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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2023 · IF 10.9

Constructing cell-membrane-mimic grain boundaries for high-performance n-type Ag2Se using high-dielectric-constant TiO2

Yi-Yan Liao,Qiang Sun,Xu-Ping Jiang,Hao Wu,Bang-Zhou Tian,Ze-Gao Wang,Kun Zheng,Lei Yang

The coupling of charge carrier and phonon transport limits the application of Ag 2 Se as a low-toxic near-room-temperature thermoelectric material. Strategies that reduce the thermal conductivity via enhancing the phonon scattering usually lead to reduced carrier mobility due to high grain boundary potential barrier. In this study, we developed a cell-membrane-mimic grain boundary engineering strategy for decoupling the charge carrier and phonon scattering through decorating high-dielectric-constant rutile TiO 2 at Ag 2 Se grain boundaries to enable the charge carrier/phonon selective permeability. The nano-sized TiO 2 with high dielectric permittivity can secure the charge carrier transport by shielding the interfacial Coulomb potential to lower the energy barrier of grain boundaries, rendering an enhanced power factor. Additionally, benefited from the enhanced phonon scattering by TiO 2 nanoparticles, a significantly decreased lattice thermal conductivity of ∼0.20 W m −1 K −1 and a high zT of ∼0.97 at 390 K are obtained in the Ag 2 Se-based nanocomposites. This work demonstrates that such cell-membrane-mimic grain boundary engineering strategy may shed light on developing high-performance thermoelectric materials.

研究领域: 材料科学 · 物理学
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JOURNAL OF PHYSICS D-APPLIED PHYSICS · 2016 ·Vol. 49 ·期 34 ·345102 · IF 2.772

Pressure-induced improvement of grain boundary properties in yttrium-doped BaZrO3

Lei Wu,LiDong Dai,HePing Li,YuKai Zhuang,KaiXiang Liu

Yttrium-doped BaZrO3 (BZY) is a promising electrolyte for intermediate-temperature protonic ceramic fuel cells. However, BZY exhibits a high resistance because of the blocking effect of the grain boundaries. In this study, the effect of pressure on undoped and 5% yttrium-doped BaZrO3 (BZY0 and BZY5) were investigated at 0.45–24.01 GPa and 273–673 K with a diamond anvil cell. Their bulk, grain boundary, and total electrical conductivities were determined by impedance spectroscopy and direct-current resistance measurement. Both samples tended to show increasing electrical conductivity with increasing pressure, although each showed a discontinuous inflexion point (at ~14.54 GPa for BZY0 and at ~11.11 GPa for BZY5) indicating a phase transition from a cubic to a tetragonal structure. The samples showed a 3.43 GPa difference in the onset pressure of the structure change. Characteristic parameters, including space charge potential, relaxation frequency, and transport activation energy, were obtained before and after the phase transition. The results suggest that pressure significantly improves oxygen ion conduction in acceptor-doped perovskites oxides.

研究领域: 材料科学 · 能源研究
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Small · 2022 ·Vol. 18 ·期 38 ·2203620 · IF 15.153

Exploration of Twin-Modified Grain Boundary Engineering in Metallic Copper Predominated Electromagnetic Wave Absorber

Hongsheng Liang,Limin Zhang,Hongjing Wu

High density and skin effect restrict the research progress of metal predominated electromagnetic wave absorbing (EMA) materials. Although some works try to solve it, they do not focus on the metal itself and do not involve the optimization of the active site of the inherent defects of the metal. In this work, the modulation of morphology, composition, interface, defects, and conductivity is achieved by adjusting the ratio of copper salt to reducing agent chitosan. Uniquely, the appearance of twin boundaries (TBs) accelerates the ability of the homogeneous interfaces to transfer charges, resists the oxidation of metal Cu 0 , keeps the high electric conductivity of Cu 0 nanoparticles, and enhances the conduction loss, which provides a boost for electromagnetic wave dissipation. As a result, the metal Cu 0 predominated absorber (Cu-NC (N-doped carbon)−10,) exhibits an ultra-width effective absorption band of 8.28 GHz (9.72–18.00 GHz) at a thickness of 2.47 mm and the minimum reflection loss ( RL ) value of −63.8 dB with a thickness of 2.01 mm. In short, this work explores the EM regulation mechanism of TBs compared with grain boundaries (GBs), which provides a new insight for the rational design of metal predominated EMA materials.

