The Role of NiO Doping in Reducing the Impact of Humidity on the Performance of SnO2‐Based Gas Sensors: Synthesis Strategies,and Phenomenological and Spectroscopic Studies

The humidity dependence of the gas‐sensing characteristics in SnO₂‐based sensors, one of the greatest obstacles in gas‐sensor applications, is reduced to a negligible level by NiO doping. In a dry atmosphere, undoped hierarchical SnO₂ nanostructures prepared by the self‐assembly of crystalline nanosheets show a high CO response and a rapid response speed. However, the gas response, response/recovery speeds, and resistance in air are deteriorated or changed significantly in a humid atmosphere. When hierarchical SnO₂ nanostructures are doped with 0.64–1.27 wt% NiO, all of the gas‐sensing characteristics remain similar, even after changing the atmosphere from a dry to wet one. According to diffuse‐reflectance Fourier transform IR measurements, it is found that the most of the water‐driven species are predominantly absorbed not by the SnO₂ but by the NiO, and thus the electrochemical interaction between the humidity and the SnO₂ sensor surface is totally blocked. NiO‐doped hierarchical SnO₂ sensors exhibit an exceptionally fast response speed (1.6 s), a fast recovery speed (2.8 s) and a superior gas response (R_a/R_g = 2.8 at 50 ppm CO (R_a: resistance in air, R_g: resistance in gas)) even in a 25% r.h. atmosphere. The doping of hierarchical SnO₂ nanostructures with NiO is a very‐promising approach to reduce the dependence of the gas‐sensing characteristics on humidity without sacrificing the high gas response, the ultrafast response and the ultrafast recovery.     

Fabrication of Ultrathin 2D Cu‐BDC Nanosheets and the Derived Integrated MOF Nanocomposites

Freestanding 2D nanosheets with many unprecedented properties have been used in a myriad of applications. In this work, 2D copper‐bearing metal‐organic frameworks (MOFs; viz., Cu‐BDC) nanosheets are successfully fabricated via a facile and benign methodology through using Cu₂O nanocubes (≈60 nm) as a confined metal ion source and 1,4‐benzenedicarboxylic acid (H₂BDC) as an organic linker. The Cu₂O nanocubes gradually release Cu⁺ ions which are further oxidized by the dissolved oxygen and serve as nutrients for construction of 2D frameworks. In contrast, the conventional solvothermal synthesis with copper salt exclusively yields bulk Cu‐BDC with edge dimensions of 2–10 µm. Interestingly, the as‐prepared Cu‐BDC nanosheets show ultrathin thickness, oriented growth, and excellent crystallinity, which can be exploited as a platform for the design of a series of 2D‐integrated nanocatalysts by loading various metal nanocrystals such as Au, Ag, Pt, and Ru, with 3‐mercaptopropionic acid as molecular link. In addition, it is found that Cu‐BDC/M composites with highly accessible active sites on the surface exhibit high catalytic activity in several condensation reactions between benzaldehyde and primary amines. The findings offer an alternative strategy for rational design and synthesis of 2D MOF nanosheets and the derived 2D nanocomposites for catalytic applications.     

Multiarray Nanopattern Electronic Nose (E‐Nose) by High‐Resolution Top‐Down Nanolithography

An electronic nose (E‐nose) is an artificial sensing device that mimics the human olfactory system using a multiarray sensor system. However, since the design and fabrication of multiarray sensing channels are significantly limited because of the requirement of time‐consuming and nonuniversal processes, the development of commercializable and high‐throughput fabrication approaches are critically required. Herein, high‐resolution top‐down lithography is developed for E‐nose fabrication for the first time. Five different metal oxide semiconductor (MOS) nanopattern channels (NiO, CuO, Cr₂O₃, SnO₂, and WO₃) are fabricated into multiarray sensors with high‐throughput using a unique lithographic approach that utilizes the sputtering of grains of the metals via low‐energy ion plasma bombardment. The nanopattern channels show i) high‐resolutions (15 nm scale), ii) high‐aspect‐ratios (11; 14 nm width and 150 nm height), and iii) ultrasmall grains (5.1 nm) with uniformity on a cm² scale, resulting in high sensitivity toward the target analytes. The E‐nose system, which is composed of five MOS nanopattern channels, can successfully distinguish seven different hazardous analytes, including volatile organic compounds and nitrogen‐containing compounds. It is expected that this unique lithography approach can provide a simple and reliable method for commercializable channel fabrication, and the E‐noses can have further applications in real‐life situations.     

