High-Efficiency Perovskite Quantum Dot Photovoltaic with Homogeneous Structure and Energy Landscape

The energy disorder originating from quantum dot (QD) size and relevant solid film inhomogeneity is detrimental to the charge transport and efficiency of QD based solar cells. The emergence of halide perovskite QDs (PQDs) have attracted great attention as promising absorbers in QD photovoltaics. However, it is currently difficult in preparing structural uniform PQD film with homogenous energetic landscape, which is essential for highly reproducible and efficient solar cells. Herein, assisted by a bidentate ligand 2,5-thiophenedicarboxylic acid, a facile solution phase anchoring (SPA) strategy is first reported for design and preparation of all-inorganic CsPbI₃ PQD film with reduced structure and energy disorder. The SPA can enhance PQD dispersion as well as dot-to-dot interaction, which is beneficial for fabricating high-quality PQD arrays and photovoltaic devices. The engineered CsPbI₃ PQD solar cell exhibits enhanced reproducibility, and higher open–circuit voltage together with a champion efficiency of 16.14%, which is among the highest report to date. These results are believed to provide design principle of uniform PQDs for high-performance optoelectronic application.     

Spray‐Coated Colloidal Perovskite Quantum Dot Films for Highly Efficient Solar Cells

A fully automated spray‐coated technology with ultrathin‐film purification is exploited for the commercial large‐scale solution‐based processing of colloidal inorganic perovskite CsPbI₃ quantum dot (QD) films toward solar cells. This process is in the air outside the glove box. To further improve the performance of QD solar cells, the short‐chain ligand of phenyltrimethylammonium bromide (PTABr) with a benzene group is introduced to partially substitute for the original long‐chain ligands of the colloidal QD surface (namely PTABr‐CsPbI₃). This process not only enhances the carrier charge mobility within the QD film due to shortening length between adjacent QDs, but also passivates the halide vacancy defects of QD by Br^? from PTABr. The colloidal QD solar cells show a power conversion efficiency (PCE) of 11.2% with an open voltage of 1.11 V, a short current density of 14.4 mA cm^?2, and a fill factor of 0.70. Due to the hydrophobic surface chemistry of the PTABr–CsPbI₃ film, the solar cell can maintain 80% of the initial PCE in ambient conditions for one month without any encapsulation. Such a low‐cost and efficient spray‐coating technology also offers an avenue to the film fabrication of colloidal nanocrystals for electronic devices.     

Short‐Chain Ligand‐Passivated Stable α‐CsPbI3 Quantum Dot for All‐Inorganic Perovskite Solar Cells

Cubic phase CsPbI₃ (α‐CsPbI₃) perovskite quantum dots (QDs) have received extensive attention due to their all‐inorganic composition and suitable band gap (1.73 eV). However, α‐CsPbI₃ QDs might convert to δ‐CsPbI₃ (orthorhombic phase with indirect band gap of 2.82 eV) due to easy loss of surface ligands. In addition, commonly used long‐chain ligands (oleic acid, OA, and oleylamine, OLA) hinder efficient charge transport in optoelectronic devices. In order to relieve these drawbacks, OA, OLA, octanoic acid, and octylamine are used as capping ligands for synthesizing high‐quality α‐CsPbI₃ QDs. The results indicate that these QDs exhibit excellent optical properties and long‐term stability compared to QDs capped only with OA and OLA. Moreover, QDs with shorter ligands exhibit an enhanced charge transport rate, which improves the power conversion efficiency of photovoltaic devices from 7.76% to 11.87%.     

Enhancing Resistive Switching Performance and Ambient Stability of Hybrid Perovskite Single Crystals via Embedding Colloidal Quantum Dots

Hybrid organic‐inorganic halide perovskites are actively pursued for optoelectronic technologies, but the poor stability is the Achilles’ heel of these materials that hinders their applications. Very recently, it has been shown that lead sulfide (PbS) quantum dots (QDs) can form epitaxial interfaces with the perovskite matrix and enhance the overall stability. In this work, it is demonstrated that embedding QDs can significantly modify the transport property of pristine perovskite single crystals, endowing them with new functionalities besides being structurally robust and free from grain boundaries. Resistive switching memory devices are constructed using solution‐processed CH₃NH₃PbBr₃ (MAPbBr₃) perovskite single crystals and the QD‐embedded counterparts. It is found that QDs could significantly enhance the charge transport and reduce the current–voltage hysteresis. The pristine singe crystal device exhibits negative differential resistance, while the QD‐embedded crystals are featured with filament‐type switching behavior and much improved device stability. This study underscores the potential of QD‐embedded hybrid perovskites as a new media for advanced electronic devices.     