研究领域: 材料科学 · 电磁学
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RSC Advances · 2024 ·Vol. 14 ·期 13 ·9072-9079 · IF 3.9

The impact of thickness-related grain boundary migration on hole concentration and mobility of p-type transparent conducting CuI films

Ruibin Xue,Gang Gao,Lei Yang,Liangge Xu,Yumin Zhang,Jiaqi Zhu

CuI films present promising optoelectronic properties for transparent conductors. However, the high hole concentration in CuI films hinders the controllable modulation of hole mobility, limiting their application in low-dimensional thin-film transistors. In this study, CuI films were prepared through a Cu film iodination method at room temperature, and a systematic investigation was conducted on the modulation of hole concentration and mobility with varying film thickness. The films exhibited a zinc blende structure (γ-phase) with increasing grain size as the thickness increased. The transmittance and optical bandgap of the films decreased with increasing thickness. The correlation of vacancy concentration with changing film thickness was analyzed through photoluminescence spectroscopy, revealing the influence of grain boundary migration on vacancy formation. The reduction in film thickness diminishes the migration of CuI grain boundaries, consequently reducing the probability of Cu vacancy and I vacancy formation, resulting in diminished hole concentration and enhanced hole mobility and film conductivity. The film with a thickness of 20 nm demonstrated optimal performance, with a transmittance of 90%, hole concentration of 4.09 × 1017 cm−3, hole mobility of 506.50 cm2 V−1 s−1, and conductivity of 33.19 S cm−1. This work deepens the understanding of hole transport such as hole concentration and mobility modulation in CuI films, highlighting the importance of controlling grain boundary migration during the film growth process.

研究领域: 材料科学 · 光学 · 半导体物理
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CATALYSIS COMMUNICATIONS · 2022 · IF 3.51

Facilitating CO2 electroreduction to C2H4 through facile regulating {100} & {111} grain boundary of Cu2O

Zhi-xiu Yang,Xiu Wen,Li-jing Gao,Jin Zhang,Rui-ping Wei,Xiao-mei Pan,Guo-min Xiao

The electrocatalytic carbon dioxide reduction provides a promising route to alleviate the greenhouse effect and energy crisis. We investigated the influencing factors that conversion of CO 2 to C 2 H 4 by preparing Cu 2 O nanoparticles (Cu 2 O-p, Cu 2 O-2p, and Cu 2 O-3p) with exposed different crystal facets, sizes, and grain boundaries. Impressively, the Cu 2 O-3p catalyst exhibits superior selectivity (57.8%) for C 2 H 4 generation due to its abundant {100} & {111} grain boundaries. The study demonstrated that rich grain boundaries have a significant effect on C C coupling for electrocatalysis CO 2 reduction, and offered a learnable route for high-efficient CO 2 reduction catalysts by regulating grain boundary.

CAS / MDL: 50-99-7 7681-11-0
研究领域: 材料科学 · 环境科学
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Nanoscale · 2024 ·Vol. 16 ·期 45 ·21031-21038 · IF 5.8

Decoupled electron–phonon transport in Ag2Se thermoelectric materials through constructing TiO2/MoS2 co-decorated cell-membrane-mimic grain boundaries

Hanwen Hu,Yiyan Liao,Shanshan Tan,Chen Li,Jun Tang,Kun Zheng,Lei Yang

Ag2Se has emerged as a promising n-type thermoelectric material; however, its application is limited mainly due to the strongly coupled charge carrier and phonon transport. Enhancing phonon scattering by constructing interfacial complexes often results in low carrier mobility due to its strong carrier scattering resulting from the high energy barrier at the multiphase interface. Inspired by the cell membrane with selective permeability, we construct bio-mimic grain boundaries with TiO2 and MoS2 co-decoration in Ag2Se to decouple electron scattering from strong phonon scattering. The nanostructured TiO2 with a high dielectric constant screens the interfacial Coulomb potential, ensuring efficient carrier transport and reducing the grain boundary barriers, while the few-layer MoS2 provides significant phonon scattering to further reduce the thermal conductivity. This method effectively enhances the zT value of Ag2Se by as much as 60% and also can significantly enhance the theoretical output performance of the thermoelectric device, which highlights the effectiveness of the bio-mimic grain boundary engineering strategy.

