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ADVANCED FUNCTIONAL MATERIALS · 2021 ·Vol. 31 ·期 11 ·2008453 · IF 18.808

Green InP/ZnSeS/ZnS Core Multi-Shelled Quantum Dots Synthesized with Aminophosphine for Effective Display Applications

Pai Liu,Yajun Lou,Shihao Ding,Wenda Zhang,Zhenghui Wu,Hongcheng Yang,Bing Xu,Kai Wang,Xiao Wei Sun

InP quantum dots (QDs) are emerging as promising materials for replacing cadmium-based QDs in view of their heavy metal-free and tunable luminescence. However, the development of InP QD materials still lags due to the expensive and flammable phosphorus precursors, and also the unsatisfactory repeatability caused by the fast nucleation rate. Adopting lowly reactive P precursor aminophosphine can overcome this issue, but their low photoluminescence quantum yield (PLQY) and widening line widths do not apply to the practical application. Through engineering, the core-shell structure of QD, significantly promoted green emissions of QDs were obtained with PLQY of 95% and full width and half maximum (FWHM) of 45 nm, which demonstrated the highest PLQY record obtained from the aminophosphine system. Moreover, due to the residue halogen atoms on the QD surface as inorganic ligands to prevent further oxidization, these InP QDs demonstrated the ultra-long operational lifetime (over 1000 h) for QDs based color enhancement film. By optimizing the device structure, an inverted green InP quantum dot light-emitting diode (QLED) with external quantum efficiency (EQE) of 7.06% was also demonstrated, which showed a significant promise of these InP QDs in highly effective optoelectronic devices.

研究领域: 材料科学 · 纳米技术 · 光电材料
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JOURNAL OF LUMINESCENCE · 2022 · IF 4.171

Photoluminescence properties of InP/GaP/ZnS core/shell/shell colloidal quantum dots treated with halogen acids

Yanqing Zhu,Cong Shen,Xueqing Xu,Jianhua Zou,Lei Wang,Xudong Cheng,Jingqiu Liang,Xiudi Xiao,Gang Xu

InP quantum dots (QDs) with low toxicity are considered to be the most promising materials. However, the oxidation problem of In and P has become to the major factor affecting the optical properties of InP QDs. In this work, the effect of luminescence properties of InP/GaP/ZnS QDs with halogen acid treatment have been studied. The results show that HF and HCl are beneficial to improve the optical properties of QDs, HBr especially HI are not conductive to promote the photoluminescence quantum yield (PL QY) of QDs. HF and HCl can etch the oxidative layer effectively, the F − and Cl − can also passivate the surface indium dangling bonds in the form of atomic ligands. The proposed model of charge carrier recombination show that the PL QY improved significantly after HA treatment attributed to the recombination of electron-hole pairs through radiative pathways mainly from the conduction band and valence band . The InP QDs with HF treatment has the best luminescence properties with high PL QY of 96%, offering great potential for advanced optoelectronic devices.

研究领域: 材料科学 · 光学
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ACS Applied Nano Materials · 2023 · IF 5.9

Sequential Growth of InP Quantum Dots and Coordination between Interfacial Heterovalency and Shell Confinement: Implication for Light-Emitting Devices

Zhongjie Cui,Shuaitao Qin,Haiyang He,Zhuoqi Wen,Dan Yang,Zhiyan Piao,Shiliang Mei,Wanlu Zhang,Ruiqian Guo

