Electro‐Optics of Colloidal Quantum Dot Solids for Thin‐Film Solar Cells

The electro‐optics of thin‐film stacks within photovoltaic devices plays a critical role for the exciton and charge generation and therefore the photovoltaic performance. The complex refractive indexes of each layer in heterojunction colloidal quantum dot (CQD) solar cells are measured and the optical electric field is simulated using the transfer matrix formalism. The exciton generation rate and the photocurrent density as a function of the quantum dot solid thickness are calculated and the results from the simulations are found to agree well with the experimentally determined results. It can therefore be concluded that a quantum dot solid may be modeled with this approach, which is of general interest for this type of materials. Optimization of the CQD solar cell is performed by using the optical simulations and a maximum solar energy conversion efficiency of 6.5% is reached for a CQD solid thickness of 300 nm.     

Transparent InP Quantum Dot Light‐Emitting Diodes with ZrO2 Electron Transport Layer and Indium Zinc Oxide Top Electrode

Because of outstanding optical properties and non‐vacuum solution processability of colloidal quantum dot (QD) semiconductors, many researchers have developed various light emitting diodes (LEDs) using QD materials. Until now, the Cd‐based QD‐LEDs have shown excellent properties, but the eco‐friendly QD semiconductors have attracted many attentions due to the environmental regulation. And, since there are many issues about the reliability of conventional QD‐LEDs with organic charge transport layers, a stable charge transport layer in various conditions must be developed for this reason. This study proposes the organic/inorganic hybrid QD‐LEDs with Cd‐free InP QDs as light emitting layer and inorganic ZrO₂ nanoparticles as electron transport layer. The QD‐LED with bottom emission structure shows the luminescence of 530 cd m^?2 and the current efficiency of 1 cd/A. To realize the transparent QD‐LED display, the two‐step sputtering process of indium zinc oxide (IZO) top electrode is applied to the devices and this study could fabricate the transparent QD‐LED device with the transmittance of more than 74% for whole device array. And when the IZO top electrode with high work‐function is applied to top transparent anode, the device could maintain the current efficiency within the driving voltage range without well‐known roll‐off phenomenon in QD‐LED devices.     

Visualization of Current and Mapping of Elements in Quantum Dot Solar Cells

The delicate influence of properties such as high surface state density and organic–inorganic boundaries on the individual quantum dot electronic structure complicates pursuits toward forming quantitative models of quantum dot thin films ab initio. This report describes the application of electron beam‐induced current (EBIC) microscopy to depleted‐heterojunction colloidal quantum dot photovoltaics (DH‐CQD PVs), a technique which affords one a “map” of current production within the active layer of a PV device. The effects of QD sample size polydispersity as well as layer thickness in CQD active layers as they pertain to current production within these PVs are imaged and explained. The results from these experiments compare well with previous estimations, and confirm the ability of EBIC to function as a valuable empirical tool for the design and betterment of DH‐CQD PVs. Lastly, extensive and unexpected PbS QD penetration into the mesoporous TiO₂ layer is observed through imaging of device cross sections by energy‐dispersive X‐ray spectroscopy combined with scanning transmission electron microscopy. The possible effects of this finding are discussed and corroborated with the EBIC studies on similar devices.     

Layer‐by‐Layer Fabrication of Nanowire Sensitized Solar Cells: Geometry‐Independent Integration

Thin film solar cells that are low in cost but still reasonably efficient comprise an important strategy for reaching price‐performance ratios competitive with fossil fuel electrical generation. Sensitized solar cells – most commonly dye but also semiconductor nanocrystal sensitized – are a thin film device option benefitting from lost cost material components and processing. Nanocrystal sensitized solar cells are predicted to outpace their dye‐based counterparts, but suffer from limited availability of approaches for integrating the nano‐sensitizers within a mesoporous oxide anode, which effectively limits the choice of sensitizer to those that are synthesized in situ or those that are easily incorporated into the oxide framework. The latter methods favor small, symmetric nanocrystals, while highly asymmetric semiconductors (e.g., nanowires, tetrapods, carbon nanotubes) have to date found limited utility in sensitized solar‐cell devices, despite their promise as efficient solar energy converters. Here, a new strategy for solar cell fabrication is demonstrated that is independent of sensitizer geometry. Nanocrystal‐sensitized solar cells are fabricated from either CdSe semiconductor quantum dots or nanowires with facile control over nanocrystal loading. Without substantial optimization and using low processing temperatures, efficiencies approaching 2% are demonstrated. Furthermore, the significance of a ‘geometry‐independent’ fabrication strategy is shown by revealing that nanowires afford important advantages compared to quantum dots as sensitizers. For equivalent nanocrystal masses and otherwise identical devices, nanowire devices yield higher power conversion efficiencies, resulting from both enhanced light harvesting efficiencies for all overlapping wavelengths and internal quantum efficiencies that are more than double those obtained for quantum dot devices.     

