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Nano Research · 2024 · IF 9.5

Bright InP quantum dots by Ga-doping for red emitters

Song Kai-Zheng,He Xiao-Hang,Chen Zhe-Yong,Tang Ge,Huang Jin-Zhao,Jiang Feng-Lei

Environment-friendly indium phosphide (InP)-based quantum dots (QDs) with efficient red-emitting properties are sufficiently needed to satisfy the requirement of burgeoning display and lighting technology. Currently, the syntheses of InP QDs using tris(trimethylsilyl)phosphine as the precursor are highly toxic and expensive. Herein, we successfully introduced gallium (Ga) ions into tris(dimethylamino)phosphine-based red InP cores through thermally-promoted cation exchange, and the obtained Ga-doped InP cores exhibited significantly increased photoluminescence quantum yields (PLQY) of up to 26%. The existence of Ga was directly confirmed by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy, and the functions of Ga were systematically studied. After subsequent coating of Ga-doped InP cores with ZnSeS and ZnS shells, the resulting Ga-InP/ZnSeS/ZnS QDs achieved a high PLQY of 62% with an emission maximum at 640 nm. In contrast, without Ga-doping, the PLQY only attained 36% using the same synthetic approach. This indicated an approximate 1.7-fold increase in PLQY. The enhancement of photoluminescence was related to the Ga 3+ , as it not only passivated surface defects of InP cores but also reduced core-shell interface stress. The Ga-InP/ZnSeS/ZnS QDs exhibited good stability towards heat treatment and ultraviolet (UV) irradiation. Moreover, the red light-emitting diode (LED) based on Ga-InP/ZnSeS/ZnS QDs performed well in a wide injected current range of 2 to 200 mA, with a maximum power efficiency of 0.68 lm/W. This work showcases Ga-doping through cation exchange as a promising strategy for enhancing the efficiency of InP-based red emitters.

研究领域: 材料科学 · 纳米技术
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Inkjet-printed blue InP/ZnS/ZnS quantum dot light-emitting diodes

Zhiwen Yang,Gongli Lin,Jieyu Bai,Lechen Li,Yangbin Zhu,Liangrui He,Zhao Jiang,Weijie Wu,Xujiang Yu,Fushan Li,Wanwan Li

Inkjet-printed quantum dot light-emitting diodes (QLEDs) are considered to be ideal candidates for use in full-color displays. However, preparation of eco-friendly blue InP QLEDs using inkjet printing techniques remains rather challenging due to the inferior optical properties of QDs. Here, we present the first efficient method for generating inkjet-printed QLEDs with high color purity using blue InP/ZnS/ZnS QDs as the emitting layer. A two-step heat-up and thick shell strategy was employed for the preparation of blue InP/ZnS/ZnS QDs with a photoluminescence (PL) peak at 465 nm, full width at half-maximum of 38 nm, and PL quantum yield (QY) of ∼ 96 %, which are the records for blue InP QDs. We found that the use of a zinc iodide precursor and anhydrous oxygen reaction environment is critical to determining InP core size, and the size distribution of InP cores can be improved by separating formation of InP magic size clusters and cores via a heat-up step at low temperature. We used two kind of zinc precursors to facilitate shell growth, and the engineered shell thickness suppresses energy transfer, enabling InP/ZnS/ZnS QDs film with high PLQYs and contributing to efficient inkjet printing of QLEDs. These results can facilitate the development of blue InP QLEDs for large-area electroluminescent full-color displays.

CAS / MDL: 112-90-3 111-66-0
研究领域: 材料科学 · 光学工程 · 纳米技术
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Coatings · 2021 ·Vol. 11 ·期 5 ·581 · IF 2.881

Synthesis of Highly Luminescent InP/ZnS Quantum Dots with Suppressed Thermal Quenching

Linyuan Lian,Youyou Li,Daoli Zhang,Jianbing Zhang

InP quantum dots (QDs) are promising down-conversion phosphors for white light LEDs. However, the mainstream InP QDs synthesis uses expensive phosphorus source. Here, economic, in situ-generated PH3is used to synthesize InP QDs and a two-step coating of ZnS shells is developed to prepare highly luminescent InP/ZnS/ZnS QDs. The QDs show a photoluminescence quantum yield as high as 78.5%. The emission can be tuned by adjusting the halide precursor and yellow emissive InP/ZnS/ZnS QDs are prepared by judiciously controlling the synthetic conditions. The yellow QDs show suppressed thermal quenching and retain >90% room temperature PL intensity at 150 °C for the growth solution. Additionally, the PL spectrum matches with the eye sensitivity function, resulting in efficient InP QD white light LEDs.Keywords:InP;quantum dots;core/shell;InP/ZnS;thermal quenching

研究领域: 材料科学 · 光学工程
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ACS Omega · 2019 · IF 2.584