Low‐Temperature Growth of SnO2 Nanorod Arrays and Tunable n–p–n Sensing Response of a ZnO/SnO2 Heterojunction for Exclusive Hydrogen Sensors

Uniform SnO₂ nanorod arrays have been deposited at low temperature by plasma‐enhanced chemical vapor deposition (PECVD). ZnO surface modification is used to improve the selectivity of the SnO₂ nanorod sensor to H₂ gas. The ZnO‐modified SnO₂ nanorod sensor shows a normal n‐type response to 100 ppm CO, NH₃, and CH₄ reducing gas whereas it exhibits concentration‐dependent n–p–n transitions for its sensing response to H₂ gas. This abnormal sensing behavior can be explained by the formation of n‐ZnO/p‐Zn‐O‐Sn/n‐SnO₂ heterojunction structures. The gas sensors can be used in highly selective H₂ sensing and this study also opens up a general approach for tailoring the selectivity of gas sensors by surface modification.     

The Role of Hierarchical Morphologies in the Superior Gas Sensing Performance of CuO‐Based Chemiresistors

The development of gas sensors with innovative designs and advanced functional materials has attracted considerable scientific interest given their potential for addressing important technological challenges. This work presents new insight towards the development of high‐performance p‐type semiconductor gas sensors. Gas sensor test devices, based on copper (II) oxide (CuO) with innovative and unique designs (urchin‐like, fiber‐like, and nanorods), are prepared by a microwave‐assisted synthesis method. The crystalline composition, surface area, porosity, and morphological characteristics are studied by X‐ray powder diffraction, nitrogen adsorption isotherms, field‐emission scanning electron microscopy and high‐resolution transmission electron microscopy. Gas sensor measurements, performed simultaneously on multiple samples, show that morphology can have a substantial influence on gas sensor performance. An assembly of urchin‐like structures is found to be most effective for hydrogen detection in the range of parts‐per‐million at 200 °C with 300‐fold larger response than the previously best reported values for semiconducting CuO hydrogen gas sensors. These results show that morphology plays an important role in the gas sensing performance of CuO and can be effectively applied in the further development of gas sensors based on p‐type semiconductors.     

Inside Front Cover: One‐Pot Synthesis and Hierarchical Assembly of Hollow Cu2O Microspheres with Nanocrystals‐Composed Porous Multishell and Their Gas‐Sensing Properties (Adv. Funct. Mater. 15/2007)

On p. 2766, Qinshan Zhu and co‐workers report on multishell hollow Cu₂O microspheres that are synthesized by a facile and one‐pot solvothermal route. A two‐step organization process, in which hollow microspheres of Cu₂(OH)₃NO₃ are formed first followed by reduction to Cu₂O by glutamic acid, leads to the special multishell and hollow microstructures. Interestingly, a Cu₂O gas sensor fabricated with the multishell microspheres shows a much higher sensitivity to ethanol than solid Cu₂O microspheres. Hierarchical assembly of hollow microstructures is of great scientific and practical value and remains a great challenge. This paper presents a facile and one‐pot synthesis of Cu₂O microspheres with multilayered and porous shells, which were organized by nanocrystals. The time‐dependent experiments revealed a two‐step organization process, in which hollow microspheres of Cu₂(OH)₃NO₃ were formed first due to the Ostwald ripening and then reduced by glutamic acid, the resultant Cu₂O nanocrystals were deposited on the hollow intermediate microspheres and organized into finally multishell structures. The special microstructures actually recorded the evolution process of materials morphologies and microstructures in space and time scales, implying an intermediate‐templating route, which is important for understanding and fabricating complex architectures. The Cu₂O microspheres obtained were used to fabricate a gas sensor, which showed much higher sensitivity than solid Cu₂O microspheres.     

