes(LEDs),showcasing the unique application of our novel photodetectors.

Significant Lifetime Enhancement in QLEDs by Reducing Interfacial Charge Accumulation via Fluorine Incorporation in the ZnO Electron Transport Layer

ZnO nanoparticles are widely used for the electron transport layers(ETLs)of quantum dots light emitting devices(QLEDs).In this work we show that incorporating fluorine(F)into the ZnO ETL results in significant enhancement in device electroluminescence stability,leading to LT50 at 100 cd m^(−2) of 2,370,000 h in red QLED,47X longer than the control devices.X-ray photo-electron spectroscopy,time-of-flight secondary ion mass spectroscopy,photoluminescence and electrical measurements show that the F passivates oxygen vacancies and reduces electron traps in ZnO.Transient photoluminescence versus bias measurements and capacitance-voltage-luminance measurements reveal that the CF4 plasma-treated ETLs lead to increased electron concentration in the QD and the QD/hole transport layer interface,subsequently decreasing hole accumulation,and hence the higher stability.The findings provide new insights into the critical roles that optimizing charge distribution across the layers play in influencing stability and present a novel and simple approach for extending QLED lifetimes.

Rational design of eco-friendly Mn-doped nonstoichiometric CuInSe/ZnSe core/shell quantum dots for boosted photoelectrochemical efficiency

Colloidal core/shell quantum dots(QDs)with environment-friendly feature and controllable optoelectronic properties are promising building blocks in emerging solar technologies.In this work,we rationally design and tailor the eco-friendly CuInSe(CISe)/ZnSe core/shell QDs by Mn doping and stoichiometric optimization(i.e.,molar ratios of Cu/In).It is demonstrated that Mn doping in In-rich CISe/ZnSe core/shell QDs can effectively engineer the charge kinetics inside the QDs,enabling efficient photogenerated electrons transfer into the shell for retarded charge recombination.As a result,a solar-driven photoelectrochemical(PEC)device fabricated using the optimized Mn-doped In-rich CISe/ZnSe core/shell QDs(Cu/In ratio of 1/2)exhibits improved charge extraction and injection,showing a~3.5-fold higher photocurrent density than that of the pristine CISe/ZnSe core/shell QDs under 1 sun AM 1.5G illumination.The findings indicate that transition metal doping in“green”nonstoichiometric core/shell QDs may offer a new strategy for achieving high-efficiency solar energy conversion applications.

Strong circularly polarized luminescence from quantum dots/2D chiral perovskites composites

Chiral perovskites(CPs)have attracted enormous attentions since they have combined chirality and optoelectrical properties well which is promising in circularly polarized luminescence(CPL)application and of great importance for future spin-optoelectronics.However,there is a key contradiction that in chiral perovskites chirality distorts the crystal structure,leading to poor photoluminescence(PL)properties.Achieving the balance between chirality and PL is a major challenge for strong CPL from chiral perovskites.Differently,two-dimensional(2D)chiral perovskite has shown fascinating chiral induced spin selectivity(CISS)effect which can act as spin injector under ambient conditions.Here,we propose an effective strategy to achieve high CPL activity generated from quantum dots(QDs)by introducing 2D chiral perovskite as a chiral source,providing spin polarized carriers through the CISS effect.The as-synthesized QDs/CP composites exhibit dissymmetry factors(glum)up to 9.06×10^(−3).For the first time,we performed grazing incident wide angle X-ray scattering(GIWAXS)measurements,showing the chirality originates from the distorted lattices caused by the large chiral organic cations.Besides,time-resolved PL(TR-PL)measurements verify the enhanced CPL activity should be attributed to the charge transport between two components.These findings provide a useful method to achieve CPL in QDs/2D chiral perovskite heterojunctions which could be promising in spinoptoelectronics application.