Photomultiplication-Type Organic Photodetectors with Fast Response Enabled by the Controlled Charge Trapping Dynamics of Quantum Dot Interlayer

A novel photomultiplication (PM)-type organic photodiode (OPD) that responds much faster (109 kHz bandwidth) than conventional PM-type OPDs is demonstrated. This fast response is achieved by introducing quantum dots (QDs) as a PM-inducing interlayer at the interface between the electrode and the photoactive layer. When the device is illuminated, the photogenerated electrons within the photoactive layer are rapidly transferred and trapped in the trap states of the QD interlayer. The electron trapping subsequently leads to charging of the QD and a consequent shift of the QD energy levels, thereby inducing hole injection from the electrode. This PM mechanism is distinct from that of conventional PM-type OPDs, whose PM usually requires a long time to induce hole (or electron) injection because of the slow transport and accumulation of electrons (or holes) within the photoactive layer. Because of its PM mechanism, the proposed QD-interlayer PM-type OPD achieves high bandwidth and high specific detectivity. In addition, it is demonstrated that the response speed of the proposed device is closely related to the charge trapping/detrapping dynamics of the QDs. This work not only offers a new concept in the design of fast-responding PM-type OPDs but also provides comprehensive understanding of the underlying device physics.     

Highly Sensitive Narrowband Photomultiplication-Type Organic Photodetectors Prepared by Transfer-Printed Technology

Narrowband photomultiplication-type organic photodetectors (PMOPDs) are realized with poly(3-hexylthiophene-2,5-diyl) (P3HT) as the optical field adjusting (OFA) layer and transfer-printed P3HT: [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) (50:1, w/w) as the photomultiplication (PM) layer. The thickness of the OFA layers is adjusted to optimize interfacial trapped electron distribution and density, which determines the external quantum efficiency (EQE) and spectral response range of PMOPDs. Narrowband PMOPDs with 2.5 µm thick P3HT as the OFA layer exhibit two narrow response peaks at 350 and 660 nm, and the corresponding EQE values at 350 and 660 nm are 180% and 760% under an applied bias of −20 V. A wide bandgap polymer poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine] (P-TPD) is deliberately incorporated into OFA layer for adjusting interfacial trapped electron distribution near Al electrode. Narrowband PMOPDs exhibit only one response peak at 660 nm with the enhanced EQE value of 1120% under the same bias. The enhanced EQE of PMOPDs with P-TPD is primarily attributed to the increased hole tunneling injection and transport, which can be ascribed to the enhanced trapped electron density near the Al electrode and the improved hole mobility, respectively. Clearly resolved images can be obtained from the imaging system with the narrowband PMOPDs as sensing pixel without any current preamplifier, indicating the promising potential of PMOPDs in imaging sense.     

Hybrid Organic/PbS Quantum Dot Bilayer Photodetector with Low Dark Current and High Detectivity

Owing to their ease of fabrication, low cost, and high flexibility, organic materials have attracted great interests in photodetector (PD) applications. However, suffering from large dark current, small photocurrent, low on–off ratio, and low sensitivity, performances of bare organic‐based PDs are not satisfactory. Integrating organic materials with other novel semiconductor materials offers an opportunity to overcome these drawbacks. Here, a lateral hybrid organic/lead sulfide (PbS) quantum dot bilayer PD is designed and fabricated, which significantly suppresses the dark current and enhances the photocurrent, leading to improved light detecting capability. Meanwhile, the bilayer PD can be made on a flexible polyimide substrate.     