A new approach to efficiency enhancement of polymer light-emitting diodes by deposition of anode buffer layers in the presence of additives

Here we report a new approach for the preparation of anode buffer layer for efficient polymer light-emitting devices (PLEDs) by using glycerol to modify relative low conductivity poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). This new type of anode buffer layer allows for a 50–90% increase in device performance for green emitting phosphorescent PLEDs in terms of luminous efficiency, and external quantum efficiency, while 90–150% in power efficiency, as compared to devices fabricated using commercially available PEDOT:PSS. The green emitting phosphorescent PLEDs with this modified anode buffer exhibit very high efficiencies, representing a significant step forward to matching and exceeding the efficiencies reported to date with vacuum-deposited small molecular devices. We anticipate that these findings can provide a simple experimental procedure for improvement of PLEDs.     

Light Extraction Efficiency Enhancement of Colloidal Quantum Dot Light‐Emitting Diodes Using Large‐Scale Nanopillar Arrays

A colloidal quantum dot light‐emitting diode (QLED) is reported with substantially enhanced light extraction efficiency by applying a layer of large‐scale, low‐cost, periodic nanopillar arrays. Zinc oxide nanopillars are grown on the glass surface of the substrate using a simple, efficient method of non‐wetting templates. With the layer of ZnO nanopillar array as an optical outcoupling medium, a record high current efficiency (CE) of 26.6 cd/A is achieved for QLEDs. Consequently, the corresponding external quantum efficiency (EQE) of 9.34% reaches the highest EQE value for green‐emitting QLEDs. Also, the underlying physical mechanisms enabling the enhanced light‐extraction are investigated, which leads to an excellent agreement of the numerical results based on the mode theory with the experimental measurements. This study is the first account for QLEDs offering detailed insight into the light extraction efficiency enhancement of QLED devices. The method demonstrated here is intended to be useful not only for opening up a ubiquitous strategy for designing high‐performance QLEDs but also with respect to fundamental research on the light extraction in QLEDs.     

Boosting the performance of solution-processed quantum dots light-emitting diodes by a hybrid emissive layer via doping small molecule hole transport materials into quantum dots

Solution-processed colloidal quantum dot light-emitting diodes (QLED) have attracted many attentions with significant progress in recent years. However, QLED devices still face some challenges. The energy barrier between Cd-base quantum dots (QDs) and commonly used hole transport materials is larger than that between QDs and electron transport materials, which leads to the imbalance of carriers in the light emitting layer (EML) and the low performance of QLED devices. Herein, we report a simple strategy to improve the device performance by doping small molecule transport material 4,4′-cyclohexylidenebis[N,N-bis(p-tolyl)aniline] (TAPC) into red CdSe/ZnS QDs. The optimized red QLED devices with TAPC-doped emissive layer at a ratio of 3.2 wt% achieve 20.0 cd/A of maximum current efficiency, 16.6 lm/W of power efficiency and 15.7% of external quantum efficiency, which is 30%, 58% and 33% higher than the control device. The improved performance of devices can be ascribed to the increase of hole current density, decrease of leakage electrons and more balanced quantity of carriers in EML. This work put forward a viewpoint to improve the performance of QLED devices via doping high hole mobility materials into emission layer.     