As a kind of luminescent nanomaterial, InP quantum dots (QDs) have been regarded as one of the most potential nontoxic alternatives for cadmium-based QDs in the light-emitting devices, and much progress has been obtained recently. However, their growth kinetics remains not fully revealed yet, and the effects of the shelling process on as-synthesized InP cores have been rarely investigated. Herein, the growth kinetics of InP QDs is investigated via the convenient method of varying halide ions, and their sequential growth is proposed according to the discontinuous evolution of their first exciton absorption peaks, especially the observed typical positions, which is different from the reported continuous evolution previously and means that the specific sized InP cores appeared during the growth stage. Moreover, the impacts of ZnS are analyzed from the quantum confinement effect of ZnS on InP cores with different sizes and interfacial heterovalent bonds. The coordination between these two aspects decides the final positions of the first exciton absorption peaks of InP/ZnS QDs. Compared with the positions of the first exciton absorption peaks of bare InP QDs, insufficient confinement of the ZnS shell to small InP cores causes the red-shift, but the heterovalent bonds at the interface cause the blue-shift. Furthermore, the emissions of final InP/ZnS QDs are influenced, and the emission from 484 to 578 nm is obtained via this facile synthetic protocol. It is thought that this study can reveal the growth of InP QDs and provide guidance to design rational InP-based QDs with desired emission and high performance, contributing to the fabrication of efficient light-emitting devices.

研究领域: 材料科学 · 纳米技术 · 光学
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Journal of Materials Chemistry C · 2021 ·Vol. 9 ·期 30 ·9599-9609 · IF 7.393

Highly luminescent InP–In(Zn)P/ZnSe/ZnS core/shell/shell colloidal quantum dots with tunable emissions synthesized based on growth-doping

Cong Shen,Yanqing Zhu,Zixiao Li,Jingling Li,Hong Tao,Jianhua Zou,Xueqing Xu,Gang Xu

InP quantum dots (QDs) are considered as the most promising alternative to Cd-based QDs with lower toxicity, and emission spectrum tunability ranging from the visible to near-infrared region. Although high-quality fluorescent InP QDs have been successfully synthesized by several groups, the rigorous synthesis conditions hinder its practical use in display devices. In this work, for the first time, we introduce Zn2+ into the growth stage of the InP QDs to prepare an InP–In(Zn)P core, and then the as-grown InP–In(Zn)P cores were consecutively coated with typical double shells of inner ZnSe and outer ZnS. The final InP–In(Zn)P/ZnSe/ZnS core/shell/shell QDs exhibited a maximum photoluminescence (PL) quantum yield (QY) of 94.3% and have tunable emissions from yellow (569 nm) to red (630 nm), showing a potential application in display devices. Above all, compared with other related studies, the excellent PL properties were obtained in relatively milder conditions (ultimate vacuum level of 400 mTorr). The results of this study provide guidance for the commercial application of InP QDs as a viable alternative to Cd-based QDs.

研究领域: 材料科学 · 光学
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MATERIALS RESEARCH BULLETIN · 2023 · IF 5.4

Passivating defects in ZnO electron transport layer for enhancing performance of red InP-based quantum dot light-emitting diodes

Meijing Ning,Ke Zhao,Lijia Zhao,Sheng Cao,Jialong Zhao,Yonghui Gao,Xi Yuan

ZnO nanoparticles (NPs) are considered the most promising materials for electron transport layer (ETL) in quantum dot light-emitting diodes (QLEDs). Herein, we employed a synergistic strategy of Mg doping and ZnMgO shell coating to modify the defect states and energy levels of ZnO NPs. Mg doping mitigated the exciton luminescence quenching caused by charge transfer. A ZnMgO shell was also applied to coat the Mg-doped ZnO (ZMO) NPs to passivate surface oxygen defects further. Consequently, QLEDs utilizing ZMO@ZnMgO ETL demonstrate external quantum efficiency and maximum current efficiency of 9.0 % and 11.5 cd A −1 . This work shows an effective defect passivation strategy to enhance the performance of red-emitting InP-based QLEDs.

