Ni Zhao

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Organization: The Chinese University of Hong Kong
Department: Department of Electronic Engineering
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Co-reporter:Yu Zhang, Jun Li, Rui Li, Dan-Tiberiu Sbircea, Alexander Giovannitti, Junling Xu, Huihua Xu, Guodong Zhou, Liming Bian, Iain McCulloch, and Ni Zhao
ACS Applied Materials & Interfaces November 8, 2017 Volume 9(Issue 44) pp:38687-38687
Publication Date(Web):October 17, 2017
DOI:10.1021/acsami.7b09384
Liquid electrolyte-gated organic field effect transistors and organic electrochemical transistors have recently emerged as powerful technology platforms for sensing and simulation of living cells and organisms. For such applications, the transistors are operated at a gate voltage around or below 0.3 V because prolonged application of a higher voltage bias can lead to membrane rupturing and cell death. This constraint often prevents the operation of the transistors at their maximum transconductance or most sensitive regime. Here, we exploit a solid–liquid dual-gate organic transistor structure, where the threshold voltage of the liquid-gated conduction channel is controlled by an additional gate that is separated from the channel by a metal-oxide gate dielectric. With this design, the threshold voltage of the “sensing channel” can be linearly tuned in a voltage window exceeding 0.4 V. We have demonstrated that the dual-gate structure enables a much better sensor response to the detachment of human mesenchymal stem cells. In general, the capability of tuning the optimal sensing bias will not only improve the device performance but also broaden the material selection for cell-based organic bioelectronics.Keywords: cell sensing; dual-gate; electrolyte-gated organic field effect transistor; organic electrochemical transistor; threshold voltage tuning;
Co-reporter:Mengyu Chen, Haipeng Lu, Nema M. Abdelazim, Ye Zhu, Zhen Wang, Wei Ren, Stephen V. Kershaw, Andrey L. Rogach, and Ni Zhao
ACS Nano June 27, 2017 Volume 11(Issue 6) pp:5614-5614
Publication Date(Web):May 19, 2017
DOI:10.1021/acsnano.7b00972
Near-to-mid-infrared photodetection technologies could be widely deployed to advance the infrastructures of surveillance, environmental monitoring, and manufacturing, if the detection devices are low-cost, in compact format, and with high performance. For such application requirements, colloidal quantum dot (QD) based photodetectors stand out as particularly promising due to the solution processability and ease of integration with silicon technologies; unfortunately, the detectivity of the QD photodetectors toward longer wavelengths has so far been low. Here we overcome this performance bottleneck through synergistic efforts between synthetic chemistry and device engineering. First, we developed a fully automated aprotic solvent, gas-injection synthesis method that allows scalable fabrication of large sized HgTe QDs with high quality, exhibiting a record high photoluminescence quantum yield of 17% at the photoluminescence peak close to 2.1 μm. Second, through gating a phototransistor structure we demonstrate room-temperature device response to reach >2 × 1010 cm Hz1/2 W–1 (at 2 kHz modulation frequency) specific detectivity beyond the 2 μm wavelength range, which is comparable to commercial epitaxial-grown photodetectors. To demonstrate the practical application of the QD phototransistor, we incorporated the device in a carbon monoxide gas sensing system and demonstrated reliable measurement of gas concentration. This work represents an important step forward in commercializing QD-based infrared detection technologies.Keywords: gas sensing; near-to-mid infrared; photodetection; phototransistor; quantum dot;
Co-reporter:Huihua Xu;Jing Liu;Jie Zhang;Guodong Zhou;Ningqi Luo
Advanced Materials 2017 Volume 29(Issue 31) pp:
Publication Date(Web):2017/08/01
DOI:10.1002/adma.201700975
Wearable photoplethysmogram (PPG) sensors offer convenient and informative measurements for evaluating daily physiological states of individuals. In this work, epidermal and flexible near-infrared (NIR) PPG sensors integrating a low-power, high-sensitivity organic phototransistor (OPT) with a high-efficiency inorganic light-emitting diode are developed. By exploiting an organic bulk heterojunction active layer and a bilayer gate dielectric design, a low voltage (<3 V) operated OPT with NIR responsivity as high as 3.5 × 105 A W−1 and noise equivalent power of 1.2 × 10−15 W Hz−1/2 is achieved, greatly surpassing commercial available silicon-based photodetectors. In addition, the ultrathin encapsulation structure renders the device highly flexible and allows transfer printing of the device directly onto human skin. It is demonstrated that the epidermal/flexible PPG sensors are capable of continuously monitoring heart rate variability and precisely tracking the changes of pulse pressure at different postures of human subjects with the aid of electrocardiogram monitoring, exhibiting more reliable performance than commercial PPG sensors while consuming less power. The study suggests that the hybrid PPG sensor design may provide a promising solution for low-power, real-time physiological monitoring.
Co-reporter:Jie Cao;Hui Yu;Shuang Zhou;Minchao Qin;Tsz-Ki Lau;Xinhui Lu;Ching-Ping Wong
Journal of Materials Chemistry A 2017 vol. 5(Issue 22) pp:11071-11077
Publication Date(Web):2017/06/06
DOI:10.1039/C7TA02228J
The use of organic hole transporting layers (HTLs) in organolead halide perovskite solar cells (PSCs) often limits the air and thermal stability of the devices. In this work, we developed a low-temperature solution process that enables the fabrication of nickel oxide (NiOx) based HTLs on top of perovskite active layers. The NiOx film exhibits a uniform and dense morphology, rendering the PSCs air-stable and thermally stable. We further found that by introducing an interfacial layer (e.g. CuSCN) between the NiOx film and the top metal electrode, the power conversion efficiency (PCE) of the PSCs can be largely improved from 10.4% to 17.2%, while the air stability continues to be excellent. The role of the interfacial layer was investigated through impedance analysis and ultraviolet photoelectron spectroscopy. Remarkably, the PSCs with the NiOx/CuSCN hybrid inorganic HTL exhibit no degradation in their PCE after being exposed to ambient air (humidity level: 50–60%) for 4 months without encapsulation.
Co-reporter:Hong-Hua Fang;Feng Wang;Sampson Adjokatse;Maria Antonietta Loi
Advanced Functional Materials 2016 Volume 26( Issue 26) pp:4653-4659
Publication Date(Web):
DOI:10.1002/adfm.201600715