Double-Shelled InP/ZnMnS/ZnS Quantum Dots for Light-Emitting Devices

Wenda Zhang,Weidong Zhuang,Ronghui Liu,Xianran Xing,Xiangwei Qu,Haochen Liu,Bing Xu,Kai Wang,Xiao Wei Sun

Traditionally, ZnS or ZnSe is chosen as the shell material for InP quantum dots (QDs). However, for green or blue InP QDs, the ZnSe shell will form a type-II structure resulting in a redshift of the emission spectrum. Although the band gap of ZnS is wider, its lattice mismatch with InP is larger (∼7.7%), resulting in more defect states and lowered quantum yield (QY). To overcome the above problems, we introduced the intermediate ZnMnS layer in InP/ZnMnS/ZnS QDs. The wide band gap of the intermediate layer (3.7 eV) can confine the electrons and holes in the core completely, and the formation of the type-II structure is avoided. As a result, green InP-based QDs with QY up to 80% were obtained. By adjusting the halogen ratios of the ZnX2 precursor, the minimum and maximum emission peaks are 470 and 620 nm, respectively, covering the whole visible range. Finally, after optimizing the coating shell process, the maximum external quantum efficiency of QD light-emitting diodes fabricated from this InP-based green light QDs can reach 2.7%.

研究领域: 材料科学 · 光电技术
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Journal of Materials Chemistry C · 2024 · IF 5.7

Ultrastable InP@Al2O3 nanocomposites with UV curable function for application in white LEDs

Xiaobo Ding,Hailong Hu,Tailiang Guo,Fushan Li

InP quantum dots have received intensive attention due to their tunable emission wavelengths, narrow bandwidths, and high color purity. Nevertheless, InP quantum dots exhibit notable instability in a complex environment due to their highly oxidizable properties. In this study, we present a strategy for synthesizing InP@Al2O3 nanocomposites that have InP quantum dots evenly embedded in a hybrid substrate containing Al2O3 and coupling-interconnection layers of Si and Al. In addition, we used high-power UV irradiation to repair the defects generated during the synthesis process, leading to photoluminescence (PL) intensity increase of more than 10 times. InP@Al2O3 nanocomposites have demonstrated up to 9 h of laser stability, 30 days of water stability and acid stability and 20 days of alkali stability. It has far exceeded that of InP quantum dots and commercially available phosphors. Distal-type light-emitting diodes (LEDs) with stable and standard white emission can be realized by combining red and green InP@Al2O3 nanocomposites with blue LED chips.

研究领域: 材料科学 · 光学工程 · 纳米技术
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ACS Applied Nano Materials · 2022 · IF 6.14

Nonblinking Core–Multishell InP/ZnSe/ZnS Quantum Dot Bioconjugates for Super-resolution Imaging

Liangliang Zhou,Bin Yu,Lilin Huang,Huiqun Cao,Danying Lin,Yingying Jing,Faiz Wali,Junle Qu

Colloidal quantum dots (QDs) are vital fluorescent probes with several optical features superior to those found in organic dyes for microscopy imaging. However, the emission blinking behavior of a single QD is an intrinsic drawback for stimulated emission depletion microscopy (STED) or structured illumination microscopy techniques. Herein, we present a rational strategy for the synthesis of a type of deterministic, environmentally friendly, small nonblinking core–multishell InP/ZnSe/ZnS QD using a hydrofluoric acid (HF) etching passivation. The strategy includes four steps: synthesis of the InP core, synthesis of oil-phase core–multishell InP/ZnSe/ZnS QDs using hydrogen fluoride and trioctylphosphine etching passivation, promotion of the water solubility of QDs modified by 3-mercaptopropionic acid (MPA), and enhanced biotargeting of core–multishell InP/ZnSe/ZnS QDs by surface coupling technology. The suppressed blinking mechanism was primarily attributed to surface wrapping shells and HF etching passivation of surface dangling bonds, which reduced surface nonradiative recombination. Nonblinking QDs exhibit high fluorescence efficiency (∼90%), good photostability (>20 min), a large Stokes shift (>135 nm), biocompatibility of the cell viability (>90%), and high targeting. Furthermore, super-resolution multifocal structured illumination microscopy imaging of subcellular structures labeled using these QDs confirmed a resolution improvement of greater than 2.6-fold compared to wide-field microscopy. The results indicate that the nonblinking QDs can function as excellent probes for use in the long-term super-resolution visualization of subcellular dynamics.