Filter-Free Narrowband Photomultiplication-Type Planar Heterojunction Organic Photodetectors

Filter-free narrowband photomultiplication-type planar heterojunction (PHJ) organic photodetectors (PM-PHOPDs) are first realized by employing a thick front donor layer and an ultrathin PC₇₁BM layer. The thick front donor layer is employed as an optical field adjusting (OFA) layer. The sequentially coated PC₇₁BM will diffuse slightly into OFA layer, which works as interfacial electron traps to capture photogenerated electrons for assisting hole tunneling injection. The P3HT/PC₇₁BM-based PM-PHOPDs exhibit narrowband response with full-width of half-maximum of 32 nm and external quantum efficiency (EQE) of 1700% at 650 nm under −20 V bias. Due to the enhanced hole transport and reduced charge recombination in PHJ compared to those in bulk heterojunction (BHJ), the EQE of P3HT/PC₇₁BM-based narrowband PM-PHOPDs is twice as P3HT:PC₇₁BM BHJ-based narrowband PM-OPDs under the same bias. The response peak of PM-PHOPDs is adjusted from 650 to 695 or 745 nm by incorporating SMPV1 or DRCN5T in OFA layers due to the red-shifted absorption edge. The EQEs of 3600% at 695 nm and 870% at 745 nm are obtained for P3HT:SMPV1 and P3HT:DRCN5T-based PM-PHOPDs under −20 V bias, respectively. This work provides a smart strategy to achieve narrowband PM-OPDs by designing different OFA layers.     

Efficient All-Polymer Photomultiplication-Type Organic Photodetectors with Prolonged Crystallization Process

With the progressive development of photomultiplication-type organic photodetectors (PM-OPDs), increasing research efforts are devoted to all-polymer PM-OPDs due to their potential in terms of device stability and stretchability. However, poor polymer-polymer miscibility and entanglement of long polymer chains are still the main challenges to form desirable active layer morphology in such systems. A smooth solidification process is favorable toward realizing a morphology that features ordered molecular orientation and high crystallinity. Herein, morphological control issue in all-polymer PM-OPDs is addressed by modifying film formation kinetics with an insulating polymer blending strategy. The prolonged crystallization process of polystyrene-blended films can form high-ordered molecular arrangements and crystallinity in donor/acceptor phases, leading to improved charge transport properties and suppressed trap states. With boosting the trap-assisted photomultiplication effect, the polystyrene-blended all-polymer PM-OPD with a high specific detectivity of 4.0 × 10¹³ Jones can be achieved due to the accumulation of enhanced photogenerated electrons at the interface and the efficient injection of external holes, which is one of the best detectivity values reported for PM-OPDs. This study not only reveals valuable insights into the effects of insulating polymers on the film formation kinetics mechanism, but also provides novel strategy to fabricate high-performance all-polymer PM-OPDs.     

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.     

Organometal Halide Perovskite Quantum Dot Light‐Emitting Diodes

Organometal halide perovskites quantum dots (OHP‐QDs) with bright, color‐tunable, and narrow‐band photoluminescence have significant advantages in display, lighting, and laser applications. Due to sparse concentrations and difficulties in the enrichment of OHP‐QDs, production of large‐area uniform films of OHP‐QDs is a challenging task, which largely impedes their use in electroluminescence devices. Here, a simple dip‐coating method has been reported to effectively fabricate large‐area uniform films of OHP‐QDs. Using this technique, multicolor OHP‐QDs light‐emitting diodes (OQ‐LEDs) emitting in blue, blue‐green, green, orange, and red color have been successfully produced by simply tuning the halide composition or size of QDs. The blue, green, and red OQ‐LEDs exhibited, respectively, a maximum luminance of 2673, 2398, and 986 cd m^?2 at a current efficiency of 4.01, 3.72, and 1.52 cd A^?1, and an external quantum efficiency of 1.38%, 1.06%, and 0.53%, which are much better than most LEDs based on OHP films. The packaged OQ‐LEDs show long‐term stability in air (humidity ≈50%) for at least 7 d. The results demonstrate the great potential of the dip‐coating method to fabricate large‐area uniform films for various QDs. The high‐efficiency OQ‐LEDs also demonstrate the promising potential of OHP‐QDs for low‐cost display, lighting, and optical communication applications.     