A Plant-inspired Light Transducer for High-performance Near-infrared Light Mediated Gas Sensing

Constructing near-infrared light (NIR) light-enhanced room temperature gas sensors is becoming more promising for practical application. In this study, learning from the structure and photosynthetic process of chlorophyll thylakoid membranes in plants, the first “Thylakoid membrane” structural formaldehyde (HCHO) sensor is constructed by matching the upconversion emission of the lanthanide-doped upconversion nanoparticles (UCNPs) and the UV–vis adsorption of the as-prepared nanocomposites. The NIR-mediated sensor exhibits excellent performances, including ultra-high response (R_a / R_g = 2.22, 1 ppm), low practical limit of detection (50 ppb), reliable repeatability, high selectivity, and broadband spectral response. The practicality of the NIR-mediated gas sensor is confirmed through the remote and external stimulation test. A study of sensing mechanism demonstrates that it is the UCNPs-based light transducer produces more light-induced oxygen species for gas response in the process of non-radiative/radiative energy transfer, playing a key role in significantly improving the sensing properties of the sensor. The universality of NIR-mediated gas sensors based on UCNPs is verified using ZnO, In₂O_3, and SnO₂ systems. This work paves a way for fabricating high-performance NIR-mediated gas sensors and will expand the application fields of NIR light.     

p‐CuO/n‐Si heterojunction solar cells with high open circuit voltage and photocurrent through interfacial engineering

Heterojunction solar cells of p‐type cupric oxide (CuO) and n‐type silicon (Si), p‐CuO/n‐Si, have been fabricated using conventional sputter and rapid thermal annealing techniques. Photovoltaic properties with an open‐circuit voltage (V_oc) of 380 mV, short circuit current (J_sc) of 1.2 mA/cm², and a photocurrent of 2.9 mA/cm² were observed for the solar cell annealed at 300 °C for 1 min. When the annealing duration was increased, the photocurrent increased, but the V_oc was found to reduce because of the degradation of interface quality. An improvement in the V_oc resulting to a record value of 509 mV and J_sc of 4 mA/cm² with a high photocurrent of ~12 mA/cm² was achieved through interface engineering and controlling the phase transformation of CuO film. X‐ray diffraction, X‐ray photoelectron spectroscopy, and high‐resolution transmission electron microscopy analysis have been used to investigate the interface properties and crystal quality of sputter‐deposited CuO thin film. The improvement in V_oc is mainly due to the enhancement of crystal quality of CuO thin film and interface properties between p‐CuO and n‐Si substrate. The enhancement of photocurrent is found to be due to the reduction of carrier recombination rate as revealed by transient photovoltage spectroscopy analysis. Copyright © 2014 John Wiley & Sons, Ltd.     

Engineering Solar Cell Absorbers by Exploring the Band Alignment and Defect Disparity: The Case of Cu‐ and Ag‐Based Kesterite Compounds

The development of kesterite Cu₂ZnSn(S,Se)₄ thin‐film solar cells is currently hindered by the large deficit of open‐circuit voltage (V_oc), which results from the easy formation of Cu_Zn antisite acceptor defects. Suppressing the formation of Cu_Zn defects, especially near the absorber/buffer interface, is thus critical for the further improvement of kesterite solar cells. In this paper, it is shown that there is a large disparity between the defects in Cu‐ and Ag‐based kesterite semiconductors, i.e., the Cu_Zn or Cu_Cd acceptor defects have high concentration and are the dominant defects in Cu₂ZnSn(S,Se)₄ or Cu₂CdSnS₄, but the Ag_Zn acceptor has only a low concentration and the dominant defects are donors in Ag₂ZnSnS₄. Therefore, the Cu‐based kesterites always show p‐type conductivity, while the Ag‐based kesterites show either intrinsic or weak n‐type conductivity. Based on this defect disparity and calculated band alignment, it is proposed that the V_oc limit of the kesterite solar cells can be overcome by alloying Cu₂ZnSn(S,Se)₄ with Ag₂ZnSn(S,Se)₄, and the composition‐graded (Cu,Ag)₂ZnSn(S,Se)₄ alloys should be ideal light‐absorber materials for achieving higher efficiency kesterite solar cells.     