研究领域: 生物成像 · 材料科学 · 光学
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Journal of Materials Chemistry A · 2015 ·Vol. 3 ·期 43 ·21922-21929 · IF 7.443

InP and Sn:InP based quantum dot sensitized solar cells

Suolong Yang,Pengxiang Zhao,Xiaochong Zhao,Liangti Qu,Xinchun Lai

Due to the ideal band gap and environmental friendliness, InP is a promising light-harvesting material in photovoltaic cells. However, “green” InP based quantum dot sensitized solar cells (QDSSCs) have been rarely reported. Herein, nearly monodispersed Sn doped InP (Sn:InP) quantum dots (QDs) were synthesized by the one-pot nucleation doping method, and used as the sensitizer in the construction of QDSSCs. High QD loadings on the TiO2 film electrodes were achieved by using the capping ligand-induced self-assembly (CLIS) sensitization technique. The resulting champion Sn:InP cell shows a power conversion efficiency (PCE) of 3.54% under AM 1.5G (simulated 1 sun illumination), which is remarkably higher than that of un-doped InP QD based ones. This improvement is ascribed to the regulation role of the band gap by Sn dopant in the InP QDs. The Sn:InP QDSSCs exhibit moderate efficiency, good reproducibility and stability. These new findings may pave the way for the performance improvements of other QD photovoltaic devices.

CAS / MDL: 107-96-0
研究领域: 材料科学 · 能源科学
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INORGANIC CHEMISTRY · 2023 · IF 4.6

Bright InP Quantum Dots by Mid-Synthetic Modification with Zinc Halides

Hui-Ling Hu,Hao Hao,Xue Ren,Zhe-Yong Chen,Meng Liu,Yi Liu,Feng-Lei Jiang

InP quantum dots (QDs) attract growing interest in recent years, owing to their environmental advantages upon applications in display and lighting. However, compared to Cd-based QDs and Pb-based perovskites, the synthesis of InP QDs with high optical quality is relatively more difficult. Here, we established a mid-synthetic modification approach to improve the optical properties of InP-based QDs. Tris(dimethylamino)phosphine ((DMA)3P) and indium iodide were used to prepare InP QDs with a green emission (∼527 nm). By introducing zinc halides (ZnX2) during the mid-synthetic process, the photoluminescence quantum yield (PLQY) of the resulting InP/ZnSeS/ZnS core/shell/shell QDs was increased to >70%, and the full-width-at-half-maximum (FWHM) could be narrowed to ∼40 nm. Transmission electron microscopy clearly showed the improvement of the QDs particle size distribution after introducing ZnX2. It was speculated that ZnX2 was bound to the surface of QDs as a Z-type ligand, which not only passivated surface defects and suppressed the emission of defect states but also prevented Ostwald ripening. The InP cores were also activated by ZnX2, which made the growth of the ZnSeS shell more favorable. The photoluminescence properties started to be improved significantly only when the amount of ZnX2 exceeded 0.5 mmol. As the amount increased, more ZnX2 was distributed around the QDs to form a ligand layer, which prevented the shell precursor from crossing the ligand layer to the surface of the InP core, thus reducing the size of the InP/ZnSeS/ZnS QDs. This work revealed a new role of ZnX2 and found a method for InP QDs with high brightness and low FWHM by the mid-synthetic modification, which would inspire the synthesis of even better InP QDs.

研究领域: 材料科学 · 纳米技术
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Advanced Optical Materials · 2024 · IF 8

High-Efficiency and Stable Green InP-QLED Enabled by Lowering Electron Injection Barrier

Mengyuan Chen,Qian Li,Yangyang Bian,Shuaibing Wang,Binbin Hu,Aiwei Tang,Fei Chen,Yanbing Lv,Huaibin Shen

The external quantum efficiencies (EQE) and luminances of red InP-based and blue ZnTeSe-based quantum dot light-emitting diodes (QLEDs) have exceeded 20% and 80 000 cd m −2 , respectively, and the T 50 @100 cd m −2 (time for the luminance decreasing by 50%) operational lifetime of red InP-based QLEDs also have exceeded 1 000 000 h, nearing industrial application standards. However, the low EQE, luminance, and inferior lifetime of green InP-based QLEDs restrict the application for their full-color Cd-free display and lighting applications. The large electron injection barrier and severe exciton quenching caused by defect states of ZnMgO (ZMO) nanoparticles (NPs) lead to lower electron concentration in the emitting layer, which results in reduced radiative recombination. Here, with the surface passivation of MgCl 2 , the exciton quenching sites are significantly suppressed, and the electron injection barrier is reduced owing to the conduction band minimum (CBM) levels upshift of ZMO. As a result, a high EQE of 21.43%, maximum luminance of 25 5985 cd m −2 , along with a long T 50 @1000 cd m −2 (over 4 600 h) and T 50 @100 cd m −2 (over 290 000 h) operational lifetime is achieved for green InP-based QLEDs. These values have all exceeded the previous best values of green InP-based QLEDs.