Photomultiplication-Type Organic Photodetectors with High EQE-Bandwidth Product by Introducing a Perovskite Quantum Dot Interlayer

A photomultiplication (PM)-type organic photodetector (OPD) that exploits the ionic motion in CsPbI₃ perovskite quantum dots (QDs) is demonstrated. The device uses a QD monolayer as a PM-inducing interlayer and a donor–acceptor bulk heterojunction (BHJ) layer as a photoactive layer. When the device is illuminated, negative ions in the CsPbI₃ QD migrate and accumulate near the interface between the QDs and the electrode; these processes induce hole injection from the electrode and yield the PM phenomenon with an external quantum efficiency (EQE) >2000% at a 3 V applied bias. It is confirmed that the ionic motion of the CsPbI₃ QDs can induce a shift in the work function of the QD/electrode interface and that the dynamics of ionic motion determines the response speed of the device. The PM OPD showed a large EQE-bandwidth product >10⁶ Hz with a −3 dB frequency of 125 kHz at 3 V, which is one of the highest response speeds reported for a PM OPD. The PM-inducing strategy that exploits ionic motion of the interlayer is a potential approach to achieving high-efficiency PM OPDs.     

Solution-Mediated Hybrid FAPbI3 Perovskite Quantum Dots for Over 15% Efficient Solar Cell

Organic–inorganic formamidinium lead triiodide (FAPbI₃) hybrid perovskite quantum dot (QD) is of great interest to photovoltaic (PV) community due to its narrow band gap, higher ambient stability, and long carrier lifetime. However, the surface ligand management of FAPbI₃ QD is still a key hurdle that impedes the design of high-efficiency solar cells. Herein, this study first develops a solution-mediated ligand exchange (SMLE) for preparing FAPbI₃ QD film with enhanced electronic coupling. By dissolving optimal methylammonium iodide (MAI) into antisolvent to treat the FAPbI₃ QD solution, the SMLE can not only effectively replace the long-chain ligands, but also passivate the A- and X-site vacancies. By combining experimental and theoretical results, this study demonstrates that the SMLE engineered FAPbI₃ QD exhibits lower defect density, which is beneficial for fabricating high-quality QD arrays with desired morphology and carrier transport. Consequently, the SMLE FAPbI₃ QD based solar cell outputs a champion efficiency of 15.10% together with improved long-term ambient storage stability, which is currently the highest reported value for hybrid perovskite QD solar cells. These results would provide new design principle of hybrid perovskite QDs toward high-performance optoelectronic application.     

All-Inorganic CsPbI3 Quantum Dot Solar Cells with Efficiency over 16% by Defect Control

All-inorganic CsPbI₃ quantum dots (QDs) have shown great potential in photovoltaic applications. However, their performance has been limited by defects and phase stability. Herein, an anion/cation synergy strategy to improve the structural stability of CsPbI₃ QDs and reduce the pivotal iodine vacancy (V_I) defect states is proposed. The Zn-doped CsPbI₃ (Zn:CsPbI₃) QDs have been successfully synthesized employing ZnI₂ as the dopant to provide Zn²⁺ and extra I⁻. Theoretical calculations and experimental results demonstrate that the Zn:CsPbI₃ QDs show better thermodynamic stability and higher photoluminescence quantum yield (PLQY) compared to the pristine CsPbI₃ QDs. The doping of Zn in CsPbI₃ QDs increases the formation energy and Goldschmidt tolerance factor, thereby improving the thermodynamic stability. The additional I⁻ helps to reduce the V_I defects during the synthesis of CsPbI₃ QDs, resulting in the higher PLQY. More importantly, the synergistic effect of Zn²⁺ and I⁻ in CsPbI₃ QDs can prevent the iodine loss during the fabrication of CsPbI₃ QD film, inhibiting the formation of new V_I defect states in the construction of solar cells. Consequently, the anion/cation synergy strategy affords the CsPbI₃ quantum dot solar cells (QDSC) a power conversion efficiency over 16%, which is among the best efficiencies for perovskite QDSCs.     

