Solar Cells,Photodetectors, and Optical Sources from Infrared Colloidal Quantum Dots

Optoelectronic devices made via spin‐coating of soft materials onto an arbitrary substrate enable ready integration, low cost, and physical flexibility. The use of solution‐processed colloidal quantum dots offers the added advantage of quantum‐size‐effect tuning of material bandgap. Tuning across the near‐ and short‐wavelength infrared (SWIR) spectral regions enables applications in fiber‐optic communications, night vision and biomedical imaging, and efficient solar energy collection. Here we review progress in infrared solar cells, light sensors, and optical sources based on solution‐processed materials. The latest solution‐processed photovoltaics now provide 4.2% power conversion efficiencies in the infrared, placing them a factor of three away from enabling a doubling in overall solar power conversion efficiency of visible‐wavelength solution‐processed photovoltaics. The best solution‐processed photodetectors now provide sensitivities of 10¹³ Jones D* (normalized detectivity), exceeding the sensitivity of the best epitaxially grown SWIR photodetectors. Infrared optical sources, both broadband light‐emitting diodes and, more recently, lasers, have now also been reported at 1.5 µm.     

Overcoming the Ambient Manufacturability‐Scalability‐Performance Bottleneck in Colloidal Quantum Dot Photovoltaics

Colloidal quantum dot (CQD) solar cells have risen rapidly in performance; however, their low‐cost fabrication under realistic ambient conditions remains elusive. This study uncovers that humid environments curtail the power conversion efficiency (PCE) of solar cells by preventing the needed oxygen doping of the hole transporter during ambient fabrication. A simple oxygen‐doping step enabling ambient manufacturing irrespective of seasonal humidity variations is devised. Solar cells with PCE > 10% are printed under high humidity at industrially viable speeds. The devices use a tiny fraction of the ink typically needed and are air stable over a year. The humidity‐resilient fabrication of efficient CQD solar cells breaks a long‐standing compromise, which should accelerate commercialization.     

Matching Charge Extraction Contact for Infrared PbS Colloidal Quantum Dot Solar Cells

Infrared solar cells (IRSCs) can supplement silicon or perovskite SCs to broaden the utilization of the solar spectrum. As an ideal infrared photovoltaic material, PbS colloidal quantum dots (CQDs) with tunable bandgaps can make good use of solar energy, especially the infrared region. However, as the QD size increases, the energy level shrinking and surface facet evolution makes us reconsider the matching charge extraction contacts and the QD passivation strategy. Herein, different to the traditional sol-gel ZnO layer, energy-level aligned ZnO thin film from a magnetron sputtering method is adopted for electron extraction. In addition, a modified hybrid ligand recipe is developed for the facet passivation of large size QDs. As a result, the champion IRSC delivers an open circuit voltage of 0.49 V and a power conversion efficiency (PCE) of 10.47% under AM1.5 full-spectrum illumination, and the certified PCE is over 10%. Especially the 1100 nm filtered efficiency achieves 1.23%. The obtained devices also show high storage stability. The present matched electron extraction and QD passivation strategies are expected to highly booster the IR conversion yield and promote the fast development of new conception QD optoelectronics.     

A Facet‐Specific Quantum Dot Passivation Strategy for Colloid Management and Efficient Infrared Photovoltaics

Colloidal nanocrystals combine size‐ and facet‐dependent properties with solution processing. They offer thus a compelling suite of materials for technological applications. Their size‐ and facet‐tunable features are studied in synthesis; however, to exploit their features in optoelectronic devices, it will be essential to translate control over size and facets from the colloid all the way to the film. Larger‐diameter colloidal quantum dots (CQDs) offer the attractive possibility of harvesting infrared (IR) solar energy beyond absorption of silicon photovoltaics. These CQDs exhibit facets (nonpolar (100)) undisplayed in small‐diameter CQDs; and the materials chemistry of smaller nanocrystals fails consequently to translate to materials for the short‐wavelength IR regime. A new colloidal management strategy targeting the passivation of both (100) and (111) facets is demonstrated using distinct choices of cations and anions. The approach leads to narrow‐bandgap CQDs with impressive colloidal stability and photoluminescence quantum yield. Photophysical studies confirm a reduction both in Stokes shift (≈47 meV) and Urbach tail (≈29 meV). This approach provides a ≈50% increase in the power conversion efficiency of IR photovoltaics compared to controls, and a ≈70% external quantum efficiency at their excitonic peak.     