Simultaneous Improvement of Charge Generation and Extraction in Colloidal Quantum Dot Photovoltaics Through Optical Management

Inverted structure heterojunction colloidal quantum dot (CQD) photovoltaic devices with an improved performance are developed using single‐step coated CQD active layers with a thickness of ≈60 nm. This improved performance is achieved by managing the device architecture to simultaneously enhance charge generation and extraction by raising optical absorption within the depletion region. The devices are composed of an ITO/PEDOT:PSS/PbS‐CQD/ZnO/Al structure, in which the p–n heterojunction is placed at the rear (i.e., opposite to the side of illumination) of the devices (denoted as R‐Cell). Sufficient optical generation is achieved at very low CQD layer thicknesses of 45–60 nm because of the constructive interference caused by the insertion of ZnO between the CQD and the Al electrode. The power conversion efficiency (PCE) of R‐Cells containing a thin CQD layers (≈60 nm) is much higher (≈6%) than that of conventional devices containing CQD layers with a thickness of ≈300 nm (PCE ≈4.5%). This optical management strategy provides a general guide to obtain the optimal trade‐off between generation and extraction in planar p–n junction solar cells. In terms of device engineering, all the layers in our R‐Cells are fabricated using single coating, which can lead to compatibility with high‐throughput processes.     

A Versatile Buffer Layer for Polymer Solar Cells: Rendering Surface Potential by Regulating Dipole

Spin‐coated film of poly(vinylidenefluoride‐hexafluoropropylene) (P(VDF‐HFP)) acts as a cathode/anode buffer layer in polymer solar cells (PSCs) with conventional/inverted device structures. Such devices show optimized performances comparable with the controlled device, making P(VDF‐HFP) a good substitute for LiF/MoO₃ as a cathode/anode buffer layer. Ultraviolet photoelectron spectroscopy (UPS) and Kelvin force microscope (KFM) measurements show that increased surface potential of active layers improves cathode contact. In piezoresponse force microscopy (PFM) measurement, P(VDF‐HFP) responds to applied bias in phase curve, showing tunable dipole. This tunable dipole renders surface potential under applied bias. As a result, open‐circuit voltage of devices alters instantly with poling voltage. Moreover, positive poling of P(VDF‐HFP) together with simultaneous oxidation of Ag gradually improves performance of inverted structure device. Integer charge transfer (ICT) model elucidates improved electrode contacts by dipole tuning, varying surface potential and vacuum level shift. Understanding the function of dipole makes P(VDF‐HFP) a promising and versatile buffer layer for PSCs.     

Quantum Dot Light‐Emitting Transistors—Powerful Research Tools and Their Future Applications

In this progress report, the recent work in the field of light‐emitting field‐effect transistors (LEFETs) based on colloidal quantum dots (CQDs) as emitters is highlighted. These devices combine the possibility of electrical switching, as known from field‐effect transistors, with the possibility of light emission in a single device. The properties of field‐effect transistors and the prerequisites of LEFETs are reviewed, before motivating the use of colloidal quantum dots for light emission. Recent reports on these quantum dot light‐emitting field‐effect transistors (QDLEFETs) include both materials emitting in the near infrared and the visible spectral range—underlining the great potential and breadth of applications for QDLEFETs. The way in which LEFETs can further the understanding of the CQD material properties—their photophysics as well as the carrier transport through films—is discussed. In addition, an overview of technology areas offering the potential for large impact is provided.     

Spatial Collection in Colloidal Quantum Dot Solar Cells

In thin‐film photovoltaic (PV) research and development, it is of interest to determine where the chief losses are occurring within the active layer. Herein, a method is developed and presented by which the spatial distribution of charge collection, operando, is ascertained, and its application in colloidal quantum dot (CQD) solar cells is demonstrated at a wide range of relevant bias conditions. A systematic computational method that relies only on knowledge of measured optical parameters and bias‐dependent external quantum efficiency spectra is implemented. It is found that, in CQD PV devices, the region near the thiol‐treated hole‐transport layer suffers from low collection efficiency, as a result of bad band alignment at this interface. The active layer is not fully depleted at short‐circuit conditions, and this accounts for the limited short‐circuit current of these CQD solar cells. The high collection efficiency outside of the depleted region agrees with a diffusion length on the order of hundreds of nanometers. The method provides a quantitative tool to study the operating principles and the physical origins of losses in CQD solar cells, and can be deployed in thin‐film solar cell device architectures based on perovskites, organics, CQDs, and combinations of these materials.     