CAS / MDL: 7791-18-6
研究领域: 材料科学 · 光电技术
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OPTICAL MATERIALS · 2024 · IF 3.8

Improved InP/ZnSe/ZnSeS/ZnS quantum dots for single-terminal carrier-injection light-emitting devices

Jianpu Lin,Shengjie Zhang,Lingfeng Du,Baiquan Zhang,Xiongtu Zhou,Yongai Zhang,Chaoxing Wu

The wavelength tunable and environmentally friendly InP quantum dots are considered one of the most powerful alternatives to cadmium-based quantum dots, and the luminescent devices prepared with them also show great potential. There is still room for improvement in the synthesis methods and device applications of InP based quantum dots. In this work, we report one pot synthesis route for InP/ZnSe/ZnSeS/ZnS green QDs based on tris(dimethylamino)phosphine (DMP) phosphorus by using the strategy of multi shell coating and gradient heating to reduce surface defects of quantum dots. The shell structure, dosage, and growth temperature have all been taken into account in order to explore better performance of InP QDs. The synthesized green quantum dots have 86 % PLQY and a full width at half maximum of 36 nm. In addition, the synthesized green InP quantum dots are applied in AC QLED devices. The experimental results show that the luminescence intensity is affected by the driving voltage and frequency, which is similar to the working mode of non-carrier-injected emitting devices. And there is a matching value between the voltage and frequency.

研究领域: 材料科学 · 纳米技术 · 光电子学
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CRYSTENGCOMM · 2020 ·Vol. 22 ·期 20 ·3474-3481 · IF 3.117

Controlling the nucleation process of InP/ZnS quantum dots using zeolite as a nucleation site

Xiaopeng Zhou,Jiejun Ren,Xuan Dong,Xicheng Wang,Takatoshi Seto,Yuhua Wang

As a representative of III–V semiconductor materials, InP/ZnS quantum dots are regarded as the star material in the field of light-emitting devices due to their low toxicity and suitable luminescence range. However, there are still some major problems in the preparation process of InP/ZnS QDs, such as phosphine precursors are expensive and difficult to preserve, the nucleation time of short wavelength InP/ZnS QDs is too short and the size distribution is too large. In this paper, we'll replace the traditional tris(trimethylsilyl)phosphine with tris(diethylamino)phosphine as a cheaper phosphine precursor and propose a novel and convenient method for adjusting the luminescence wavelength of InP/ZnS QDs. Different from the traditional method to adjust the emission wavelength by changing the nucleation time, the emission wavelength of InP/ZnS QDs was regulated by changing the number of initially formed cores. Zeolites provide a nucleation site for the InP cores. InP/ZnS QDs that emit between 522 nm and 589 nm were obtained. Moreover, the obtained InP/ZnS QDs have good monochromaticity, and the minimum half-width (half-full width) is up to 48 nm. This method provides a new way to adjust the size of quantum dots with good performance.

CAS / MDL: 557-05-1
研究领域: 材料科学 · 化学工程
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Bioresources and Bioprocessing · 2022 ·Vol. 9 ·期 1 ·1-14 · IF 4.983

Light-driven progesterone production by InP–(M. neoaurum) biohybrid system

Liu Kun,Wang Feng-Qing,Liu Ke,Zhao Yunqiu,Gao Bei,Tao Xinyi,Wei Dongzhi

Progesterone is one of the classical hormone drugs used in medicine for maintaining pregnancy. However, its manufacturing process, coupled with organic reagents and poisonous catalysts, causes irreversible environmental pollution. Recent advances in synthetic biology have demonstrated that the microbial biosynthesis of natural products, especially difficult-to-synthesize compounds, from building blocks is a promising strategy. Herein, overcoming the heterologous cytochrome P450 enzyme interdependency in Mycolicibacterium neoaurum successfully constructed the CYP11A1 running module to realize metabolic conversion from waste phytosterols to progesterone. Subsequently, progesterone yield was improved through strategies involving electron transfer and NADPH regeneration. Mutant CYP11A1 (mCYP11A1) and adrenodoxin reductase (ADR) were connected by a flexible linker (L) to form the chimera mCYP11A1-L-ADR to enhance electron transfer. The chimera mCYP11A1-L-ADR, adrenodoxin (ADX), and ADR-related homolog ARH1 were expressed in M. neoaurum, showed positive activity and produced 45 mg/L progesterone. This electron transfer strategy increased progesterone production by 3.95-fold compared with M. neoaurum expressing mCYP11A1, ADR, and ADX. Significantly, a novel inorganic–biological hybrid system was assembled by combining engineered M. neoaurum and InP nanoparticles to regenerate NADPH, which was increased 84-fold from the initial progesterone titer to 235 ± 50 mg/L. In summary, this work highlights the green and sustainable potential of obtaining synthetic progesterone from sterols in M. neoaurum.

CAS / MDL: 22398-80-7
研究领域: 合成生物学 · 生物技术 · 环境科学 · 药学 · 微生物学
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