Formamidinium lead iodide (FAPbI3) has a broader absorption spectrum and better thermal stability than the most famous methylammonium lead iodide, thus exhibiting great potential for photovoltaic applications. In this report, the light-induced photoluminescence (PL) evolution in FAPbI3 thin films is investigated. The PL intensity evolution is found to be strongly dependent on the atmosphere surrounding the samples. When the film is exposed to air, its photoluminescence intensity is enhanced more than 140 times after continuous ultraviolet laser illumination for 2 h, and the average lifetime is prolonged from 17 to 389 ns. The enhanced photoluminescence implies that the trap density is significantly reduced. The comparative study of the photoluminescence properties in air, nitrogen, and oxygen/helium environment suggests that moisture is important for the PL enhancement. This is explained in terms of moisture-assisted light-healing effect in FAPbI3 thin films. With this study, a new method is demonstrated to increase and control the quality of hybrid perovskite thin films.

Co-reporter:Ningqi Luo;Wenxuan Dai;Chenglin Li;Zhiqiang Zhou;Liyuan Lu;Carmen C. Y. Poon;Shih-Chi Chen;Yuanting Zhang
Advanced Functional Materials 2016 Volume 26( Issue 8) pp:1178-1187
Publication Date(Web):
DOI:10.1002/adfm.201504560

Noninvasive and real-time cuffless blood pressure (BP) measurement realizes the idea of unobtrusive and continuous BP monitoring which is essential for diagnosis and prevention of cardiovascular diseases associated with hypertension. In this paper, a wearable sensor patch system that integrates flexible piezoresistive sensor (FPS) and epidermal electrocardiogram (ECG) sensors for cuffless BP measurement is presented. By developing parametric models on the FPS sensing mechanism and optimizing operational conditions, a highly stable epidermal pulse monitoring method is established and beat-to-beat BP measurement from the ECG and epidermal pulse signals is demonstrated. In particular, this study highlights the compromise between sensor sensitivity and signal stability. As compared with the current optical-based cuffless BP measurement devices, the sensing patch requires much lower power consumption (3 nW) and is capable of detecting subtle physiological signal variations, e.g., pre and postexercises, thus providing a promising solution for low-power, real-time, and home-based BP monitoring.

Co-reporter:Hui Yu;Haipeng Lu;Fangyan Xie;Shuang Zhou
Advanced Functional Materials 2016 Volume 26( Issue 9) pp:1411-1419
Publication Date(Web):
DOI:10.1002/adfm.201504997

Despite the high power conversion efficiency and ease of fabrication, planar-junction organolead halide perovskite solar cells often exhibit anomalous hysteretic current–voltage (I–V) characteristics. In this work, the origin of the I–V hysteresis is studied by fine-tuning the precursor ratio of methylammonium lead iodide and thus varying the native defects in the material. It is shown that the perovskites synthesized from “PbI2 excess,” “methylammonium iodide excess,” and “stoichiometric” precursors exhibit identical film morphology but different I–V hysteresis in a planar solar cell configuration. Through a comparative analysis on the temperature-dependent continuous and stepwise-stabilized I–V responses of the three devices, a model involving transport and trapping of the ionic native defects is proposed. The active energy of the transport process is estimated to be between 0.10 and 0.18 eV, most likely associated with the vacancy-mediated iodide ion migration. The lower activation energy of the “PbI2 excess” and “Stoichiometric” samples indicates that the presence of methylammonium vacancies may provide a favorable pathway for the migration of iodide ions due to reduced steric hindrance. Furthermore, the slow trapping and release processes of iodide ions at the TiO2/perovskite interface are accounted for the long time scale current decay (or raise) following a voltage change.

Co-reporter:Feng Wang;Jiale Ma;Fangyan Xie;Linkai Li;Jian Chen;Jun Fan
Advanced Functional Materials 2016 Volume 26( Issue 20) pp:3417-3423
Publication Date(Web):
DOI:10.1002/adfm.201505127

The applications of organotin halide perovskites are limited because of their chemical instability under ambient conditions. Upon air exposure, Sn2+ can be rapidly oxidized to Sn4+, causing a large variation in the electronic properties. Here, the role of organic cations in degradation is investigated by comparing methylammonium tin iodide (MASnI3) and formamidinium tin iodide (FASnI3). Through chemical analyses and theoretical calculations, it is found that the organic cation strongly influences the oxidation of Sn2+ and the binding of H2O molecules to the perovskite lattice. On the one hand, Sn2+ can be easily oxidized to Sn4+ in MASnI3, and replacing MA with FA reduces the extent of Sn oxidation; on the other hand, FA forms a stronger hydrogen bond with H2O than does MA, leading to partial expansion of the perovskite network. The two processes compete in determining the material's conductivity. It is noted that the oxidation is a difficult process to prevent, while the water effect can be largely suppressed by reducing the moisture level. As a result, FASnI3-based conductors and photovoltaic cells exhibit much better reproducibility as compared to MASnI3-based devices. This study sheds light on the development of stable Pb-free perovskite optoelectronic devices through new material design.