研究领域: 材料科学 · 物理学
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COMPOSITES PART B-ENGINEERING · 2025 · IF 14.2

Simultaneous enhancement of strength and ductility in AlCu alloy via trans-granular graphene nano-shells

Xiangren Bai,Xiang Zhang,Dongdong Zhao,Xudong Rong,Naiqin Zhao,Chunnian He

Strain localization at grain boundaries (GBs) is one of the key factors contributing to the trade-off between strength and ductility in engineering alloys. To address this issue, we developed a unique perpendicular interlocking structure connecting the matrix GBs by introducing trans -granular graphene nano-shells (SGSs) via a two-step targeted localized Cu–Al interdiffusion process. In the as-built structure, the original GBs served as the soft component, while the perpendicularly intersecting SGSs acted as the hard component. This configuration not only promotes sustainable dislocation accumulation in the vicinity of the GBs but also facilitates plastic strain delocalization through stress shielding effects from the SGSs. By effectively impeding the extension of shear bands and redirecting crack propagation towards the grain interiors, these hetero-structured GBs contribute to reducing the intrinsic brittleness of GBs. Consequently, the SGS/AlCu composite demonstrates a remarkable balance of tensile strength (∼574 MPa) and ductility (∼17 %). Our findings suggest that restructuring the geometry of GBs in metallic alloys presents a promising strategy for mitigating strain localization at GBs, offering potential for enhancing the properties of metallic alloys in various engineering applications.

CAS / MDL: 1317-38-0
研究领域: 材料科学 · 力学工程
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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Grain size and grain boundary characteristics on the out-plane thermal conductivity of <111>-oriented CVD 3C–SiC

Wei Ding,Pengjian Lu,Qingfang Xu,Chitengfei Zhang,Rong Tu,Song Zhang

In the integrated circuit industry, heat is transferred through the contact between wafers and the chemical vapor deposited (CVD) 3C–SiC wafer susceptor . Understanding the out-plane thermal conductivity of CVD 3C–SiC is crucial in this context. The influence of grain size and grain boundary characteristics on out-plane thermal conductivity for <111>-oriented CVD 3C–SiC was discussed in this study. The out-plane thermal conductivity sharply decreases from 146.4 W/m⸱K to 122.3 W/m⸱K when the grain size approaches 11.04 μm. This paper suggests that the significant accumulation of dislocations at high-angle grain boundaries is the primary cause of this phenomenon. The substantial lattice strain impedes phonon transfer between grain boundaries, reducing overall phonon mobility. These findings suggest that manipulating the grain boundary angle is an effective means to fine-tune heat transfer in <111>-oriented CVD 3C–SiC.

CAS / MDL: 10026-04-7
研究领域: 材料科学 · 热物理学
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Nature Communications · 2024 ·Vol. 15 ·期 1 ·1-9 · IF 14.7

Approaching crystal’s limit of thermoelectrics by nano-sintering-aid at grain boundaries

Lei Jingdan,Zhao Kunpeng,Liao Jincheng,Yang Shiqi,Zhang Ziming,Wei Tian-Ran,Qiu Pengfei,Zhu Min,Chen Lidong,Shi Xun

Grain boundary plays a vital role in thermoelectric transports, leading to distinct properties between single crystals and polycrystals. Manipulating the grain boundary to realize good thermoelectric properties in polycrystals similar as those of single crystals is a long-standing task, but it is quite challenging. Herein, we develop a liquid-phase sintering strategy to successfully introduce Mg 2 Cu nano-sintering-aid into the grain boundaries of Mg 3 (Bi, Sb) 2 -based materials. The nano-aid helps to enlarge the average grain size to 23.7 μm and effectively scatter phonons, leading to excellent electrical transports similar as those of single crystals and ultralow lattice thermal conductivity as well as exceptional thermoelectric figure of merit (1.5 at 500 K) and conversion efficiency (7.4% under temperature difference of 207 K). This work provides a simple but effective strategy for the fabrication of high-performance polycrystals for large-scale applications.

研究领域: 材料科学 · 物理学
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METALLURGICAL AND MATERIALS TRANSACTIONS A-PHYSICAL METALLURGY AND MATERIALS SCIENCE · 2020 ·Vol. 51 ·期 10 ·5328-5338 · IF 2.05

Formation Mechanism of In Situ Intergranular CaZrO3 Phases in Sintered Magnesia Refractories