Flexible Transparent Bifunctional Capacitive Sensors with Superior Areal Capacitance and Sensing Capability based on PEDOT:PSS/MXene/Ag Grid Hybrid Electrodes

Flexible transparent supercapacitors (FTSs) have aroused considerable attention. Nonetheless, balancing energy storage capability and transparency remains challenging. Herein, a new type of FTSs with both excellent energy storage and superior transparency is developed based on PEDOT:PSS/MXene/Ag grid ternary hybrid electrodes. The hybrid electrodes can synergistically utilize the high optoelectronic properties of Ag grids, the excellent capacitive performance of MXenes, and the superior chemical stability of PEDOT:PSS, thus, simultaneously demonstrating excellent optoelectronic properties (T: ≈89%, R_s: ≈39 Ω sq⁻¹), high areal specific capacitance, superior mechanical softness, and excellent anti-oxidation capability. Due to the excellent comprehensive performances of the hybrid electrodes, the resulting FTSs exhibit both high optical transparency (≈71% and ≈60%) and large areal specific capacitance (≈3.7 and ≈12 mF cm⁻²) besides superior energy storage capacity (P: 200.93, E: 0.24 µWh cm⁻²). Notably, the FTSs show not only excellent energy storage but also exceptional sensing capability, viable for human activity recognition. This is the first time to achieve FTSs that combine high transparency, excellent energy storage and good sensing all-in-one, which make them stand out from conventional flexible supercapacitors and promising for next-generation smart flexible energy storage devices.     

Printed,Flexible, Organic Nano‐Floating‐Gate Memory: Effects of Metal Nanoparticles and Blocking Dielectrics on Memory Characteristics

The effects of using a blocking dielectric layer and metal nanoparticles (NPs) as charge‐trapping sites on the characteristics of organic nano‐floating‐gate memory (NFGM) devices are investigated. High‐performance NFGM devices are fabricated using the n‐type polymer semiconductor, poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} (P(NDI2OD‐T2)), and various metal NPs. These NPs are embedded within bilayers of various polymer dielectrics (polystyrene (PS)/poly(4‐vinyl phenol) (PVP) and PS/poly(methyl methacrylate) (PMMA)). The P(NDI2OD‐T2) organic field‐effect transistor (OFET)‐based NFGM devices exhibit high electron mobilities (0.4–0.5 cm² V^?1 s^?1) and reliable non‐volatile memory characteristics, which include a wide memory window (≈52 V), a high on/off‐current ratio (I_on/I_off ≈ 10⁵), and a long extrapolated retention time (>10⁷ s), depending on the choice of the blocking dielectric (PVP or PMMA) and the metal (Au, Ag, Cu, or Al) NPs. The best memory characteristics are achieved in the ones fabricated using PMMA and Au or Ag NPs. The NFGM devices with PMMA and spatially well‐distributed Cu NPs show quasi‐permanent retention characteristics. An inkjet‐printed flexible P(NDI2OD‐T2) 256‐bit transistor memory array (16 × 16 transistors) with Au‐NPs on a polyethylene naphthalate substrate is also fabricated. These memory devices in array exhibit a high I_on/I_off (≈10^{4 ± 0.85}), wide memory window (≈43.5 V ± 8.3 V), and a high degree of reliability.     

Novel Atmospheric Growth Technique to Improve Both Light Absorption and Charge Collection in ZnO/Cu2O Thin Film Solar Cells

In low temperature grown ZnO/Cu₂O solar cells, there is a discrepancy between collection length and depletion width in the Cu₂O which makes the simultaneous achievement of efficient charge collection and high open‐circuit voltage problematic. This is addressed in this study by fabricating ZnO/Cu₂O/Cu₂O⁺ back surface field devices using an atmospheric atomic layer deposition (AALD) printing method to grow a sub‐200‐nm Cu₂O⁺ film on top of electrodeposited ZnO and Cu₂O layers. The AALD Cu₂O⁺ has a carrier concentration around 2 orders of magnitude higher than the electrodeposited Cu₂O, allowing the electrodeposited Cu₂O layer thickness in a back surface field cell to be reduced from 3 μm to the approximate charge collection length, 1 μm, while still allowing a high potential to be built into the cell. The dense conformal nature of the AALD layer also blocks shunt pathways allowing the voltage enhancement to be maintained. The thinner cell design reduces recombination losses and increases charge collection from both incident light and light reflected off the back electrode. Using this design, a short circuit current density of 6.32 mA cm^?2 is achieved–the highest reported J_SC for an atmospherically deposited ZnO/Cu₂O device to date.     