研究领域: 材料科学 · 光电技术
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LANGMUIR · 2020 · IF 3.557

Optical and Morphological Properties of Single-Phased and Dual-Emissive InP/ZnS Quantum Dots via Transition Metallic and Inorganic Ions

Xian Wei,Shiliang Mei,Bobo Yang,Zhihao Chen,Hanqing Dai,Zhe Hu,Guilin Zhang,Fengxian Xie,Wanlu Zhang,Ruiqian Guo

Single-phased and dual-emissive nanocrystals with broad emission are attractive fluorescent materials for optoelectronic devices due to their unique properties. Until now, the effect of different metallic cations and inorganic anions on III–V group quantum dots (QDs) concerning luminescence features and crystalline growth has been less explored. In this work, dual-emissive InP/ZnS QDs single-doped with transition-metal compounds (Cu2+, Ag+, or Mn2+) are synthesized to compare their optical and morphological properties. The corresponding doping concentrations to realize dual emission with comparative intensity for Cu, Ag, and Mn are 0.8, 6, and 80%, which vary greatly and might be attributed to different precursor reactivities. As for the morphological and internal structures, transmission electron microscopy (TEM) images indicate that transition-metal ions have no obvious effect on the morphological properties and a higher concentration of chloride anions binding with an In-rich interface could conduce to a homogeneous distribution and triangular growth through the comparison of different metal chlorides as precursors. X-ray photoelectron spectroscopy (XPS) results further demonstrate that the high-resolution In 3d spectrum of Mn-doped InP/ZnS QDs with MnCl2 is mainly dominated by In–P bonds, indicating fewer intermediate chemical states. These results concerning well-defined InP/ZnS QDs could promote more diverse insight into surface chemistry and help to better understand the growth mechanism, thus making it possible to regulate InP/ZnS QDs into desired formats for different practical applications like white light-emitting diodes (LEDs).

研究领域: 材料科学 · 纳米技术 · 光学
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Nanoscale Research Letters · 2021 ·Vol. 16 ·期 1 ·1-9 · IF 4.703

Thermodynamics Controlled Sharp Transformation from InP to GaP Nanowires via Introducing Trace Amount of Gallium

Tian Zhenzhen,Yuan Xiaoming,Zhang Ziran,Jia Wuao,Zhou Jian,Huang Han,Meng Jianqiao,He Jun,Du Yong

Growth of high-quality III–V nanowires at a low cost for optoelectronic and electronic applications is a long-term pursuit of research. Still, controlled synthesis of III–V nanowires using chemical vapor deposition method is challenge and lack theory guidance. Here, we show the growth of InP and GaP nanowires in a large area with a high density using a vacuum chemical vapor deposition method. It is revealed that high growth temperature is required to avoid oxide formation and increase the crystal purity of InP nanowires. Introduction of a small amount of Ga into the reactor leads to the formation of GaP nanowires instead of ternary InGaP nanowires. Thermodynamic calculation within the calculation of phase diagrams (CALPHAD) approach is applied to explain this novel growth phenomenon. Composition and driving force calculations of the solidification process demonstrate that only 1 at.% of Ga in the catalyst is enough to tune the nanowire formation from InP to GaP, since GaP nucleation shows a much larger driving force. The combined thermodynamic studies together with III–V nanowire growth studies provide an excellent example to guide the nanowire growth.

研究领域: 材料科学 · 半导体物理 · 纳米科技 · 热力学 · 化学气相沉积 · 晶体生长
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Small · 2022 ·Vol. 18 ·期 15 ·2108120 · IF 15.153

Synergistic Effect of Halogen Ions and Shelling Temperature on Anion Exchange Induced Interfacial Restructuring for Highly Efficient Blue Emissive InP/ZnS Quantum Dots

Zhongjie Cui,Shiliang Mei,Zhuoqi Wen,Dan Yang,Shuaitao Qin,Zhiyong Xiong,Bobo Yang,Haiyang He,Rui Bao,Yi Qiu,Yuanyuan Chen,Wanlu Zhang,Fengxian Xie,Guichuan Xing,Ruiqian Guo