Near‐Unity Quantum Yields from Chloride Treated CdTe Colloidal Quantum Dots

Colloidal quantum dots (CQDs) are promising materials for novel light sources and solar energy conversion. However, trap states associated with the CQD surface can produce non‐radiative charge recombination that significantly reduces device performance. Here a facile post‐synthetic treatment of CdTe CQDs is demonstrated that uses chloride ions to achieve near‐complete suppression of surface trapping, resulting in an increase of photoluminescence (PL) quantum yield (QY) from ca. 5% to up to 97.2 ± 2.5%. The effect of the treatment is characterised by absorption and PL spectroscopy, PL decay, scanning transmission electron microscopy, X‐ray diffraction and X‐ray photoelectron spectroscopy. This process also dramatically improves the air‐stability of the CQDs: before treatment the PL is largely quenched after 1 hour of air‐exposure, whilst the treated samples showed a PL QY of nearly 50% after more than 12 hours.     

硫化铜量子点的研究进展

硫化铜量子点作为一种p型半导体纳米晶,具有很强的表面等离子体共振效应、低的毒性以及独特的光学和电学性能,在光催化、生物技术、光电转换材料领域受到了极大关注。由于单分散的硫化铜量子点的制备过程复杂,效率较低,并且纯的硫化铜量子点电导率较低,这极大地限制了其在能量存储器件方面的应用。此外,由于硫化铜量子点复杂的能带结构和独特的p型半导体特性,针对硫化铜量子点的光学性能调控尚不成熟。基于此,本文综述了硫化铜量子点在制备方面的研究现状与取得的进展,介绍了硫化铜量子点的能带结构、晶体结构,及其在量子点敏化太阳能电池、光催化降解污染物、肿瘤细胞诊断与治疗等方面的研究进展,并对硫化铜量子点或Cu系量子点更进一步的研究、开发应用提出了几点建议。     

25th Anniversary Article: Colloidal Quantum Dot Materials and Devices: A Quarter‐Century of Advances

Colloidal quantum dot (CQD) optoelectronics offers a compelling combination of low‐cost, large‐area solution processing, and spectral tunability through the quantum size effect. Since early reports of size‐tunable light emission from solution‐synthesized CQDs over 25 years ago, tremendous progress has been made in synthesis and assembly, optical and electrical properties, materials processing, and optoelectronic applications of these materials. Here some of the major developments in this field are reviewed, touching on key milestones as well as future opportunities.     

量子点的制备技术及进展

量子点是一种三维受限的低维材料,由于其潜在的应用价值受到了人们的广泛关注.对近年来量子点的各种制备方法进行了总结和评述.     

Pseudohalide‐Exchanged Quantum Dot Solids Achieve Record Quantum Efficiency in Infrared Photovoltaics

Application of pseudohalogens in colloidal quantum dot (CQD) solar‐cell active layers increases the solar‐cell performance by reducing the trap densities and implementing thick CQD films. Pseudohalogens are polyatomic analogs of halogens, whose chemistry allows them to substitute halogen atoms by strong chemical interactions with the CQD surfaces. The pseudohalide thiocyanate anion is used to achieve a hybrid surface passivation. A fourfold reduced trap state density than in a control is observed by using a suite of field‐effect transistor studies. This translates directly into the thickest CQD active layer ever reported, enabled by enhanced transport lengths in this new class of materials, and leads to the highest external quantum efficiency, 80% at the excitonic peak, compared with previous reports of CQD solar cells.     