Air‐Stable Cesium Lead Iodide Perovskite for Ultra‐Low Operating Voltage Resistive Switching

CsPbX₃ (X = halide, Cl, Br, or I) all‐inorganic halide perovskites (IHPs) are regarded as promising functional materials because of their tunable optoelectronic characteristics and superior stability to organic–inorganic hybrid halide perovskites. Herein, nonvolatile resistive switching (RS) memory devices based on all‐inorganic CsPbI₃ perovskite are reported. An air‐stable CsPbI₃ perovskite film with a thickness of only 200 nm is successfully synthesized on a platinum‐coated silicon substrate using low temperature all‐solution process. The RS memory devices of Ag/polymethylmethacrylate (PMMA)/CsPbI₃/Pt/Ti/SiO₂/Si structure exhibit reproducible and reliable bipolar switching characteristics with an ultralow operating voltage (<+0.2 V), high on/off ratio (>10⁶), reversible RS by pulse voltage operation (pulse duration < 1 ms), and multilevel data storage. The mechanical flexibility of the CsPbI₃ perovskite RS memory device on a flexible substrate is also successfully confirmed. With analyzing the influence of phase transition in CsPbI₃ on RS characteristics, a mechanism involving conducting filaments formed by metal cation migration is proposed to explain the RS behavior of the memory device. This study will contribute to the understanding of the intrinsic characteristics of IHPs for low‐voltage resistive switching and demonstrate the huge potential of them for use in low‐power consumption nonvolatile memory devices on next‐generation computing systems.     

Synergistic Effect of Hybrid PbS Quantum Dots/2D‐WSe2 Toward High Performance and Broadband Phototransistors

The transitionmetal dichalcogenides‐based phototransistors have demonstrated high transport mobility but are limited to poor photoresponse, which greatly blocks their applications in optoelectronic fields. Here, light sensitive PbS colloidal quantum dots (QDs) combined with 2D WSe₂ to develop hybrid QDs/2D‐WSe₂ phototransistors for high performance and broadband photodetection are utilized. The device shows a responsivity up to 2 × 10⁵ A W^–1, which is orders of magnitude higher than the counterpart of individual material‐based devices. The detection spectra of hybrid devices can be extended to near infrared similar to QDs' response. The high performance of hybrid 0D‐2D phototransistor is ascribed to the synergistic function of photogating effect. PbS QDs can efficiently absorb the input illumination and 2D WSe₂ supports a transport expressway for injected photocarriers. The hybrid phototransistors obtain a specific detectivity over 10¹³ Jones in both ON and OFF state in contrast to the depleted working state (OFF) for other reported QDs/2D phototransistors. The present device construction strategy, photogating enhanced performance, and robust device working conditions contain high potential for future optoelectronic devices.     

Controlled Fabrication of PbS Quantum‐Dot/Carbon‐Nanotube Nanoarchitecture and its Significant Contribution to Near‐Infrared Photon‐to‐Current Conversion

A solution‐processed nanoarchitecture based on PbS quantum dots (QDs) and multi‐walled carbon nanotubes (MWCNTs) is synthesized by simply mixing the pre‐synthesized high‐quality PbS QDs and oleylamine (OLA) pre‐functionalized MWCNTs. Pre‐functionalization of MWCNTs with OLA is crucial for the attachment of PbS QDs and the coverage of QDs on the surface of MWCNTs can be tuned by varying the ratio of PbS QDs to MWCNTs. The apparent photoluminescence (steady‐state emission and fluorescence lifetime) “quenching” effect indicates efficient charge transfer from photo‐excited PbS QDs to MWCNTs. The as‐synthesized PbS‐QD/MWCNT nanoarchitecture is further incorporated into a hole‐conducting polymer poly(3‐hexylthiophene)‐(P3HT), forming the P3HT:PbS‐QD/MWCNT nanohybrid, in which the PbS QDs act as a light harvester for absorbing irradiation over a wide wavelength range of the solar spectrum up to near infrared (NIR, ≈1430 nm) range; whereas, the one‐dimensional MWCNTs and P3HT are used to collect and transport photoexcited electrons and holes to the cathode and anode, respectively. Even without performing the often required “ligand exchange” to remove the long‐chained OLA ligands, the built nanohybrid photovoltaic (PV) device exhibits a largely enhanced power conversion efficiency (PCE) of 3.03% as compared to 2.57% for the standard bulk hetero‐junction PV cell made with P3HT and [6,6]‐Phenyl‐C₆₁‐Butyric Acid Methyl Ester (PCBM) mixtures. The improved performance of P3HT:PbS‐QD/MWCNT nanohybrid PV device is attributed to the significantly extended absorption up to NIR by PbS QDs as well as the effectively enhanced charge separation and transportation due to the integrated MWCNTs and P3HT. Our research results suggest that properly integrating QDs, MWCNTs, and polymers into nanohybrid structures is a promising approach for the development of highly efficient PV devices.     