InP quantum dots (QDs) have attracted much attention owing to their nontoxic properties and shown great potential in optoelectronic applications. Due to the surface defects and lattice mismatch, the interfacial structure of InP/ZnS QDs plays a significant role in their performance. Herein, the formation of In–S and S x –In–P 1− x interlayers through anion exchange at the shell-growth stage is revealed. More importantly, it is proposed that the composition of interface is dependent on the synergistic effect of halogen ions and shelling temperature. High shelling temperature contributes to the optical performance improvement resulting from the formation of interlayers, besides the thicker ZnS shell. Moreover, the effect relates to the halogen ions where I − presents more obvious enhancement than Br − and Cl − , owing to their different ability to coordinate with In dangling bonds, which are inclined to form In–S and S x –In–P 1− x bonds. Further, the anion exchange under I − -rich environment causes a blue-shift of emission wavelength with shelling temperature increasing, unobserved in a Cl − - or Br − -rich environment. It contributes to the preparation of highly efficient blue emissive InP/ZnS QDs with emission wavelength of 473 nm, photoluminescence quantum yield of ≈50% and full width at half maximum of 47 nm.

研究领域: 材料科学 · 光学
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Journal of Physical Chemistry C · 2020 · IF 4.189

Mg-Doped ZnO Nanoparticle Films as the Interlayer between the ZnO Electron Transport Layer and InP Quantum Dot Layer for Light-Emitting Diodes

Lishuang Wang,Jie Lin,Xingyuan Liu,Sheng Cao,Yunjun Wang,Jialong Zhao,Bingsuo Zou

Because of the wide emission spectrum tunability that ranges from the visible region to the near-infrared, InP-based colloidal quantum dots (QDs) show great promise for use in the next-generation full-color displays and solid-state lighting. The performance-improved InP QD-based light-emitting devices (QLEDs) were fabricated by using Mg-doped ZnO nanoparticles (ZnMgO NPs) as an interlayer between the ZnO electron transport layer and active InP QD layer. It is found that ZnMgO NPs can reduce electron injection and suppress exciton quenching, which are attributed to the improvement of charge balance in the devices. We successfully demonstrated higher maximum current efficiencies of 5.46 and 5.91 cd/A than the references (2.31 and 2.36 cd/A) without the ZnMgO NP layer in highly efficient red and green QLEDs, respectively. These results signify an effective approach to improve heavy-metal-free QLEDs for commercial applications.

CAS / MDL: 142-72-3
研究领域: 材料科学 · 光电技术
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Applied Materials Today · 2025 · IF 6.9

Rapid thermally driven color-switching in dual cation-modified InP/ZnS quantum dots for visible fluorescence thermometers

Shuaitao Qin,Maoyuan Huang,Bo Tan,Haiyang Li,Jun Wang,Shiliang Mei,Wanlu Zhang,Pengfei Tian,Ruiqian Guo

Indium phosphide (InP) quantum dots (QDs), as an environmentally benign semiconductor material, exhibit significant potential in optoelectronic devices. The incorporation of metal ions is a widely adopted strategy to modulate the optical properties of InP QDs, thereby expanding their application scope. In this study, rapid thermochromic response was achieved in InP/ZnS QDs through dual cation (Nd 3+ &Mn 2+ ) modification. The introduction of Mn 2+ endowed the QDs with dual emission characteristics, while Nd 3+ stabilized the intrinsic emission at the pure blue wavelength of 470 nm by suppressing QD growth via interface anchoring. Investigations revealed that temperature elevation activated the carrier re-excitation process, leading to enhanced intrinsic emission and enabling dynamic fluorescence color switching from orange-yellow to blue. Leveraging this property, a ratiometric fluorescence thermometer with a detection range of 293–533 K and a response time of <5 s was developed. Furthermore, variable-power excitation experiments elucidated the saturation behavior of Mn 2+ impurity emission, corroborating the competitive mechanism between intrinsic and impurity emissions. This work provides novel insights into the multifunctional fluorescence modulation of cadmium-free QDs, with significant implications for smart sensing and eco-friendly display technologies.