量子点红外探测器的研究进展

量子点红外探测器（QDIP）在红外探测领域具有十分广阔的应用前景,同时由于QDIP的有效载流子寿命长、暗电流低、工作温度高、对垂直入射光响应等优势,近年来高性能QDIP已经成为研究的热点。文章首先简要介绍了QDIP的基本原理,然后重点介绍了目前国际上在提高QDIP性能方面的研究进展,分别从如何降低暗电流、实现多色探测、提高探测率等三个方面进行了讨论。     

Passivating {100} Facets of PbS Colloidal Quantum Dots via Perovskite Bridges for Sensitive and Stable Infrared Photodiodes

Solution-processed PbS colloidal quantum dots (CQDs) are promising optoelectronic materials for next-generation infrared imagers due to their monolithic integratability with silicon readout circuit and tunable bandgap controlled by CQDs size. However, large-size PbS CQDs (diameter >4 nm) for longer shortwave-infrared photodetection consist mainly of {100} facets with incomplete surface passivation and unsatisfied stability. Here, it is reported that perovskite-bridged PbS CQDs, in which the {100} facets of the CQDs are epitaxially bridged with CsPbI_3–xBr_x perovskite, can achieve improved passivation and enhanced stability in comparison with the traditional strategies. The resultant infrared CQDs photodiodes exhibit significantly reduced dark current, nearly 50% enhanced photoresponse, and improved work stability. These superior properties synergistically produce the most balanced performance (with a high −3 dB bandwidth of 42 kHz and an impressive specific detectivity of 6.2 × 10¹² Jones) among the reported CQDs photodetectors.     

End-Group Functionalization of Non-Fullerene Acceptors for High External Quantum Efficiency over 150 000% in Photomultiplication Type Organic Photodetectors

Photomultiplication-type organic photodetectors (PM-OPDs) with high external quantum efficiency (EQE) of over 100% are attracting increasing attention due to their potential importance in detecting weak incident light. Considering that the gain of PM-OPD is determined by the ratio of carrier lifetime over carrier transit time, a systematic study on the effect of the end-functionalization of a new extended aromatic fused-ring non-fullerene acceptor (NFA) on the carrier trap/transit time of the PM-OPD. Photophysical analyses by means of ultraviolet-visible absorption, ultraviolet photoelectron spectroscopy, and photoluminescence combined with structural analyses through grazing-incidence wide-angle X-ray scattering show that fluorination of the NFA with the deepest lowest unoccupied molecular orbital level and non-isotropic molecular ordering can yield the longest carrier lifetime. Furthermore, surface energy study show that fluorination of the NFA can also yield the most hydrophobic nature, which can allow the most efficient injection barrier thinning/lowering of the active layer/cathode interface under illumination due to the localized acceptor distribution toward cathode, maximizing the hole injection efficiency from cathode. As a result, an unprecedentedly high EQE of 156 000% is obtained from the optimized PM-OPD. This work shows the importance of the molecular design of acceptor molecules in fabricating high-performance PM-OPDs.     

Solution‐Processed Flexible Broadband Photodetectors with Solution‐Processed Transparent Polymeric Electrode

Room‐temperature solution‐processed flexible photodetectors with spectral response from 300 to 2600 nm are reported. Solution‐processed polymeric thin film with transparency ranging from 300 to 7000 nm and superior electrical conductivity as the transparent electrode is reported. Solution‐processed flexible broadband photodetectors with a “vertical” device structure incorporating a perovskite/PbSe quantum dot bilayer thin film based on the above solution‐processed transparent polymeric electrode are demonstrated. The utilization of perovskite/PbSe quantum dot bilayer thin film as the photoactive layer extends spectral response to infrared region and boosts photocurrent densities in both visible and infrared regions through the trap‐assisted photomultiplication effect. Operated at room temperature and under an external bias of ‐1 V, the solution‐processed flexible photodetectors exhibit over 230 mA W^‐1 responsivity, over 1011 cm Hz1/2/W photodetectivity from 300 to 2600 nm and ≈70 dB linear dynamic ranges. It is also found that the solution‐processed flexible broadband photodetectors exhibit fast response time and excellent flexibility. All these results demonstrate that this work develop a facile approach to realize room‐temperature operated ultrasensitive solution‐processed flexible broadband photodetectors with “vertical” device structure through solution‐processed transparent polymeric electrode.     