Quantum Junction Solar Cells: Development and Prospects

Nanocrystals, called semiconductor quantum dots (QDs), contain excitons that are three-dimensionally bound. QDs exhibit a discontinuous electronic energy level structure that is similar to that of atoms and exhibit a distinct quantum confinement effect. As a result, QDs have unique electrical, optical, and physical characteristics that can be used in a variety of optoelectronic device applications, including solar cells. In this review article, the stable and controllable synthesis of QD materials is outlined for upscaling solar cells, including material development and device performance enhancement. It includes a systematic variety of device structures for the fabrication of solar cells, such as QD, hybrid QD/organic, hybrid QD/inorganic, perovskite QD, and hybrid 2D MXene QD/perovskite. The mechanisms for the improvement of stability by QD treatment are examined. For example, the 2D MXene QD and/or Cu_1.8S nanocrystal doping significantly increases the long-term light and ambient stability of perovskite solar cells, resulting from improved perovskite crystallization, reduced hole transport layer (HTL) aggregation and crystallization of films, and reduced UV-induced photocatalytic activity of the electron transport layer (ETL). For the advancement of QD solar cells and their interaction with various materials, the conclusions from this review are crucial. Finally, future prospects for the development of QD solar cells as well as current challenges are discussed.     

Light-emitting diodes based on colloidal silicon quantum dots

Colloidal silicon quantum dots (Si QDs) hold great promise for the development of printed Si electronics. Given their novel electronic and optical properties, colloidal Si QDs have been intensively investigated for optoelectronic applications. Among all kinds of optoelectronic devices based on colloidal Si QDs, QD light-emitting diodes (LEDs) play an important role. It is encouraging that the performance of LEDs based on colloidal Si QDs has been significantly increasing in the past decade. In this review, we discuss the effects of the QD size, QD surface and device structure on the performance of colloidal Si-QD LEDs. The outlook on the further optimization of the device performance is presented at the end.     

Improved Stability and Photodetector Performance of CsPbI3 Perovskite Quantum Dots by Ligand Exchange with Aminoethanethiol

A surface engineering strategy aimed at improving the stability of CsPbI₃ perovskite quantum dots (QDs) both in solution and as films is demonstrated, by performing partial ligand exchange with a short chain ligand, 2‐aminoethanethiol (AET), in place of the original long chain ligands, oleic acid (OA) and oleylamine (OAm), used in synthesis. This results in the formation of a compact ligand barrier around the particles, which prevents penetration of water molecules and thus degradation of the films and, in addition, at the same time improves carrier mobility. Moreover, the AET ligand can passivate surface traps of the QDs, leading to an enhanced photoluminescence (PL) efficiency. As a result, AET‐CsPbI₃ QDs maintain their optical performance both in solution and as films, retaining more than 95% of the initial PL intensity in water after 1 h, and under ultraviolet irradiation for 2 h. Photodetectors based on the AET‐CsPbI₃ QD films exhibit remarkable performance, such as high photoresponsivity (105 mA W^?1) and detectivity (5 × 10¹³ Jones at 450 nm and 3 × 10¹³ Jones at 700 nm) without an external bias. The photodetectors also show excellent stability, retaining more than 95% of the initial responsivity in ambient air for 40 h without any encapsulation.     