Co-reporter:Jie Cao, Feng Wang, Hui Yu, Yang Zhou, Haipeng Lu, Ni Zhao and Ching-Ping Wong  
Journal of Materials Chemistry A 2016 vol. 4(Issue 26) pp:10223-10230
Publication Date(Web):01 Jun 2016
DOI:10.1039/C6TA03121H
Two-step sequential deposition has been widely used for the fabrication of organolead halide perovskites due to its efficient pore-filling in mesostructured perovskite solar cells (PSCs) and great controllability of the perovskite film morphology. However, due to the limited diffusivity of the organic salt, it is often difficult to fully convert a >150 nm compact PbI2 precursor film to perovskite during a sequential deposition process. Consequently, the uncontrollable amount of remnant PbI2 may not only affect the device reproducibility but also harm the air stability of the perovskite films. In this work, we developed a new method to synthesize PbI2 thin films with nano-pores and tunable crystal sizes. We found that the porous structure and small crystal size of the synthesized PbI2 can facilitate its conversion to CH3NH3PbI3 perovskite, resulting in a PbI2-free and highly oriented perovskite film. PSCs based on such perovskite films exhibit superior power conversion efficiencies as compared to the ones synthesized from compact PbI2 films; more importantly, the stability of the perovskite films and PSCs has been greatly improved.
Co-reporter:Linkai Li
The Journal of Physical Chemistry C 2016 Volume 120(Issue 5) pp:2536-2541
Publication Date(Web):January 12, 2016
DOI:10.1021/acs.jpcc.5b11627
Organometal halide perovskite solar cells exhibit a strong polarization effect under light illumination. This unique property, although widely observed, has not been well understood. In this work, we carried out a systematic investigation on this phenomenon by varying the perovskite composition and device configurations. We find that the light-enhanced strong polarization is a general phenomenon that occurs in all tested perovskite materials. The organic molecular dipoles affect the polarization at high frequency range, while the photoexcited free carriers and the interface between perovskite and its neighboring layers dominate the low-frequency response. In particular, our study suggests that the giant low-frequency capacitance enhancement originates from native defects and their accompanying defect dipoles, which need to be activated by photogenerated charge carriers. The high flexibility of the perovskite lattice facilitates the formation of these defects, and the dipole effect is enhanced at the interface regions where an electric double-layer capacitor is formed. This work sheds light on the understanding of the light-induced polarization mechanisms of perovskite materials.
Co-reporter:Shuang Zhou;Linkai Li;Hui Yu;Jizhang Chen;Ching-Ping Wong
Advanced Electronic Materials 2016 Volume 2( Issue 7) pp:
Publication Date(Web):
DOI:10.1002/aelm.201600114

Organometal halide perovskites exhibit not only extraordinary electronic properties but also interesting ionic responses due to the ease of forming and moving native defects in the perovskite lattice. In this work such dual (electronic and ionic) conduction property is exploited to fabricate a thin film electrochemical capacitor (EC) based on organolead triiodide perovskite. The EC cells show excellent cyclability with stable capacitance output beyond 10 000 cycles. By performing electrochemical characterizations on the cells with different electrolytes and perovskite thickness, it is found that the perovskite layer serves not only as an electrode but also a solid electrolyte. Through circuit modeling of the electrochemical impedance spectra, the density of mobile ions (i.e., ionic native defects) in the perovskite films is extracted and is found to be lower than those estimated from perovskite electronic devices, e.g., solar cells. The result suggests that the ion formation and transport processes in organometal halide perovskites may largely be activated by the current of free charge carriers as well as specific interface defects.

Co-reporter:Jizhang Chen, Junling Xu, Shuang Zhou, Ni Zhao, Ching-Ping Wong
Nano Energy 2016 Volume 21() pp:145-153
Publication Date(Web):March 2016
DOI:10.1016/j.nanoen.2015.12.029
•Amorphous nanostructured fishscale-like FeOOH is deposited on the Ni foam.•Amorphous flower-like Co–Ni double hydroxides are grown on the Ni foam.•The fabrication process is facile, scalable, and cost-effective.•The FeOOH and Co–Ni double hydroxides show great pseudocapacitive performances.•The asymmetric supercapacitor delivers high energy and power densities.Amorphous fish-scale-like FeOOH and flower-like Co–Ni double hydroxides (Co–Ni-DH) have been synthesized through one-step electrodeposition. The unique nanostructures of the hydroxides provide a large number of surface active sites, while the amorphous nature of the material systems facilitates the diffusion and reaction of electrolyte ions and enables an isotropic charging/discharging process. Because of these advantages, the FeOOH and Co–Ni-DH electrodes exhibit high pseudocapacitances of 1.11 F cm−2/867 F g−1 and 1.48 F cm−2/1201 F g−1, respectively. In addition, high rate capabilities and superior cyclabilities are achieved. By using the FeOOH and Co–Ni-DH as the anode and cathode, respectively, we have assembled an aqueous asymmetric supercapacitor that delivers a high energy density of 86.4 W h kg−1/0.723 mW h cm−3 and a high power density of 11.6 kW kg−1/0.973 mW cm−3. Moreover, the fabrication process presented in this work is facile, scalable, cost-effective, and environmentally benign, offering a feasible solution for manufacturing next-generation high-performance energy storage devices.
Co-reporter:Jizhang Chen, Junling Xu, Shuang Zhou, Ni Zhao, Ching-Ping Wong
Nano Energy 2016 Volume 25() pp:193-202
Publication Date(Web):July 2016
DOI:10.1016/j.nanoen.2016.04.037
•Free-standing nitrogen-doped hierarchically porous carbon foam is fabricated.•The fabrication route is facile, scalable, and cost-effective.•The obtained carbon foam exhibits high gravimetric and volumetric capacitances.•Great performance is achieved after in-situ growing NiCo2S4 onto the carbon foam.•The asymmetric supercapacitor delivers high energy and power densities.Free-standing 3D carbonaceous materials offer many advantages and therefore hold great potential for a wide range of applications. However, the synthesis of these materials often involves complicated processes that may lead to low yields and high costs. In this study, this issue is addressed through developing a facile, scalable, and cost-effective synthesis strategy. Nitrogen-doped hierarchically porous carbon foam (HP-CF) is fabricated by annealing of soft-template-casted melamine foam, and its application for supercapacitors is highlighted. The HP-CF integrates a large number of macropores and micropores, thus providing sufficient space for ion transport while offering a large amount of surface sites for energy storage, thanks to which the HP-CF exhibits a high capacitance of 238 F g–1 (or 11.9 F cm–3). In addition, the HP-CF performs greatly when acting as the mechanical support for pseudocapacitive materials such as NiCo2S4 and Fe2O3, based on which an asymmetric supercapacitor (ASC, can also be described as aqueous battery) is assembled. The ASC exhibits a high energy density of 93.9 Wh kg–1 (or 3.55 mWh cm–3) and a high power density of 21.1 kW kg–1 (or 799 mW cm–3), among the highest reported values for ASCs.
Co-reporter:Hong-Hua Fang, Feng Wang, Sampson Adjokatse, Ni Zhao, Jacky Even and Maria Antonietta Loi
Light: Science & Applications 2016 5(4) pp:e16056
Publication Date(Web):2015-12-25
DOI:10.1038/lsa.2016.56
Formamidinium lead iodide (FAPbI3) is a newly developed hybrid perovskite that potentially can be used in high-efficiency solution-processed solar cells. Here, the temperature-dependent dynamic optical properties of three types of FAPbI3 perovskite films (fabricated using three different precursor systems) are comparatively studied. The time-resolved photoluminescence (PL) spectra reveal that FAPbI3 films made from the new precursor (a mixture of formamidinium iodide and hydrogen lead triiodide) exhibit the longest lifetime of 439 ns at room temperature, suggesting a lower number of defects and lower non-radiative recombination losses compared with FAPbI3 obtained from the other two precursors. From the temperature-dependent PL spectra, a phase transition in the films is clearly observed. Meanwhile, exciton-binding energies of 8.1 and 18 meV for the high- and low-temperature phases are extracted, respectively. Importantly, the PL spectra for all of the samples show a single peak at room temperature, whereas at liquid-helium temperature the emission features two peaks: one in higher energy displaying a fast decay (0.5 ns) and a second red-shifted peak with a decay of up to several microseconds. These two emissions, separated by ~18 meV, are attributed to free excitons and bound excitons with singlet and triplet characters, respectively.
Co-reporter:Feng Wang;Hui Yu;Haihua Xu
Advanced Functional Materials 2015 Volume 25( Issue 7) pp:1120-1126
Publication Date(Web):
DOI:10.1002/adfm.201404007

