Pub Date : 2025-07-25DOI: 10.1016/j.jmat.2025.101110
Kun Yang , Hyojun Choi , Ji Sang Ahn , Eun Ji Ju , Dong In Han , Se Hyun Kim , Ju Yong Park , Heejin Hong , Kwan Hyun Park , Jeong Hwan Han , Min Hyuk Park
The impact of oxygen content in the Ru electrode, grown using atomic layer deposition on ferroelectricity in Hf0.5Zr0.5O2 film is investigated. The oxygen content in Ru can be modulated by simply adjusting the deposition temperature from 210 °C to 300 °C. Higher oxygen content in Ru reduces the oxygen vacancy concentration in subsequently grown Hf0.5Zr0.5O2 film, thereby mitigating the wake-up effect. However, the monoclinic phase fraction increased with decreasing Ru deposition temperature, resulting in a decrease in remanent polarization. The decreased oxygen vacancy concentration by oxygen diffusion from Ru electrode deposited at 210 °C could decrease the leakage current density compared to that grown at higher temperatures. Nonetheless, the switching endurance of Hf0.5Zr0.5O2 film grown on Ru deposited at 210 °C was shorter than those on Ru deposited at 300 °C by 2 order of magnitude, being attributed to the oxygen diffusion caused interfacial damages. This observation suggests that the interfacial redox reactions between the electrode and Hf0.5Zr0.5O2 critically influence defect concentration, polymorphism, and the resulting ferroelectricity when using an atomic layer deposited Ru electrode to examine the impact of interfacial redox chemistry.
{"title":"Utilization of oxygen content modulated Ru electrode to examine the interfacial redox chemistry of ferroelectric Hf0.5Zr0.5O2","authors":"Kun Yang , Hyojun Choi , Ji Sang Ahn , Eun Ji Ju , Dong In Han , Se Hyun Kim , Ju Yong Park , Heejin Hong , Kwan Hyun Park , Jeong Hwan Han , Min Hyuk Park","doi":"10.1016/j.jmat.2025.101110","DOIUrl":"10.1016/j.jmat.2025.101110","url":null,"abstract":"<div><div>The impact of oxygen content in the Ru electrode, grown using atomic layer deposition on ferroelectricity in Hf<sub>0.5</sub>Zr<sub>0.5</sub>O<sub>2</sub> film is investigated. The oxygen content in Ru can be modulated by simply adjusting the deposition temperature from 210 °C to 300 °C. Higher oxygen content in Ru reduces the oxygen vacancy concentration in subsequently grown Hf<sub>0.5</sub>Zr<sub>0.5</sub>O<sub>2</sub> film, thereby mitigating the wake-up effect. However, the monoclinic phase fraction increased with decreasing Ru deposition temperature, resulting in a decrease in remanent polarization. The decreased oxygen vacancy concentration by oxygen diffusion from Ru electrode deposited at 210 °C could decrease the leakage current density compared to that grown at higher temperatures. Nonetheless, the switching endurance of Hf<sub>0.5</sub>Zr<sub>0.5</sub>O<sub>2</sub> film grown on Ru deposited at 210 °C was shorter than those on Ru deposited at 300 °C by 2 order of magnitude, being attributed to the oxygen diffusion caused interfacial damages. This observation suggests that the interfacial redox reactions between the electrode and Hf<sub>0.5</sub>Zr<sub>0.5</sub>O<sub>2</sub> critically influence defect concentration, polymorphism, and the resulting ferroelectricity when using an atomic layer deposited Ru electrode to examine the impact of interfacial redox chemistry.</div></div>","PeriodicalId":16173,"journal":{"name":"Journal of Materiomics","volume":"11 6","pages":"Article 101110"},"PeriodicalIF":9.6,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144710635","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-23DOI: 10.1016/j.jmat.2025.101109
Han Sol Park, Joong Chan Shin, Kyung Do Kim, Seong Jae Shin, Jae Hee Song, Seung Kyu Ryoo, In Soo Lee, Suk Hyun Lee, Hyunwoo Nam, Cheol Seong Hwang
This study clarifies the influence of single-layer (TiN, HfN, W) and bi-layer (HfN/TiN, W/TiN) bottom electrodes (BEs) on the ferroelectric performance and reliability of the 10-nm-thick Hf0.5Zr0.5O2 (HZO) thin films. A smaller thermal expansion coefficient in HfN or W imposes higher in-plane tensile stress on the HZO thin films, facilitating the polar orthorhombic (o-) phase fraction and enhancing remanent polarization (Pr). However, thicker interfacial layers formed when HfN or W single-layer BE and HZO contacted directly, leading to excessive leakage current and degraded ferroelectric performance. These excessive interfacial layers were effectively suppressed by inserting a thin (5 nm–20 nm) TiN layer on the HfN or W BEs. As a result, the HZO thin films on the HfN/TiN and W/TiN bi-layer BEs decrease the HZO grain size, facilitating the o-phase formation (increasing Pr) and lowering the film's coercive field. However, the higher surface roughness of the W/TiN bi-layer BEs induced excessive leakage current and reliability degradation. In contrast, the HfN BEs with a 10- or 20-nm-thick upper TiN layer lower the surface roughness of the BEs, thereby eliminating the adverse effects. As a result, the HfN 40 nm/TiN 10 nm/HZO/TiN stack exhibited enhanced ferroelectric performance up to 109 switching cycles with a lower cycling field of 2.7 MV/cm than the TiN 50 nm/HZO/TiN stack with a cycling field of 3.7 MV/cm.