Semiconductor‐Type MEMS Gas Sensor for Real‐Time Environmental Monitoring Applications

Low power consuming and highly responsive semiconductor‐type microelectromechanical systems (MEMS) gas sensors are fabricated for real‐time environmental monitoring applications. This subsystem is developed using a gas sensor module, a Bluetooth module, and a personal digital assistant (PDA) phone. The gas sensor module consists of a NO₂ or CO gas sensor and signal processing chips. The MEMS gas sensor is composed of a microheater, a sensing electrode, and sensing material. Metal oxide nanopowder is drop‐coated onto a substrate using a microheater and integrated into the gas sensor module. The change in resistance of the metal oxide nanopowder from exposure to oxidizing or deoxidizing gases is utilized as the principle mechanism of this gas sensor operation. The variation detected in the gas sensor module is transferred to the PDA phone by way of the Bluetooth module.     

Water‐Induced Scandium Oxide Dielectric for Low‐Operating Voltage n‐ and p‐Type Metal‐Oxide Thin‐Film Transistors

Solution‐processed metal‐oxide thin films based on high dielectric constant (k) materials have been extensively studied for use in low‐cost and high‐performance thin‐film transistors (TFTs). Here, scandium oxide (ScO_x) is fabricated as a TFT dielectric with excellent electrical properties using a novel water‐inducement method. The thin films are annealed at various temperatures and characterized by using X‐ray diffraction, atomic‐force microscopy, X‐ray photoelectron spectroscopy, optical spectroscopy, and a series of electrical measurements. The optimized ScO_x thin film exhibits a low‐leakage current density of 0.2 nA cm^?2 at 2 MV cm^?1, a large areal capacitance of 460 nF cm^?2 at 20 Hz and a permittivity of 12.1. To verify the possible applications of ScO_x thin films as the gate dielectric in complementary metal oxide semiconductor (CMOS) electronics, they were integrated in both n‐type InZnO (IZO) and p‐type CuO TFTs for testing. The water‐induced full oxide IZO/ScO_x TFTs exhibit an excellent performance, including a high electron mobility of 27.7 cm² V^?1 s^?1, a large current ratio (I_on/I_off) of 2.7 × 10⁷ and high stability. Moreover, as far as we know it is the first time that solution‐processed p‐type oxide TFTs based on a high‐k dielectric are achieved. The as‐fabricated p‐type CuO/ScO_x TFTs exhibit a large I_on/I_off of around 10⁵ and a hole mobility of 0.8 cm² V^?1 at an operating voltage of 3 V. To the best of our knowledge, these electrical parameters are among the highest performances for solution‐processed p‐type TFTs, which represents a great step towards the achievement of low‐cost, all‐oxide, and low‐power consumption CMOS logics.     

Strong Facet Effects on Interfacial Charge Transfer Revealed through the Examination of Photocatalytic Activities of Various Cu2O–ZnO Heterostructures

Confirming the photocatalytic inactivity of Cu₂O nanocubes through the formation of Au‐decorated–Cu₂O heterostructures, spiky ZnO nanostructures are grown on Cu₂O cubes, octahedra, and rhombic dodecahedra to demonstrate that charge transfer across semiconductor heterojunctions is also strongly facet dependent. Unintended CuO formation in the growth of ZnO on perfect Cu₂O cubes makes them slightly active toward methyl orange photodegradation. Under optimal ZnO growth conditions without CuO presence, Cu₂O cubes remain inactive, while rhombic dodecahedra show an enhanced photocatalytic activity due to better charge transfer according to normal Cu₂O–ZnO band alignment. Surprisingly, photocatalytically active Cu₂O octahedra become inactive after ZnO deposition. An extensive interfacial microscopic examination reveals preferential formation of the ZnO (101) planes on the {111} surfaces of Cu₂O octahedra, while different ZnO lattice planes are observed to deposit on Cu₂O cubes and rhombic dodecahedra. The photocatalytic inactivity of ZnO‐decorated Cu₂O octahedra is explained in terms of an unfavorable band alignment arising from an unusual degree of band bending for the ZnO {101} face relative to the band energy of the Cu₂O {111} surface. The efficiency of charge transfer across semiconductor heterojunctions strongly depends on the band edge energies of the contacting planes.     