Recently, there have been extensive research efforts on developing high performance organolead halide based perovskite solar cells. While most studies focused on optimizing the deposition processes of the perovskite films, the selection of the precursors has been rather limited to the lead halide/methylammonium (or formamidium) halide combination. In this work, we developed a new precursor, HPbI3, to replace lead halide. The new precursor enables formation of highly uniform formamidium lead iodide (FAPbI3) films through a one-step spin-coating process. Furthermore, the FAPbI3 perovskite films exhibit a highly crystalline phase with strong (110) preferred orientation and excellent thermal stability. The planar heterojunction solar cells based on these perovskite films exhibit an average efficiency of 15.4% and champion efficiency of 17.5% under AM 1.5 G illumination. By comparing the morphology and formation process of the perovskite films fabricated from the formamidium iodide (FAI)/HPbI3, FAI/PbI2, and FAI/PbI2 with HI additive precursor combinations, it is shown that the superior property of the HPbI3 based perovskite films may originate from 1) a slow crystallization process involving exchange of H+ and FA+ ions in the PbI6 octahedral framework and 2) elimination of water in the precursor solution state.

Co-reporter:Jizhang Chen, Junling Xu, Shuang Zhou, Ni Zhao and Ching-Ping Wong  
Journal of Materials Chemistry A 2015 vol. 3(Issue 33) pp:17385-17391
Publication Date(Web):17 Jul 2015
DOI:10.1039/C5TA04164C
A facile and scalable one-step anodization method has been developed to fabricate three-dimensional (3-D) Cu(OH)2 nanoporous nanorods on a copper foil substrate, a product that can be used directly as a binder-free electrode for supercapacitors. The unique morphology of the nanorods provides a large amount of active sites for redox reactions, which can be easily accessed by electrolyte ions. Benefiting from that, a high capacitance of 213 mF cm−2 is obtained, and superior rate capability (62.3% capacitance retention when the scan rate is increased to 10 times) and excellent cyclability (92.0% capacitance retention after 5000 cycles) are achieved. In addition, a flexible and foldable solid-state asymmetric supercapacitor is assembled using the Cu(OH)2 and activated carbon as the positive and negative electrodes, respectively. The devices deliver a high energy density of 3.68 mW h cm−3 and a high power density of 5314 mW cm−3, demonstrating great potential for next-generation high-rate energy storage systems.
Co-reporter:Yang Bai, Hui Yu, Zonglong Zhu, Kui Jiang, Teng Zhang, Ni Zhao, Shihe Yang and He Yan  
Journal of Materials Chemistry A 2015 vol. 3(Issue 17) pp:9098-9102
Publication Date(Web):23 Dec 2014
DOI:10.1039/C4TA05309E
Hybrid organic/inorganic perovskite solar cells are among the most competitive emerging photovoltaic technologies. Here, we report on NiO-based inverted structure perovskite solar cells with a high power conversion efficiency of 10.68%, which is achieved by adding a small percentage (1.5 wt%) of high molecular weight polystyrene (PS) into the PCBM electron transport layer (ETL). The addition of PS facilitates the formation of a highly smooth and uniform PCBM ETL that is more effective in preventing undesirable electron–hole recombination between the perovskite layer and the top electrode. As a result, the VOC of the PCBM:PS-based cells is increased from 0.97 V to 1.07 V, which leads to significantly enhanced power conversion efficiencies of the solar cells. Our study provides a simple and low-cost approach to improving the ETL film quality and the performance of inverted perovskite solar cells.
Co-reporter:Haihua Xu
The Journal of Physical Chemistry C 2015 Volume 119(Issue 45) pp:25598-25605
Publication Date(Web):October 26, 2015
DOI:10.1021/acs.jpcc.5b07810
The polymer/fullerene interface (PFI) in polymer solar cells (PSCs) provides an energetic offset for exciton dissociation while at the same time influencing local transport of photocarriers adjacent to the interface. In this paper, we introduce a heterojunction field-effect transistor (FET) structure in charge modulation spectroscopy (CMS) to enable in situ probing of the charge transport process at PFIs. The PFIs formed by fullerene/crystalline polymer and fullerene/amorphous polymer systems are studied and compared, respectively. By correlating the steady-state and frequency-dependent CMS responses of pure polymer, polymer/fullerene bilayer, and polymer/fullerene blend FETs, we demonstrate that through different charge localization effects the interface fullerene molecules can influence the hole transport in both crystalline and amorphous polymer phases. We propose a trade-off between charge transfer and charge transport at PFIs with an aim to enhance the engineering of molecular orientation and packing at the donor–acceptor interface for high-performance PSCs.
Co-reporter:Shuang Zhou, Junling Xu, Yubin Xiao, Ni Zhao, Ching-Ping Wong
Nano Energy 2015 Volume 13() pp:458-466
Publication Date(Web):April 2015
DOI:10.1016/j.nanoen.2015.03.010
•Curved graphene is produced with metal particle-assisted low-temperature (650 °C) APCVD method.•Growth mechanism is studied and correlated with previous theoretical models.•Curved graphene electrodes show excellent electrochemical properties and render supercapacitors high performance.Atmospheric pressure chemical vapor deposition (APCVD) using gas phase carbon sources, e.g. methane, has been shown to yield high-quality graphene with excellent reproducibility. So far high temperatures, typically between 900 and 1000 °C, are widely adopted for such deposition process. In this work, we demonstrated that the deposition temperature can be reduced to 650 °C when using micron-sized Ni particles as the template/catalyst to produce curved graphene. The effects of growth temperature and particle size were systematically studied and correlated with previous theoretical models on graphene growth. The results suggest that the low temperature growth is enabled by the large amount of atomic step edges present at the Ni particle surface, which facilitate methane decomposition, graphene formation and defect healing. The curved graphene was used as an electrode material and demonstrated a specific capacitance of 203.4 F g−1 in KOH electrolyte. Two-electrode supercapacitor constructed with the curved graphene also showed outstanding electrochemical properties, such as high energy density (40.9 Wh kg−1) and power density (70 kW kg−1), as well as long-term stability.
Co-reporter:Xiaojing Wu
The Journal of Physical Chemistry C 2015 Volume 119(Issue 2) pp:1253-1259
Publication Date(Web):November 24, 2014
DOI:10.1021/jp511314a
In this work we investigate the compositional dependence of electric dipole moment in AMX3 (A: organic; M: metal; X: halogen) perovskite structures using modulation electroabsorption (EA) spectroscopy. By sampling various device structures, we show that the second harmonic EA spectra reflect the intrinsic dipolar property of perovskite films in a layered configuration. A quantitative analysis of the EA spectra of CH3NH3PbI3, NH2CHNH2PbI3, and CH3NH3Sn0.4Pb0.6I3 is provided to compare the impact of the organic and metal cations on the photoinduced response of dipole moment. Based on the EA results, we propose that the A and M cations could both largely affect the dielectric and dipolar properties of the perovskite materials, but through different mechanisms, such as ionic polarization, rotation of molecular dipoles and charge migration. These processes occur at different time scales and thus result in a frequency-dependent dipole response.
Co-reporter:Jizhang Chen, Junling Xu, Shuang Zhou, Ni Zhao, Ching-Ping Wong
Nano Energy 2015 Volume 15() pp:719-728
Publication Date(Web):July 2015
DOI:10.1016/j.nanoen.2015.05.021
•Graphene and porous Fe2O3 nanocomposite is fabricated by a nanocasting process.•This nanocomposite shows excellent pseudocapacitive performances.•The asymmetric pseudocapacitor delivers high energy and power densities.Composition design and morphology control can lead to high performance electrode materials for energy storage devices. In this work a graphene/porous Fe2O3 nanocomposite anode material is fabricated via a template-assisted nanocasting process. This nanocomposite consists of graphene scaffold with high electronic conductivity and interconnected Fe2O3 with porous structure, thus exposing ample active sites for redox reactions and offering sufficient contacts with the electrolyte. Owing to these morphological advantages, the nanocomposite outperforms nearly all the reported Fe-based anode materials by delivering a high specific capacitance of 1095 F g−1 at a current density of 3 A g−1. In addition, the material shows great rate capability and good cycling stability. Asymmetric supercapacitors are fabricated by assembling the graphene/porous Fe2O3 nanocomposite (as the anode material) with a CoNi-layered double hydroxide/carbon nanotube composite (as the cathode material). The devices exhibit high energy and power densities of 98.0 W h kg−1 and 22,826 W kg−1, which are among the best performances reported to date for asymmetric supercapacitors.
Co-reporter:Hui Yu;Feng Wang;Fangyan Xie;Wenwu Li;Jian Chen
Advanced Functional Materials 2014 Volume 24( Issue 45) pp:7102-7108
Publication Date(Web):
DOI:10.1002/adfm.201401872

CH3NH3PbI3-xClx is a commonly used chemical formula to represent the methylammonium lead halide perovskite fabricated from mixed chlorine- and iodine-containing salt precursors. Despite the rapid progress in improving its photovoltaic efficiency, fundamental questions remain regarding the atomic ratio of Cl in the perovskite as well as the reaction mechanism that leads to its formation and crystallization. In this work we investigated these questions through a combination of chemical, morphological, structural and thermal characterizations. The elemental analyses reveal unambiguously the negligible amount of Cl atoms in the CH3NH3PbI3-xClx perovskite. By studying the thermal characteristics of methylammonium halides as well as the annealing process in a polymer/perovskite/FTO glass structure, we show that the formation of the CH3NH3PbI3-xClx perovskite is likely driven by release of gaseous CH3NH3Cl (or other organic chlorides) through an intermediate organometal mixed halide phase. Furthermore, the comparative study on CH3NH3I/PbCl2 and CH3NH3I/PbI2 precursor combinations with different molar ratios suggest that the initial introduction of a CH3NH3+ rich environment is critical to slow down the perovskite formation process and thus improve the growth of the crystal domains during annealing; accordingly, the function of Cl is to facilitate the release of excess CH3NH3+ at a relatively low annealing temperatures.