Small molecule ternary solar cell with two synergistic electron acceptors for enhanced photovoltaic performance

In recent years, tremendous progresses have been achieved for solution processed organic solar cells (OSCs). The strategy of adding a third component to fabricate ternary solar cells has emerged as an effective method to enhance the power conversion efficiency (PCE) of devices. Furthermore, small molecules feature as lower viscosity and excellent repeatability which facilitate the effective morphology control during fabrication process for enhanced photovoltaic performance. Herein, we report a series of ternary solar cells based on a liquid crystal molecule BTR and two electron acceptors of PC₇₁BM and Y6. These molecules show complementary absorption to broaden spectra coverage and form energy levels cascade for efficient charge transfer. Meanwhile, thanks to the improved molecular packing and formed efficient charge transport network in the ternary blend film, the optimal ternary device possesses the improved charge dynamics and suppressed charge recombination. Thus, ternary solar cells deliver the highest PCE of 11.82% with simultaneously enhanced parameters of J_SC, V_OC and FF. This finding further illustrates the important roles of synergistic effect of fullerenes and non-fullerene acceptors in fabricating highly efficient ternary solar cells.     

Composition Engineering of All‐Inorganic Perovskite Film for Efficient and Operationally Stable Solar Cells

Cesium‐based inorganic perovskites have recently attracted great research focus due to their excellent optoelectronic properties and thermal stability. However, the operational instability of all‐inorganic perovskites is still a main hindrance for the commercialization. Herein, a facile approach is reported to simultaneously enhance both the efficiency and long‐term stability for all‐inorganic CsPbI_2.5Br_0.5 perovskite solar cells via inducing excess lead iodide (PbI₂) into the precursors. Comprehensive film and device characterizations are conducted to study the influences of excess PbI₂ on the crystal quality, passivation effect, charge dynamics, and photovoltaic performance. It is found that excess PbI₂ improves the crystallization process, producing high‐quality CsPbI_2.5Br_0.5 films with enlarged grain sizes, enhanced crystal orientation, and unchanged phase composition. The residual PbI₂ at the grain boundaries also provides a passivation effect, which improves the optoelectronic properties and charge collection property in optimized devices, leading to a power conversion efficiency up to 17.1% with a high open‐circuit voltage of 1.25 V. More importantly, a remarkable long‐term operational stability is also achieved for the optimized CsPbI_2.5Br_0.5 solar cells, with less than 24% degradation drop at the maximum power point under continuous illumination for 420 h.     

Efficient PTB7-Th:Y6:PC71BM ternary organic solar cell with superior stability processed by chloroform

Blend morphology is crucial for the efficiency and stability of organic solar cells. Exploring and understanding the correlations between is meaningful and greatly desired. In this work, based on polymer donor (PTB7-Th), fullerene and non-fullerene acceptors (PC₇₁BM and Y6), we systematically study the influence of ternary strategy and solvent system on device performance and stability. It is found that insufficient and excessive phase separation of blend could result in the depressed performance of corresponding devices. Appropriate phase separation/blend morphology can be achieved by utilizing a ternary strategy or suitable solvent. Chloroform-processed ternary blend PTB7-Th:Y6:PC₇₁BM delivers efficiency of 9.55%, with dramatically enhanced J_SC of 24.68 mA cm⁻² due to optimized absorption, blend morphology and optoelectronic properties. More importantly, superior device stability is demonstrated for the optimal ternary device under both thermal stress and maximum power point operation, by maintaining 80% of initial efficiency at 85 °C for 880 h and presenting almost zero efficiency decay in 200 h under MPP operation.     

Rational Design of Colloidal Core/Shell Quantum Dots for Optoelectronic Applications

Colloidal core/shell quantum dots (QDs) are promising for solar technologies because of their excellent optoelectronic properties including tunable light absorption/emission spectra, high photoluminescence quantum yield (PLQY), suppressed Auger recombination, efficient charge separation/transfer, and outstanding photo-/thermal-/chemical stability. In this review, engineered core/shell QDs with various types of band structures and corresponding device performance in luminescent solar concentrators (LSCs), light-emitting diodes (LEDs), solar-driven photoelectrochemical (PEC) devices, and QDs-sensitized solar cells (QDSCs) are summarized. In particular, the applications of interfacial layer engineering and eco-friendly, heavy metal-free core/shell QDs in optoelectronic devices are highlighted. Finally, strategies towards the developments and practical perspectives of core/shell QDs are briefly mentioned to offer guidelines for achieving prospective high-efficiency and long-term stable QD devices.     