Hybrid Perovskite Quantum Dot/Non-Fullerene Molecule Solar Cells with Efficiency Over 15%

Organic-inorganic hybrid film using conjugated materials and quantum dots (QDs) are of great interest for solution-processed optoelectronic devices, including photovoltaics (PVs). However, it is still challenging to fabricate conductive hybrid films to maximize their PV performance. Herein, for the first time, superior PV performance of hybrid solar cells consisting of CsPbI₃ perovskite QDs and Y6 series non-fullerene molecules is demonstrated and further highlights their importance on hybrid device design. In specific, a hybrid active layer is developed using CsPbI₃ QDs and non-fullerene molecules, enabling a type-II energy alignment for efficient charge transfer and extraction. Additionally, the non-fullerene molecules can well passivate the QDs, reducing surface defects and energetic disorder. The champion CsPbI₃ QD/Y6-F hybrid device has a record-high efficiency of 15.05% for QD/organic hybrid PV devices, paving a new way to construct solution-processable hybrid film for efficient optoelectronic devices.     

In Situ Inkjet Printing Strategy for Fabricating Perovskite Quantum Dot Patterns

Perovskite quantum dots are emerging as attractive materials for photonic and optoelectronic applications. Patterning is an important step to incorporate them into display, anti‐counterfeiting, and optical chip applications. In this work, an in situ inkjet printing strategy is demonstrated for fabricating perovskite quantum dots patterns by printing perovskite precursor solutions onto a polymeric layer. Importantly, this strategy can achieve bright photoluminescence with a quantum yield up to 80% and shows broad applicability to a variety of perovskites and polymers. Moreover, the as‐fabricated perovskite quantum dots patterns are composed of a microdisks array on the surface of polymeric layer. The size of these microdisks can be varied by adjusting the printing temperature. To demonstrate the potential use in display and advanced anti‐counterfeiting applications, color pixel patterns and 2D code pattern are fabricated by varying the precursor solutions. The combination of superior photoluminescence properties, simple process, and low cost makes the in situ inkjet printing strategy very promising for patterning perovskite quantum dots toward photonic integrations.     

Trade-Off Between Efficiency and Stability of CsPbBr3 Perovskite Quantum Dot-Based Light-Emitting Diodes by Optimized Passivation Ligands for Br/Pb

Although significant progress has been made in improving the external quantum efficiencies (EQEs) of perovskite quantum dot (QD) light-emitting diodes (QLEDs), understanding the degradation mechanism and enhancing stability remain a challenge. Herein,  increasing the content of Br-based passivation ligands is shown to enhance the EQE up to 16.1% by reducing the defects of CsPbBr₃ QDs in a Br-rich environment. However, the operational lifetimes of perovskite QLEDs gradually decrease with the increase of halide content, owing to the intensified ion migration under continuous electric field confirmed by the current behavior of QLEDs and time-of-flight secondary-ion mass spectrometry. Furthermore, a thorough analysis of the relationship between electricity and luminance of QLEDs suggests that a small amount of residue oleic acid ligands could weaken ion migration. Accordingly, a halide- and acid-hybrid (HAH) co-passivation strategy is proposed to optimize the content of Br- and acid-based ligands, and achieve a maximum EQE of 18.6% and an operational lifetime (T₅₀, extrapolated) of 213 h for CsPbBr₃ QLEDs. This approach for passivating QDs combines the high efficiency of Br-based ligands with the improved stability of acid-based ligands. The study elucidates the correlation between ligands and device performance, highlighting the significance of two or even multiple ligands for efficient and stable perovskite QLEDs.     