Co-reporter:Mengyu Chen;Hui Yu;Stephen V. Kershaw;Haihua Xu;Shuchi Gupta;Frederik Hetsch;Andrey L. Rogach
Advanced Functional Materials 2014 Volume 24( Issue 1) pp:53-59
Publication Date(Web):
DOI:10.1002/adfm.201301006

The ability to detect near-infrared and mid-infrared radiation has spawned great interest in colloidal HgTe quantum dots (QDs). In contrast to the studies focused on extending the spectral range of HgTe QD devices, the temporal response, another figure of merit for photodetectors, is rarely investigated. In this work, a single layer, aqueous HgTe QD based photoconductor structure with very fast temporal response (up to 1 MHz 3 dB bandwidth) is demonstrated. The device is fabricated using a simple spray-coating process and shows excellent stability in ambient conditions. The origin of the remarkably fast time response is investigated by combining light intensity-dependent transient photocurrent, temperature-dependent photocurrent, and field-effect transistor (FET) measurements. The charge carrier mobility, as well as the energy levels and carrier lifetimes associated with the trap states in the QDs, are identified. The results suggest that the temporal response is dominated by a fast bimolecular recombination process under high light intensity and by a trap-mediated recombination process at low light intensity. Interestingly, it was found that the gain and time response of aqueous HgTe QD-based photoconductors can be tuned by controlling the QD size and surface chemistry, which provides a versatile approach to optimize the photodetectors with selectable sensitivity and operation bandwidth.