MoS2 Van der Waals p–n Junctions Enabling Highly Selective Room‐Temperature NO2 Sensor

Van der Waals p–n junctions of 2D materials present great potential for electronic devices due to the fascinating properties at the junction interface. In this work, an efficient gas sensor based on planar 2D van der Waals junctions is reported by stacking n‐type and p‐type atomically thin MoS₂ films, which are synthesized by chemical vapor deposition (CVD) and soft‐chemistry route, respectively. The electrical conductivity of the van der Waals p–n junctions is found to be strongly affected by the exposure to NO₂ at room temperature (RT). The MoS₂ p–n junction sensor exhibits an outstanding sensitivity and selectivity to NO₂ at RT, which are unavailable in sensors based on individual n‐type or p‐type MoS₂. The sensitivity of 20 ppm NO₂ is improved by 60 times compared to a p‐type MoS₂ sensor, and an extremely low limit of detection of 8 ppb is obtained under ultraviolet irradiation. Complete and very fast sensor recovery is achieved within 30 s. These results are superior to most of the previous reports related to NO₂ detection. This work establishes an entirely new sensing platform and proves the feasibility of using such materials for the high‐performance detection of gaseous molecules at RT.     

Phase relations in Cu- RO1.5- O (R < Ho,Er, Yb) and gibbs energy of formation of Cu2R2O5 (R < Ho,Er, Yb) between 1000 and 1325K

Phase relations in Cu-RO_1.5-O(R < Ho,Er,Yb) ternary systems at 1273K have been established by isothermal equilibration of samples containing different ratios of Cu:R(R < Ho,Er,Yb) in flowing air or high purity argon atmosphere for four days. The samples were then rapidly cooled to ambient temperature and the coexisting phases were identified by powder x-ray diffraction analysis. Only one ternary oxide, Cu₂R₂O₅(R < Ho,Er,Yb) was found to be stable. The chemical potential of oxygen for the coexistence of the three phase assemblage, Cu₂O + R₂O₃ + Cu₂R₂O₅(R < Ho,Er,Yb) has been measured by employing the solid-state galvanic cells,< (−) Pt, Cu₂O + Ho₂O₃+ Cu₂Ho₂O₅//CSZ//Air (Po₂< 2.12 × 10⁴ Pa), Pt (+) (−) Pt, Cu₂O + Er₂O₃+ Cu₂Er₂O//CSZ//Air (Po₂< 2.12 × 10⁴ Pa), Pt (+) (−) Pt, Cu₂O + Yb₂O₃ + Cu₂Yb₂O₅//CSZ//Air (Po₂ < 2.12 × 10⁴ Pa), Pt (+) in the temperature range of 1000 to 1325K. Combining the measured emf of the above cells with the chemical potential of oxygen at the reference electrode, using the Nernst relationship, gives for the reactions, 2Cu₂O(s) + 2Ho₂O₃(s) + O₂(g) → 2Cu₂Ho₂O₅(s) (1) 2Cu₂O(s) + 2Er₂O₃(s) + O₂(g) → 2Cu₂Er₂O₅(s) (2) and 2Cu₂O(s) + 2Yb₂O₃(s) + O₂(g) → 2Cu₂Yb₂O₅(s) (3) δΜo₂ = −219,741.3 + 145.671 T (±100) Jmol⁻¹ (4) δΜo₂ = −222,959.8 + 147.98 T(±100) Jmol⁻¹ (5) and δΜo₂ = −231,225.2 + 151.847 T(±100) Jmol⁻¹ (6) respectively. Combining the chemical potential of oxygen for the coexistence of Cu₂O + R₂O₃ + Cu₂R₂O₅(R− Ho,Er,Yb) obtained in this study with the oxygen potential for Cu₂O + CuO equilibrium gives for the reactions, 2 CuO(s) + Ho₂O₃(s) → Cu₂Ho₂O₅(s) (7) 2 CuO(s) + Er₂O₃(s) → Cu₂Er₂O₅(s) (8) and 2 CuO(s) + Yb₂O₃(s) → Cu₂Yb₂O₅(s) (9) δG‡ < 22,870.3 − 23.160 T (±100) Jmol⁻¹ (10) δG‡ < 21,261.1 − 22.002 T (±100) Jmol⁻¹ (11) and δG‡ < 17,128.4 - 20.072 T (±100) Jmol^-1 (12) It can be clearly seen that the formation of Cu₂R₂O₅R < Ho,Er,Yb) from the component oxides is endothermic. Further, Cu₂R₂O₅(R < Ho,Er,Yb) are an entropy stabilized phases. Based on the results obtained in this study, the oxygen potential diagram for Cu-R-O(R < Ho,Er,Yb) ternary system at 1273K has been composed.     