Origin of Enhanced Hole Injection in Inverted Organic Devices with Electron Accepting Interlayer

Conventional organic light emitting devices have a bottom buffer interlayer placed underneath the hole transporting layer (HTL) to improve hole injection from the indium tin oxide (ITO) electrode. In this work, a substantial enhancement in hole injection efficiency is demonstrated when an electron accepting interlayer is evaporated on top of the HTL in an inverted device along with a top hole injection anode compared with the conventional device with a bottom hole injection anode. Current–voltage and space‐charge‐limited dark injection (DI‐SCLC) measurements were used to characterize the conventional and inverted N,N′‐diphenyl‐N,N′‐bis(1‐naphthyl)(1,1′biphenyl)‐4,4′diamine (NPB) hole‐only devices with either molybdenum trioxide (MoO₃) or 1,4,5,8,9,11‐hexaazatriphenylene hexacarbonitrile (HAT‐CN) as the interlayer. Both normal and inverted devices with HAT‐CN showed significantly higher injection efficiencies compared to similar devices with MoO₃, with the inverted device with HAT‐CN as the interlayer showing a hole injection efficiency close to 100%. The results from doping NPB with MoO₃ or HAT‐CN confirmed that the injection efficiency enhancements in the inverted devices were due to the enhanced charge transfer at the electron acceptor/NPB interface.     

Graphene Doping Improved Device Performance of ZnMgO/PbS Colloidal Quantum Dot Photovoltaics

Lead sulfide (PbS) colloidal quantum dots (CQDs) solar cells possess the advantages of absorption into the infrared, solution processing, and multiple exciton generation, making them very competitive as a low‐cost photovoltaic alternative. Employing an n‐i‐p ZnO/tetrabutylammonium (TBAI)–PbS/ethanedithiol (EDT)–PbS device configuration, the present study reports a 9.0% photovoltaic device through ZnMgO electrode engineering and graphene doping. Sol–gel‐derived Zn_0.9Mg_0.1O buffer layer shows better transparency and higher conduction band maximum than ZnO, and incorporation of graphene and chlorinated graphene oxide into the TBAI–PbS and EDT–PbS layer respectively boosts carrier collection, leading to device with significantly enhanced open circuit voltage and short‐circuit current density. It is believed that incorporation of graphene into PbS CQD film as proposed here, and more generally nanosheets of other materials, would potentially open a simple and powerful avenue to overcome the carrier transport bottleneck of CQD optoelectronic device, thus pushing device performance to a new level.     

PbS量子点同质P-N结光电探测器

PbS胶体量子点因其带隙可调、可溶液加工、吸收系数高等优异特性而广泛应用于光电探测器领域。然而基于光电二极管结构的PbS量子点光电探测器通常会使用不同的材料来制备N型层,从而增加了器件设计和工艺的复杂性,不利于这类光电探测器未来在面阵成像芯片中的应用。为简化制备工艺,提出了一种PbS量子点同质P-N结光电探测器,仅通过一种工艺过程实现了器件P型层和N型层的制备。经测试,探测器对不同入射光强度的探测表现出了良好的线性响应;在0.5 V反向偏压作用下,器件在700 nm处的响应度为0.11 A/W,比探测率为3.41×1011 Jones,展现出了其对弱光探测的优异能力。结果表明文中提出的PbS量子点同质PN结光电探测器有助于推动其在面阵成像领域中的发展。     

采用 Al2O3/ITO 阳极的有机电致发光器件

在采用α-naphtylphenyliphenyl diamine (NPB)和 tris-8-hydroxyquinoline almninura (Alq3 材料的双层有机电致发光器件(OLED)中,在阳极与有机层间插入纳米级厚度的氧化铝作为缓冲层来提高器件的效率.研究了氧化铝的厚度对器件性能的影响,并提出一种模型解释该现象.实验发现,当氧化铝的厚度为 0.3 nm 时,器件的亮度提高 30%,同时在相同电压下,提高了器件电流、量子效率与能量效率,同时降低了器件的阈值电压.相信由于简单与高效,该工艺会对 OLED 技术有很好的影响.     

缓冲层与透明阳极结构对GCT通态特性的影响

在建立GCT器件模型的基础上,研究了缓冲层与透明阳极结构对GCT性能影响。模拟结果表明,缓冲层与透明阳极各自区域中的总杂质量是决定GCT的通态压降的关键因素。通过协调各自区域的峰值掺杂浓度与厚度,可以合理地控制该区域的总杂质量,降低GCT的通态压降。此外,缓冲层和透明阳极相结合结构加速了器件关断过程中载流子的泄放,改善了GCT关断性能。这些结果对于进一步优化GCT器件设计与制造有着重要的参考价值。     