Co-reporter:Mengyu Chen, Lei Shao, Stephen V. Kershaw, Hui Yu, Jianfang Wang, Andrey L. Rogach, and Ni Zhao
ACS Nano 2014 Volume 8(Issue 8) pp:8208
Publication Date(Web):July 14, 2014
DOI:10.1021/nn502510u
The near-field effects of noble metal nanoparticles can be utilized to enhance the performance of inorganic/organic photosensing devices, such as solar cells and photodetectors. In this work, we developed a well-controlled fabrication strategy to incorporate Au nanostructures into HgTe quantum dot (QD)/ZnO heterojunction photodiode photodetectors. Through an electrostatic immobilization and dry transfer protocol, a layer of Au nanorods with uniform distribution and controllable density is embedded at different depths in the ZnO layer for systematic comparison. More than 80 and 240% increments of average short-circuit current density (Jsc) are observed in the devices with Au nanorods covered by ∼7.5 and ∼4.5 nm ZnO layers, respectively. A periodic finite-difference time-domain (FDTD) simulation model is developed to analyze the depth-dependent property and confirm the mechanism of plasmon-enhanced light absorption in the QD layer. The wavelength-dependent external quantum efficiency spectra suggest that the exciton dissociation and charge extraction efficiencies are also enhanced by the Au nanorods, likely due to local electric field effects. The photodetection performance of the photodiodes is characterized, and the results show that the plasmonic structure improves the overall infrared detectivity of the HgTe QD photodetectors without affecting their temporal response. Our fabrication strategy and theoretical and experimental findings provide useful insight into the applications of metal nanostructures to enhance the performance of organic/inorganic hybrid optoelectronic devices.Keywords: exciton; heterojunction; quantum dot; surface plasmon
Co-reporter:Lei Ye ; Hai-Hua Xu ; Hui Yu ; Wang-Ying Xu ; Hao Li ; Han Wang ; Ni Zhao ;Jian-Bin Xu
The Journal of Physical Chemistry C 2014 Volume 118(Issue 35) pp:20094-20099
Publication Date(Web):August 13, 2014
DOI:10.1021/jp504365y
To explore the potential of ternary blend bulk heterojunction (BHJ) solar cells as a general platform for improving the performance of organic photovoltaics, we studied a ternary BHJ system based on poly(3-hexylthiophene) (P3HT), [6,6]-phenyl C61 butyric acid methyl ester (PC61BM), and DTDCTB. The optimized ternary structure containing a weight ratio of 20% DTDCTB as the cascade material demonstrates a ∼25% improvement of the power conversion efficiency (PCE) as compared to the binary P3HT/PC61BM solar cells. A systematic spectroscopic study is carried out to elucidate the underlying mechanism of charge transfer in the ternary system. Wavelength-dependent external quantum efficiency measurement confirms the contribution of DTDCTB to the enhanced photocurrent. Photoinduced absorption spectroscopy and transient photovoltage measurement reveal unambiguously that charges generated in DTDCTB are efficiently transferred to and subsequently transported in P3HT and PC61BM. The results also suggest that despite the realization of cascade charge transfer, the bimolecular charge recombination process in the ternary system is still dominated by the P3HT/PC61BM interface.
Co-reporter:Haihua Xu ; Jun Li ; Jiangquan Mai ; Ting Xiao ; Xinhui Lu
The Journal of Physical Chemistry C 2014 Volume 118(Issue 10) pp:5600-5605
Publication Date(Web):February 12, 2014
DOI:10.1021/jp5013126
The intramolecular arrangement of the donor (D) and acceptor (A) moieties can greatly influence the electronic properties of D–A conjugated copolymers. Here, we report a comparative study on a class of copolymers with either alternatively or randomly arranged D and A moieties. Through combination of the grazing incidence X-ray scattering, charge modulation spectroscopy and temperature-dependent field-effect mobility measurement, we provide direct evidence that the alternating D–A arrangement generates a relatively high degree of crystallinity, resulting in predominant two-dimensional delocalization of polaronic charge carriers, low energetic disorder, and thus good charge-transport property. On the other hand, the randomly arranged D–A structure, although providing broad-band absorption, gives rise to short-range ordered aggregates surrounded by amorphous region. Accordingly, a transition from a delocalized to a localized polaronic regime is observed as the charge carrier concentration increases, and disorder broadening of density of states is also revealed.
Co-reporter:Haihua Xu, Jun Li, Billy H. K. Leung, Carmen C. Y. Poon, Beng S. Ong, Yuanting Zhang and Ni Zhao  
Nanoscale 2013 vol. 5(Issue 23) pp:11850-11855
Publication Date(Web):24 Sep 2013
DOI:10.1039/C3NR03989G
High-gain photodetectors with near-infrared (NIR) sensitivity are critical for biomedical applications such as photoplethysmography and optical coherence tomography where detected optical signals are relatively weak. Current photodetection technologies rely on avalanche photodiodes and photomultipliers to achieve high sensitivity. These devices, however, require a high operation voltage and are not compatible with CMOS based read-out circuits (ROCs). In this work we demonstrate a solution-proceeded NIR phototransistor structure based on a bulk heterojunction (BHJ) of a narrow bandgap polymer, poly(N-alkyl diketopyrrolo-pyrrole dithienylthieno[3,2-b]thiophene) (DPP-DTT), and [6,6]-phenyl-C61-butyric acid methylester (PCBM). The device exhibits ultrahigh responsivity (∼5 × 105 A W−1) as well as wide tunability (>1 × 104) of photoconductive gain. Using the current–voltage and transient