{"title":"Enhancing ferroelectric properties of Hf0.5Zr0.5O2 thin films using the HfN/TiN and W/TiN bi-layer bottom electrodes","authors":"Han Sol Park, Joong Chan Shin, Kyung Do Kim, Seong Jae Shin, Jae Hee Song, Seung Kyu Ryoo, In Soo Lee, Suk Hyun Lee, Hyunwoo Nam, Cheol Seong Hwang","doi":"10.1016/j.jmat.2025.101109","DOIUrl":"10.1016/j.jmat.2025.101109","url":null,"abstract":"<div><div>This study clarifies the influence of single-layer (TiN, HfN, W) and bi-layer (HfN/TiN, W/TiN) bottom electrodes (BEs) on the ferroelectric performance and reliability of the 10-nm-thick Hf<sub>0.5</sub>Zr<sub>0.5</sub>O<sub>2</sub> (HZO) thin films. A smaller thermal expansion coefficient in HfN or W imposes higher in-plane tensile stress on the HZO thin films, facilitating the polar orthorhombic (o-) phase fraction and enhancing remanent polarization (<em>P</em><sub>r</sub>). However, thicker interfacial layers formed when HfN or W single-layer BE and HZO contacted directly, leading to excessive leakage current and degraded ferroelectric performance. These excessive interfacial layers were effectively suppressed by inserting a thin (5 nm–20 nm) TiN layer on the HfN or W BEs. As a result, the HZO thin films on the HfN/TiN and W/TiN bi-layer BEs decrease the HZO grain size, facilitating the o-phase formation (increasing <em>P</em><sub>r</sub>) and lowering the film's coercive field. However, the higher surface roughness of the W/TiN bi-layer BEs induced excessive leakage current and reliability degradation. In contrast, the HfN BEs with a 10- or 20-nm-thick upper TiN layer lower the surface roughness of the BEs, thereby eliminating the adverse effects. As a result, the HfN 40 nm/TiN 10 nm/HZO/TiN stack exhibited enhanced ferroelectric performance up to 10<sup>9</sup> switching cycles with a lower cycling field of 2.7 MV/cm than the TiN 50 nm/HZO/TiN stack with a cycling field of 3.7 MV/cm.</div></div>","PeriodicalId":16173,"journal":{"name":"Journal of Materiomics","volume":"11 6","pages":"Article 101109"},"PeriodicalIF":9.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684682","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-18DOI: 10.1016/j.jmat.2025.101101
Seong Jae Shin, Hani Kim, Seungyong Byun, Jonghoon Shin, Jinwoo Choi, Suk Hyun Lee, Kyung Do Kim, Jae Hee Song, Dong Hoon Shin, Soo Hyung Lee, In Soo Lee, Hyunwoo Nam, Cheol Seong Hwang
This study examined the effects of deposition temperature on Hf0.5Zr0.5O2 (HZO) thin films deposited using atomic layer deposition (ALD) with Tetrakis(ethylmethylamino) (TEMA) Hf, Zr, and cyclopentadienyl (CP)-linked Hf, Zr precursors. The discrete feeding method was utilized to stabilize the growth per cycle, addressing challenges related to CP-linked precursors' high viscosity and molecular mass. The ALD temperature windows for HfO2 and ZrO2 films using the CP-linked precursors were 330–370 °C and 290–330 °C, respectively, higher than those using the TEMA precursors (250–280 °C). Films deposited at higher temperatures with CP-linked precursors showed higher density and lower leakage currents than those with TEMA precursors, showing ferroelectric hysteresis loops from Hf0.5Zr0.5O2 (HZO) film at thicknesses as low as 5 nm without a wake-up process. In contrast, the film using TEMA precursor required a minimum thickness of 18 nm to exhibit similar properties. Crystallographic analysis revealed improved crystallization, larger grain sizes, and lower tensile stress in films deposited at higher temperatures. Also, in-situ crystallization was achievable for HZO films thicker than 6 nm when deposited at elevated temperatures. These findings demonstrate that higher temperature deposition by adopting CP-linked precursors enhances HZO thin film properties, making them suitable for advanced ferroelectric memory applications.