The Effect of Nanoparticle Shape on the Photocarrier Dynamics and Photovoltaic Device Performance of Poly(3‐hexylthiophene):CdSe Nanoparticle Bulk Heterojunction Solar Cells

The charge separation and transport dynamics in CdSe nanoparticle:poly(3‐hexylthiophene) (P3HT) blends are reported as a function of the shape of the CdSe‐nanoparticle electron acceptor (dot, rod, and tetrapod). For optimization of organic photovoltaic device performance it is crucial to understand the role of various nanostructures in the generation and transport of charge carriers. The sample processing conditions are carefully controlled to eliminate any processing‐related effects on the carrier generation and on device performance with the aim of keeping the conjugated polymer phase constant and only varying the shape of the inorganic nanoparticle acceptor phase. The electrodeless, flash photolysis time‐resolved microwave conductivity (FP‐TRMC) technique is used and the results are compared to the efficiency of photovoltaic devices that incorporate the same active layer. It is observed that in nanorods and tetrapods blended with P3HT, the high aspect ratios provide a pathway for the electrons to move away from the dissociation site even in the absence of an applied electric field, resulting in enhanced carrier lifetimes that correlate to increased efficiencies in devices. The processing conditions that yield optimum performance in high aspect ratio CdSe nanoparticles blended with P3HT result in poorly performing quantum dot CdSe:P3HT devices, indicating that the latter devices are inherently limited by the absence of the dimensionality that allows for efficient, prolonged charge separation at the polymer:CdSe interface.     

以ZnO为空穴缓冲层的高效率有机电致发光器件

研制了在传统双层有机电致发光器件(OLED) ITO/NPB/AlQ/Al的阳极与空穴传输层间加入ZnO缓冲层的新型器件.研究了加入缓冲层后对OLED性能的影响,并比较了新型与传统OLED的性能,结果表明,新型器件比传统器件的耐压能力有了显著提高;当电压达到7 V时,发光效率提高了35%.分析认为,ZnO缓冲层的加入,改善了界面, 减少了漏电流,并且阻碍了空穴的注入,有利于改善空穴和电子的注入平衡,提高复合效率.     

发光层厚度对基于CdSSe/ZnS量子点LED性能的影响

采用粒径约为10 nm的CdSSe/ZnS量子点层作为发光层,制备了叠层结构的量子点发光器件,研究了量子点层厚度对其薄膜形貌及量子点发光二极管性能的影响.原子力显微镜测试结果表明:量子点层过厚时,量子点颗粒发生团聚,且随着厚度的降低,团聚现象减弱;当量子点层厚度和量子点粒径相当时(约为10 nm),量子点呈单层排列且团聚现象基本消失;而量子点层厚度低于10 nm时,薄膜出现孔洞缺陷.器件的电流-电压-亮度等测试结果表明:量子点发光二极管中量子点层厚度与器件的光电特性密切相关,量子点层厚度为10 nm的器件光电性能最优,具有最低的启亮电压4.2V,最高的亮度446 cd/m2及最高的电流效率0.2 cd/A.这种通过控制旋涂转速改变量子点层厚度的方法操作简单、重复性好,对QD-LED的研究具有一定应用价值.     

Light‐Emitting Electrochemical Cells Based on Color‐Tunable Inorganic Colloidal Quantum Dots

Large‐area, ultrathin light‐emitting devices currently inspire architects and interior and automotive designers all over the world. Light‐emitting electrochemical cells (LECs) and quantum dot light‐emitting diodes (QD‐LEDs) belong to the most promising next‐generation device concepts for future flexible and large‐area lighting technologies. Both concepts incorporate solution‐based fabrication techniques, which makes them attractive for low cost applications based on, for example, roll‐to‐roll fabrication or inkjet printing. However, both concepts have unique benefits that justify their appeal. LECs comprise ionic species in the active layer, which leads to the omission of additional organic charge injection and transport layers and reactive cathode materials, thus LECs impress with their simple device architecture. QD‐LEDs impress with purity and opulence of available colors: colloidal quantum dots (QDs) are semiconducting nanocrystals that show high yield light emission, which can be easily tuned over the whole visible spectrum by material composition and size. Emerging technologies that unite the potential of both concepts (LEC and QD‐LED) are covered, either by extending a typical LEC architecture with additional QDs, or by replacing the entire organic LEC emitter with QDs or perovskite nanocrystals, still keeping the easy LEC setup featured by the incorporation of mobile ions.