研究领域: 材料科学 · 纳米技术 · 光电子学 · 荧光传感 · 热检测
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TALANTA · 2017 · IF 4.162

Fluorescent ligand fishing combination with in-situ imaging and characterizing to screen Hsp 90 inhibitors from Curcuma longa L. based on InP/ZnS quantum dots embedded mesoporous nanoparticles

Yue Hu,Anchen Fu,Zhaoyi Miao,Xiaojing Zhang,Tianlin Wang,An Kang,Jinjun Shan,Dong Zhu,Wei Li

Although ligand fishing has been shown to be an efficient technique for the identification of bioactive components from complex mixtures such as natural products , it cannot be applied to biomedical image processing. Herein, a specific fluorescent ligand fishing combined with in situ imaging approach is presented for the identification of heat shock protein 90 (Hsp 90) inhibitors from complex matrixes, Curcuma longa L. , using N-terminus immobilized Hsp 90α functionalized InP/ZnS quantum dots embedded mesoporous nanoparticles ( i.e. Hsp 90α (NT)-FQDNs) as extraction sorbents and fluorescent tracer. The fished ligands were identified by liquid chromatography time-of-flight/mass spectrometry (LC-TOF/MS) and gas chromatography-mass spectrometry (GC-MS). Moreover, in situ imaging by confocal laser scanning microscopy (CLSM) was applied for evaluating the effect of fished-ligands on bioactivity-induced apoptosis morphologically in HeLa cells. MTT assay verified the bioactivity of the ligands and molecular docking results further provided convincing information to verify the feasible binding mode between ligands and protein. Twelve ligands as potential Hsp 90 inhibitors were ultimately fished and identified from Curcuma longa L. crude extracts. The proposed approach based on Hsp 90α functionalized nanocomposites is superior in the combination of highly specific screening efficiency and concurrent visual in situ imaging, which could have great promise for the development of other plant-derived Hsp 90 inhibitors, and providing a rapid and reliable platform for discovering biologically active molecules in natural products.

研究领域: 药理学 · 生物化学 · 分子生物学 · 纳米技术
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Journal of Materials Chemistry B · 2017 ·Vol. 5 ·期 41 ·8152-8160 · IF 4.543

InP/ZnSe/ZnS quantum dots with strong dual emissions: visible excitonic emission and near-infrared surface defect emission and their application in in vitro and in vivo bioimaging

Jie Zhang,Jie Wang,Tong Yan,Yanan Peng,Dajun Xu,Dawei Deng

Quantum dots (QDs) exhibit many unique optical properties, and show great promise as fluorescent markers in molecular, cellular and in vivo imaging. In this thematic issue, a major concern is their cytotoxicity. Among various Cd-free alternatives, InP-based QDs without highly toxic heavy metal elements have received the most attention. This article first focuses on the synthetic control of oil-soluble InP/ZnSe/ZnS QDs, exhibiting strong dual emissions, namely, visible excitonic emission and near-infrared (NIR) surface defect emission. Next, the organic-to-aqueous phase transfer of the dual emissive QDs was explored systematically. It was found that the dual emissions are relatively stable against the water transfer strategies used here; among them, aqueous dual emissive QDs obtained by wrapping oil-soluble QDs with a poly(acrylic acid)-octylamine (PAA-based) amphiphilic polymer (or modified with the cRGD peptide) exhibit enhanced NIR emission. Finally, using in vitro cell and in vivo small animal optical imaging techniques, the bioactivities of the cRGD-modified amphiphilic polymer-wrapped QDs were also investigated. The results confirm that single-wavelength excitation with strong dual emissions ranging from 550 to >1000 nm will endow the InP-based QDs with the capability for biomedical optical imaging across different spatial scales, as a promising alternative for Cd- and Pb-based QDs.

研究领域: 材料科学 · 纳米技术 · 生物医学工程 · 光学成像
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