Design and Directional Growth of (Mg1−xZnx)(Al1−yCry)2O4 Single-Crystal Fibers for High-Sensitivity and High-Temperature Sensing Based on Lattice Doping Engineering and Acoustic Anisotropy

High-performance temperature sensors for the harsh environment are vital components for meeting the increasing demands for the development of existing and emerging technologies. In this study, specifically oriented (Mg_1−xZn_x)(Al_1−yCr_y)₂O₄ single-crystal fibers (SCF) are grown by the laser-heated pedestal growth technique and used as acoustic waveguides for ultrasonic temperature sensors (UTS) for the first time. The anisotropic sensor performance of the MgAl₂O₄ SCF-UTS are investigated under a longitudinal wave and transverse wave conditions, and the [110]-oriented MgAl₂O₄ SCF-UTS is found to have the highest sensitivity and resolution among all the MgAl₂O₄ SCF-UTS. On this basis, a unit sensitivity of 40.38–67.50 ns °C⁻¹ m⁻¹ and a resolution of 1.24–0.74 °C are achieved for the [110]-oriented (Mg_0.9Zn_0.1)(Al_0.995Cr_0.005)₂O₄ SCF-UTS in the range of 20–1200 °C, both of which represent the best sensor performance achieved by a SCF-UTS to date. The positive temperature-dependent sensor performance, accompanied by a high working temperature (≈2000 °C) and outstanding anti-oxidation, indicates that the [110]-oriented (Mg_0.9Zn_0.1)(Al_0.995Cr_0.005)₂O₄ SCF-UTS is a promising candidate for ultra-high temperature sensors. This study demonstrates a feasible strategy for the rational design of high-performance temperature sensors through a combination of crystal design, acoustic anisotropy, and lattice doping engineering.     

基于石墨烯的CO和CO2气体传感器研究进展

室温下石墨烯具有电子迁移率高、比表面积大、机械强度高、化学稳定性和热稳定性优异、导电性好等独特性能,是当今最受关注的二维材料之一。与传统无机氧化物材料相比,石墨烯气体传感器具有工作温度低、能耗小、恢复性高的优点。文章对两种石墨烯气体传感器的研究进展进行了综述。根据气体选择性不同,将石墨烯气体传感器分为检测CO和CO₂气体传感器。分别对其灵敏度、气体响应灵敏度和响应时间等特性进行分析对比。此研究对此类传感器的应用与推广具有一定的指导意义。     

Thermochromic Lead‐Free Halide Double Perovskites

Lead‐free halide double perovskites with diverse electronic structures and optical responses, as well as superior material stability show great promise for a range of optoelectronic applications. However, their large bandgaps limit their applications in the visible light range such as solar cells. In this work, an efficient temperature‐derived bandgap modulation, that is, an exotic fully reversible thermochromism in both single crystals and thin films of Cs₂AgBiBr₆ double perovskites is demonstrated. Along with the thermochromism, temperature‐dependent changes in the bond lengths of Ag? Br (R_{Ag? Br}) and Bi? Br (R_{Bi? Br}) are observed. The first‐principle molecular dynamics simulations reveal substantial anharmonic fluctuations of the R_{Ag? Br} and R_{Bi? Br} at high temperatures. The synergy of anharmonic fluctuations and associated electron–phonon coupling, and the peculiar spin–orbit coupling effect, is responsible for the thermochromism. In addition, the intrinsic bandgap of Cs₂AgBiBr₆ shows negligible changes after repeated heating/cooling cycles under ambient conditions, indicating excellent thermal and environmental stability. This work demonstrates a stable thermochromic lead‐free double perovskite that has great potential in the applications of smart windows and temperature sensors. Moreover, the findings on the structure modulation‐induced bandgap narrowing of Cs₂AgBiBr₆ provide new insights for the further development of optoelectronic devices based on the lead‐free halide double perovskites.