photocurrent measurements we show that the high responsivity is due to the combined effects of fast transport of holes in the polymer matrix and slow detrapping of electrons from the isolated PCBM domains. The wide gain tunability and the efficient suppression of noise current are achieved through the use of the optically tunable gate terminal. We demonstrate that our phototransistor can be used as the detection unit in a photoplethysmography sensor for non-invasive, continuous finger pulse wave monitoring. The high-sensitivity of the phototransistor allows the use of a low-power light source, thus reducing the overall power consumption of the sensor. This, together with the solution processibility and the simple device configuration (which is compatible with conventional ROCs), make the phototransistor a very promising component for the next generation low-cost, mobile biomedical devices for health monitoring and remote diagnostics.
Co-reporter:Yaorong Su, Mingdong Wang, Fangyan Xie, Jian Chen, Weiguang Xie, Ni Zhao, Jianbin Xu
Organic Electronics 2013 Volume 14(Issue 3) pp:775-781
Publication Date(Web):March 2013
DOI:10.1016/j.orgel.2012.12.025
We demonstrate low-voltage pentacene thin film transistors (TFTs) using in situ modified low-cost Cu (M-Cu) as source–drain (S/D) electrodes and solution-processed high capacitance (200 nF/cm2) gate dielectrics. Under a gate voltage of −3 V, the device with M-Cu electrodes shows a much higher apparent mobility (1.0 cm2/V s), a positively shifted threshold voltage (−0.62 V), a lower contact resistance (0.11 MΩ) and a larger transconductance (12 μS) as compared to the device with conventional Au electrodes (corresponding parameters are 0.71 cm2/V s, −1.44 V, 0.41 MΩ, and 5.7 μS, respectively). The enhancement in the device performance is attributed to the optimized interface properties between S/D electrodes and pentacene. Moreover, after encapsulation the M-Cu electrodes with a thin layer of Au in the aim of suppressing unfavorable surface oxidation, the electronic characteristics of the device are further improved, and highly enhanced apparent mobility (2.3 cm2/V s) and transconductance (19 μS) can be achieved arising from the increased conductivity of the electrode itself. Our study provides a simple and feasible approach to achieve high performance low-voltage OTFTs with low-cost S/D electrodes, which is desirable for large area applications.Graphical abstractHighlights► Low-voltage pentacene OTFTs with solution-processed dielectric. ► In situ modification of low-cost Cu (M-Cu) as S/D electrodes. ► M-Cu based device show higher performance than Au and Cu. ► Mobility reaches 2.0 cm2/V s with Au encapsulated M-Cu (Au/M-Cu) electrodes. ► The mechanism of this phenomenon is studied in detail.
Co-reporter:Mingdong Wang, Shizhao Zheng, Xi Wan, Yaorong Su, Ning Ke, Ni Zhao, King Young Wong, Jianbin Xu
Solar Energy Materials and Solar Cells 2013 108() pp: 17-21
Publication Date(Web):
DOI:10.1016/j.solmat.2012.08.005
Co-reporter:Haihua Xu, Yuqian Jiang, Jun Li, Beng S. Ong, Zhigang Shuai, Jianbin Xu, and Ni Zhao
The Journal of Physical Chemistry C 2013 Volume 117(Issue 13) pp:6835-6841
Publication Date(Web):March 5, 2013
DOI:10.1021/jp4003388
Recent advances in developing donor–acceptor conjugated copolymers have led to great performance improvement in both organic photovoltaic cells and field-effect transistors. In contrast to the extensive spectroscopic studies on the photoinduced charge transfer and separation processes in these copolymers, little has been done to probe their charge-transport properties on a microscopic scale. In this work, we combine charge modulation spectroscopy (CMS), photoinduced absorption, and chemical doping spectroscopy to interrogate separately the nature of hole and electron transport in a recently developed high-mobility copolymer poly(N-alkyl diketopyrrolo-pyrrole dithienylthieno[3,2-b]thiophene) (DPP-DTT). It is found that both hole and electron polarons exhibit two-dimensional delocalization in the DPP-DTT films due to the strong intermolecular coupling. A new subgap charge induced optical transition is observed, which has not been reported before in homopolymers. The origin of this transition is studied by combing the temperature and gate voltage dependent CMS and quantum chemical calculation. The results reveal that this transition could be related to the existence of staggered dimer stacking in copolymers due to the asymmetrical volume fractions of donor and acceptor moieties.
Co-reporter:Yaorong Su, Chengliang Wang, Weiguang Xie, Fangyan Xie, Jian Chen, Ni Zhao, and Jianbin Xu
ACS Applied Materials & Interfaces 2011 Volume 3(Issue 12) pp:4662
Publication Date(Web):October 19, 2011
DOI:10.1021/am201078v
In this study, low-voltage copper phthalocyanine (CuPc)-based organic field-effect transistors (OFETs) are demonstrated utilizing solution-processed bilayer high-k metal-oxide (Al2Oy/TiOx) as gate dielectric. The high-k metal-oxide bilayer is fabricated at low temperatures (< 200 °C) by a simple spin-coating technology and can be controlled as thin as 45 nm. The bilayer system exhibits a low leakage current density of less than 10-5 A/cm2 under bias voltage of 2 V, a very smooth surface with RMS of about 0.22 nm and an equivalent k value of 13.3. The obtained low-voltage CuPc based OFETs show high electric performance with high hole mobility of 0.06 cm2/(V s), threshold voltage of −0.5 V, on/off ration of 2 × 103 and a very small subthreshold slope of 160 mV/dec when operated at −1.5 V. Our study demonstrates a simple and robust approach that could be used to achieve low-voltage operation with solution-processed technique.Keywords: Al2Oy/TiOx; CuPc; high-k; low-voltage; OFETs; solution-processed;