In Vivo Plain X-Ray Imaging of Cancer Using Perovskite Quantum Dot Scintillators

Real-time in vivo detection of cancer via attenuation-based plain X-ray imaging is proposed to fundamentally overcome the penetration depth limits of current fluorescence-based imaging techniques. Using cesium lead bromide (CsPbBr₃, CPB) quantum dot (QD) scintillators, real-time X-ray detection of 5 mm-sized Panc-1 cell tumors grown in a mouse is successfully performed. The QDs are rapidly co-synthesized and double-encapsulated with silicon dioxide (SiO₂) to completely prevent them from being aggregated, decomposed, or released; they are then conjugated with antibodies to target pancreatic cancer. Due to the dramatic X-ray attenuation, the X-ray signal from the CPB QDs placed under the 2 cm-thick tissue is clearly observed, while their fluorescence signal is not detected at all. In in vivo mouse experiments, the injection of a tiny amount (2.8 μg on a QD basis) of the CPB–SiO₂@SiO₂–Ab nanoparticles gives rise to a bright spot at the location of the tumor. Cell viability assay and histological analysis confirm the biocompatibility and nontoxicity of the nanoparticles.     

Self-Powered Organic Photodetectors with High Detectivity for Near Infrared Light Detection Enabled by Dark Current Reduction

Organic photodetectors (OPDs) for near infrared (NIR) light detection represents cutting-edge technology for optical communication, environmental monitoring, biomedical imaging, and sensing. Herein, a series of self-powered OPDs with high detectivity are constructed by the sequential deposition (SD) method. The dark currents (J_d) of SD devices are effectively reduced in comparison to blend casting (BC) ones due to the vertical phase segregation structure. Impressively, the J_d values of SD devices based on D18 and Y6 system is reduced to be 2.1 × 10⁻¹¹ A cm⁻² at 0 V, which is two orders of magnitude lower than those of the BC devices. The D* value of the SD device is superior to that of BC device under different bias voltages (0, −0.5, −1.0, and −2.0 V) due to the reduction of dark current, which originates from the fine vertical phase separation structure of the SD device. The mechanism studies shows that the vertical phase segregation structure can effectively suppress the unfavorable charge injection, thus reducing the dark current. Also, the surface energy is proven to play a key role in the photocurrent stability. In addition, the flexible OPDs demonstrate excellent performance in photoplethysmography test.     

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.     

宽带和窄带有机光电倍增探测器研究进展

有机光电倍增探测器因具有可大面积加工、柔性、光谱响应范围可调、低成本和轻质等优点而备受关注,在智能监测、通信、生物医疗、图像传感器和荧光显微镜等领域具有潜在的应用价值。根据光谱响应范围,有机光电倍增探测器可分为宽带和窄带有机光电探测器。文章首先详细介绍了有机光电倍增探测器的结构、工作原理及关键性能参数,其次阐述了宽带和窄带有机光电倍增探测器的研究进展,最后对宽带和窄带有机光电倍增探测器未来的发展前景进行了展望。     

室温合成的钙钛矿量子点及其电致发光二极管

采用室温合成法制备出CsPbBr3钙钛矿量子点,并采用乙酸乙酯对量子点进行了一次、二次和三次清洗,以控制其表面配体密度。然后,利用合成并经过清洗的钙钛矿量子点制备了结构为ITO/PEDOT∶PSS/PTAA/CsPbBr3 QD/TPBi/LiF/Al的电致发光二极管(QLED)。研究了经不同清洗次数的量子点材料制备的器件的光电性能。结果表明,清洗2次的量子点在电荷注入与溶液稳定性之间得到平衡,利用其制备的钙钛矿QLED获得了最大亮度为1405cd/m²、外量子效率为0.6%、色坐标为(0.127,0.559)的绿光发射。     

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.