Zou Yongshun,Gu Huazhi,Huang Ao,Fu Lvping

Sintered magnesia refractories combined by in situ intergranular CaZrO 3 phases were synthesized using natural MgO-containing natural minerals with CaO and SiO 2 impurities and nano-sized ZrO 2 additive. A homogenous distribution of intergranular CaZrO 3 , independent from the intergranular CaO-MgO-SiO 2 phases, was formed in situ within the sintered magnesia aggregates by introducing 0.75 wt pct nano-sized ZrO 2 into the magnesite. The formation mechanism of the in situ intergranular CaZrO 3 phases was determined. The nano-sized ZrO 2 was introduced and uniformly distributed at grain boundaries of the magnesia due to the micron-nano-sized particles composite system and wetting grinding process. Then the CaO in impurities were prior to SiO 2 to react with the ZrO 2 for generating CaZrO 3 at the grain boundaries by increasing sintering temperature. Nevertheless, the nano-sized ZrO 2 particles were encapsulated in the MgO crystallites with similar particle size decomposed from brucite and prevented from reacting with CaO impurities in magnesite. The mixing homogeneity of magnesite particles and ZrO 2 particles and the direct contact between ZrO 2 and CaO impurities in magnesite has a crucial effect on the formation of intergranular CaZrO 3 phases. Furthermore, the intergranular CaZrO 3 phases could enhance the bonding of magnesia grains and have great potential for improving the service performance of magnesia.

CAS / MDL: 1309-48-4
研究领域: 材料科学 · 无机非金属材料
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Polymeric gel-mediated grain boundary self-healing for the fabrication of high-performance and durable organic thin-film transistors

Haikun Zhu,Jinquan Huang,Zhenxin Yang,Junzhan Wang,Xuanhe Li,Dengke Wang,Zhenghong Lu,Qiang Zhu

Electrical degradation caused by grain boundaries in organic semiconductor (OSC) films is a prevalent issue that limits the large-area applications of organic electronics. Here, we report a polymer gel composed of polyethyleneimine and polydimethylsiloxane, which enables a of grain-boundary self-healing (GBSH) treatment within as-deposited OSC films by providing ionic conductivity across grain boundaries. The gel-based GBSH treatment demonstrates universal efficacy across a variety of OSC-based films for enhancing the operational performance of OTFTs. Typically, it enhances the field-effect mobilities of p -type rubrene-based and n -type PTCDI-C8-based OTFTs by 43 times and 25 times, respectively, while increasing their on/off ratio by 14.2-fold and 7.9-fold, respectively. Moreover, the GBSH treatment enables the enhanced stability of OTFTs under ambient conditions. The field-effect mobility of rubrene-based OTFTs, which decreased by 64 % within 11 days, was reduced to only a 29 % decrease over 90 days following the GBSH treatment. Additionally, the GBSH treatment mitigates the adverse impact of grain boundary anisotropy on device uniformity. The coefficient of variation for the field-effect mobility of rubrene-based OTFT arrays was reduced from 95 % to 13 % following the GBSH treatment, satisfying the industry standard for silicon-based devices. Moreover, the GBSH treatment is a post-fabrication process that is easy to implement. By conveniently depositing the gel onto OSC films via either spin-coating or drop-casting, it enables the in-situ repair of damaged grain boundaries within operational devices, thereby restoring device performance beyond that of freshly fabricated devices. The GBSH strategy represents a significant advancement toward high-performance organic electronics tailored for large-area applications.

研究领域: 材料科学 · 有机电子学 · 高分子科学 · 半导体器件 · 薄膜技术
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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Regulating Strain and Electronic Structure of Indium Tin Oxide Supported IrOx Electrocatalysts for Highly Efficient Oxygen Evolution Reaction in Acid

Weiwei Han,Xinuo Cai,Jiahong Liao,Yi He,Chunlin Yu,Xingwang Zhang

The development of proton exchange membrane water electrolysis is a promising technology for hydrogen production, which has always been restricted by the slow kinetics of the oxygen evolution reaction (OER). Although IrOx is one of the benchmark acidic OER electrocatalysts, there are still challenges in designing highly active and stable Ir-based electrocatalysts for commercial application. Herein, a Ru-doped IrOx electrocatalyst with abundant twin boundaries (TB-Ru0.3Ir0.7Ox@ITO) is reported, employing indium tin oxide with high conductivity as the support material. Combing the TB-Ru0.3Ir0.7Ox nanoparticles with ITO support could expose more active sites and accelerate the electron transfer. The TB-Ru0.3Ir0.7Ox@ITO exhibits a low overpotential of 203 mV to achieve 10 mA cm–2 and a high mass activity of 854.45 A g–1noble metal at 1.53 V vs RHE toward acidic OER, which exceeds most reported Ir-based OER catalysts. Moreover, improved long-term stability could be obtained, maintaining the reaction for over 110 h at 10 mA cm–2 with negligible deactivation. DFT calculations further reveal the activity enhancement mechanism, demonstrating the synergistic effects of Ru doping and strains on the optimization of the d-band center (εd) position and the adsorption free energy of oxygen intermediates. This work provides ideas to realize the trade-off between high catalytic activity and good stability for acidic OER electrocatalysts.

研究领域: 材料科学 · 电化学 · 催化科学
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