Co-reporter:Jie Cao, Hui Yu, Shuang Zhou, Minchao Qin, Tsz-Ki Lau, Xinhui Lu, Ni Zhao and Ching-Ping Wong
Journal of Materials Chemistry A 2017 - vol. 5(Issue 22) pp:NaN11077-11077
Publication Date(Web):2017/05/04
DOI:10.1039/C7TA02228J
The use of organic hole transporting layers (HTLs) in organolead halide perovskite solar cells (PSCs) often limits the air and thermal stability of the devices. In this work, we developed a low-temperature solution process that enables the fabrication of nickel oxide (NiOx) based HTLs on top of perovskite active layers. The NiOx film exhibits a uniform and dense morphology, rendering the PSCs air-stable and thermally stable. We further found that by introducing an interfacial layer (e.g. CuSCN) between the NiOx film and the top metal electrode, the power conversion efficiency (PCE) of the PSCs can be largely improved from 10.4% to 17.2%, while the air stability continues to be excellent. The role of the interfacial layer was investigated through impedance analysis and ultraviolet photoelectron spectroscopy. Remarkably, the PSCs with the NiOx/CuSCN hybrid inorganic HTL exhibit no degradation in their PCE after being exposed to ambient air (humidity level: 50–60%) for 4 months without encapsulation.
Co-reporter:Yang Bai, Hui Yu, Zonglong Zhu, Kui Jiang, Teng Zhang, Ni Zhao, Shihe Yang and He Yan
Journal of Materials Chemistry A 2015 - vol. 3(Issue 17) pp:NaN9102-9102
Publication Date(Web):2014/12/23
DOI:10.1039/C4TA05309E
Hybrid organic/inorganic perovskite solar cells are among the most competitive emerging photovoltaic technologies. Here, we report on NiO-based inverted structure perovskite solar cells with a high power conversion efficiency of 10.68%, which is achieved by adding a small percentage (1.5 wt%) of high molecular weight polystyrene (PS) into the PCBM electron transport layer (ETL). The addition of PS facilitates the formation of a highly smooth and uniform PCBM ETL that is more effective in preventing undesirable electron–hole recombination between the perovskite layer and the top electrode. As a result, the VOC of the PCBM:PS-based cells is increased from 0.97 V to 1.07 V, which leads to significantly enhanced power conversion efficiencies of the solar cells. Our study provides a simple and low-cost approach to improving the ETL film quality and the performance of inverted perovskite solar cells.
Co-reporter:Jie Cao, Feng Wang, Hui Yu, Yang Zhou, Haipeng Lu, Ni Zhao and Ching-Ping Wong
Journal of Materials Chemistry A 2016 - vol. 4(Issue 26) pp:NaN10230-10230
Publication Date(Web):2016/06/01
DOI:10.1039/C6TA03121H
Two-step sequential deposition has been widely used for the fabrication of organolead halide perovskites due to its efficient pore-filling in mesostructured perovskite solar cells (PSCs) and great controllability of the perovskite film morphology. However, due to the limited diffusivity of the organic salt, it is often difficult to fully convert a >150 nm compact PbI2 precursor film to perovskite during a sequential deposition process. Consequently, the uncontrollable amount of remnant PbI2 may not only affect the device reproducibility but also harm the air stability of the perovskite films. In this work, we developed a new method to synthesize PbI2 thin films with nano-pores and tunable crystal sizes. We found that the porous structure and small crystal size of the synthesized PbI2 can facilitate its conversion to CH3NH3PbI3 perovskite, resulting in a PbI2-free and highly oriented perovskite film. PSCs based on such perovskite films exhibit superior power conversion efficiencies as compared to the ones synthesized from compact PbI2 films; more importantly, the stability of the perovskite films and PSCs has been greatly improved.
Co-reporter:Jizhang Chen, Junling Xu, Shuang Zhou, Ni Zhao and Ching-Ping Wong
Journal of Materials Chemistry A 2015 - vol. 3(Issue 33) pp:NaN17391-17391
Publication Date(Web):2015/07/17
DOI:10.1039/C5TA04164C
A facile and scalable one-step anodization method has been developed to fabricate three-dimensional (3-D) Cu(OH)2 nanoporous nanorods on a copper foil substrate, a product that can be used directly as a binder-free electrode for supercapacitors. The unique morphology of the nanorods provides a large amount of active sites for redox reactions, which can be easily accessed by electrolyte ions. Benefiting from that, a high capacitance of 213 mF cm−2 is obtained, and superior rate capability (62.3% capacitance retention when the scan rate is increased to 10 times) and excellent cyclability (92.0% capacitance retention after 5000 cycles) are achieved. In addition, a flexible and foldable solid-state asymmetric supercapacitor is assembled using the Cu(OH)2 and activated carbon as the positive and negative electrodes, respectively. The devices deliver a high energy density of 3.68 mW h cm−3 and a high power density of 5314 mW cm−3, demonstrating great potential for next-generation high-rate energy storage systems.
Zinc, [5,15-bis[2,6-bis(dodecyloxy)phenyl]-10-[2-(3,5-dibromophenyl)ethynyl]-20-[2-(1-pyrenyl)ethynyl]-21H,23H-porphinato(2-)-κN21,κN22,κN23,κN24]-,
Propanedinitrile, 2-[[7-[5-[bis(4-methylphenyl)amino]-2-thienyl]-2,1,3-benzothiadiazol-4-yl]methylene]-
PDPP-TT
Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]
2-ethenylbenzenesulfonic acid
Nickelous Nitrate
TELLANE
1-methylethyl 7-methyl-2-({3-[3-methyl-4-(prop-2-en-1-yloxy)phenyl]-1-phenyl-1H-pyrazol-4-yl}methylidene)-5-[4-(methylsulfanyl)phenyl]-3-oxo-2,3-dihydro-5H-[1,3]thiazolo[3,2-a]pyrimidine-6-carboxylate
Formamide, N,N-dimethyl-