Constructing All-Inorganic Perovskite/Fluoride Nanocomposites for Efficient and Ultra-Stable Perovskite Solar Cells

Organic-inorganic hybrid perovskite solar cells (PSCs) have rapidly developed over the past decade and have achieved the latest certified power conversion efficiency (PCE) up to 25.5%. However, unsatisfactory long-term operational stability for these hybrid PSCs remains a huge obstacle to further development and commercialization. Herein, a unique hetero-structured CsPbI₃/CaF₂ perovskite/fluoride nanocomposites (PFNCs) is fabricated via a newly developed facile two-step hetero-epitaxial growth strategy to deliver efficient and ultra-stable PSCs. After being incorporated into the crystal lattice of α-phase CsPbI₃ perovskite, the cubic-phase CaF₂ in the resultant CsPbI₃/CaF₂ PFNCs can not only passivate the intrinsic defects of CsPbI₃ perovskite itself but also effectively suppress the notorious ion migration in hybrid perovskite Cs_0.05FA_0.81MA_0.14PbI_2.55Br_0.45 (CsFAMA) thin-films of PSCs. As such, the CsFAMA PSC devices based on CsPbI₃/CaF₂-deposited perovskite thin-film achieve a mean PCE of 20.45%, in sharp contrast to 19.33% of the control devices without deposition. Specifically, the CsPbI₃/CaF₂-deposited PSC retains 85% of its original PCE after 1000 h continuous operation at the maximum power point under AM 1.5G solar light, far better than those of the control and CsPbI₃-deposited PSCs with a device T₈₅ lifetime of 315 and 125 h, respectively.     

Dependence of Photocurrent Enhancements in Quantum Dot (QD)‐Sensitized MoS2 Devices on MoS2 Film Properties

This report demonstrates highly efficient nonradiative energy transfer (NRET) from alloyed CdSeS/ZnS semiconductor nanocrystal quantum dots (QDs) to MoS₂ films of varying layer thicknesses, including pristine monolayers, mixed monolayer/bilayer, polycrystalline bilayers, and bulk‐like thicknesses, with NRET efficiencies of over 90%. Large‐area MoS₂ films are grown on Si/SiO₂ substrates by chemical vapor deposition. Despite the ultrahigh NRET efficiencies there is no distinct increase in the MoS₂ photoluminescence intensity. However, by studying the optoelectronic properties of the MoS₂ devices before and after adding the QD sensitizing layer photocurrent enhancements as large as ≈14‐fold for pristine monolayer devices are observed, with enhancements on the order of ≈2‐fold for MoS₂ devices of mixed monolayer and bilayer thicknesses. For the polycrystalline bilayer and bulk‐like MoS₂ devices there is almost no increase in the photocurrent after adding the QDs. Industrially scalable techniques are specifically utilized to fabricate the samples studied in this report, demonstrating the viability of this hybrid structure for commercial photodetector or light harvesting applications.     

Suppressing Ion Migration of Mixed-Halide Perovskite Quantum Dots for High Efficiency Pure-Red Light-Emitting Diodes

Perovskite-based light-emitting diodes (PeLEDs) with a mixed halide composition can be used to obtain the “pure red” emission, i.e., in the 620–650 nm range, required for high-definition displays. However, fast halide ion migration induces phase separation in these materials under electric fields, resulting in poor spectral stability and low efficiency. Herein, a method for producing mixed halide CsPbI_3-xBr_x quantum dots (QDs) is reported in which ion migration is suppressed. The mixed halide composition is first achieved by anion exchange between CsPbI₃ QDs and hydrobromic acid (HBr), during that the bromine ions efficiently passivate the iodine vacancies of the QDs. The original oleic acid ligands are then exchanged for 1-dodecanethiol (1-DT), which suppresses halide ion migration via the strong binding of the sulfhydryl group with the QD surface. PeLEDs based on these QDs exhibit a pure-red electroluminescence (EL) peak at 637 nm, a maximum external quantum efficiency (EQE) of 21.8% with an average value of 20.4%, a peak luminance of 2653 cd m⁻², and low EQE decease with increasing luminance. The EL spectrum of these devices is stable even at 6.7 V and they have an EQE half-life of 70 min at an initial luminance of 150 cd m⁻².