Quantum Dot-Siloxane Anchoring on Colloidal Quantum Dot Film for Flexible Photovoltaic Cell

Lead sulfide (PbS) colloidal quantum dots (CQDs) are promising materials for next-generation flexible solar cells because of near-infrared absorption, facile bandgap tunability, and superior air stability. However, CQD devices still lack enough flexibility to be applied to wearable devices owing to the poor mechanical properties of CQD films. In this study, a facile approach is proposed to improve the mechanical stability of CQDs solar cells without compromising the high power conversion efficiency (PCE) of the devices. (3-aminopropyl)triethoxysilane (APTS) is introduced on CQD films to strengthen the dot-to-dot bonding via QD-siloxane anchoring, and as a result, crack pattern analysis reveals that the treated devices become robust to mechanical stress. The device maintains 88% of the initial PCE under 12 000 cycles at a bending radius of 8.3 mm. In addition, APTS forms a dipole layer on CQD films, which improves the open circuit voltage (V_OC) of the device, achieving a PCE of 11.04%, one of the highest PCEs in flexible PbS CQD solar cells.     

PbS量子点/ZnO纳米片复合膜的制备及其光电化学性能

通过两步法合成PbS量子点(QDs)修饰ZnO纳米片复合膜. 首先利用电化学法在掺氟的SnO₂导电玻璃(FTO)上生长ZnO纳米片, 然后在ZnO纳米片上通过逐次化学浴法沉积PbS量子点形成PbS/ZnO复合膜. 利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)详细表征了样品的表面形貌和晶体结构, 并研究了PbS/ZnO复合膜作为量子点敏化太阳能电池光阳极的紫外-可见吸收谱、光电化学性能和表面光电压谱. 对比ZnO纳米片经PbS量子点修饰前后, 发现PbS量子点修饰后光阳极的光吸收和光伏响应均从紫外区拓宽到了可见光区, 同时光电化学性能有了显著提高, 短路电流密度从敏化前的0.1 mA/cm²增加到0.7 mA/cm², 效率由0.04%增加到0.57%. 与单一ZnO纳米片相比, PbS/ZnO复合膜的表面光伏响应强度明显增强, 说明PbS与ZnO之间形成了有利于光生电荷分离的异质结, 从而导致了PbS/ZnO复合膜光电性能的增加.     

A Chemically Orthogonal Hole Transport Layer for Efficient Colloidal Quantum Dot Solar Cells

Colloidal quantum dots (CQDs) are of interest in light of their solution-processing and bandgap tuning. Advances in the performance of CQD optoelectronic devices require fine control over the properties of each layer in the device materials stack. This is particularly challenging in the present best CQD solar cells, since these employ a p-type hole-transport layer (HTL) implemented using 1,2-ethanedithiol (EDT) ligand exchange on top of the CQD active layer. It is established that the high reactivity of EDT causes a severe chemical modification to the active layer that deteriorates charge extraction. By combining elemental mapping with the spatial charge collection efficiency in CQD solar cells, the key materials interface dominating the subpar performance of prior CQD PV devices is demonstrated. This motivates to develop a chemically orthogonal HTL that consists of malonic-acid-crosslinked CQDs. The new crosslinking strategy preserves the surface chemistry of the active layer beneath, and at the same time provides the needed efficient charge extraction. The new HTL enables a 1.4× increase in charge carrier diffusion length in the active layer; and as a result leads to an improvement in power conversion efficiency to 13.0% compared to EDT standard cells (12.2%).     

量子点敏化太阳能电池TiO2光阳极研究进展

不同结构的TiO_2光阳极对量子点敏化太阳能电池(QDSCs)性能有着重要影响,通过构筑不同纳米结构的TiO_2光阳极,能够有效提升电池性能。介绍了QDSCs的结构和基本原理,重点综述了不同结构的TiO_2光阳极,如零维(0-D)纳米结构、1-D纳米结构、2-D纳米结构及其它复合纳米结构在QDSCs中的应用现状和发展趋势,同时讨论了不同结构TiO_2光阳极的优缺点。最后,指出了可能提升QDSCs效率的有效途径。