{"title":"Influence of deposition temperature and precursor chemistry on the properties of atomic layer deposited Hf0.5Zr0.5O2 thin films","authors":"Seong Jae Shin, Hani Kim, Seungyong Byun, Jonghoon Shin, Jinwoo Choi, Suk Hyun Lee, Kyung Do Kim, Jae Hee Song, Dong Hoon Shin, Soo Hyung Lee, In Soo Lee, Hyunwoo Nam, Cheol Seong Hwang","doi":"10.1016/j.jmat.2025.101101","DOIUrl":"10.1016/j.jmat.2025.101101","url":null,"abstract":"<div><div>This study examined the effects of deposition temperature on Hf<sub>0.5</sub>Zr<sub>0.5</sub>O<sub>2</sub> (HZO) thin films deposited using atomic layer deposition (ALD) with Tetrakis(ethylmethylamino) (TEMA) Hf, Zr, and cyclopentadienyl (CP)-linked Hf, Zr precursors. The discrete feeding method was utilized to stabilize the growth per cycle, addressing challenges related to CP-linked precursors' high viscosity and molecular mass. The ALD temperature windows for HfO<sub>2</sub> and ZrO<sub>2</sub> films using the CP-linked precursors were 330–370 °C and 290–330 °C, respectively, higher than those using the TEMA precursors (250–280 °C). Films deposited at higher temperatures with CP-linked precursors showed higher density and lower leakage currents than those with TEMA precursors, showing ferroelectric hysteresis loops from Hf<sub>0.5</sub>Zr<sub>0.5</sub>O<sub>2</sub> (HZO) film at thicknesses as low as 5 nm without a wake-up process. In contrast, the film using TEMA precursor required a minimum thickness of 18 nm to exhibit similar properties. Crystallographic analysis revealed improved crystallization, larger grain sizes, and lower tensile stress in films deposited at higher temperatures. Also, <em>in-situ</em> crystallization was achievable for HZO films thicker than 6 nm when deposited at elevated temperatures. These findings demonstrate that higher temperature deposition by adopting CP-linked precursors enhances HZO thin film properties, making them suitable for advanced ferroelectric memory applications.</div></div>","PeriodicalId":16173,"journal":{"name":"Journal of Materiomics","volume":"11 6","pages":"Article 101101"},"PeriodicalIF":9.6,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319426","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-18DOI: 10.1016/j.jmat.2025.101103
Junxi Yu , Yuan Zhang , Songjie Yang , Chunlin Song , Shiyao Xu , Boyuan Huang , Qingyuan Wang , Jiangyu Li
Two-dimensional (2D) molybdenum disulfide (MoS2) has shown considerable potential for photodetection, yet existing MoS2-based photodetectors require either external voltage bias or complex heterojunctions. In this work, we present a new device concept based on flexoelectric engineering of bulk photovoltaic effect (BPVE) of 2HMoS2, simplifying the device configuration considerably while enhancing its self-powered photodetection performance. By introducing a strain gradient in the suspended 2HMoS2, we break its inversion symmetry, resulting in BPVE in the otherwise centrosymmetric system. The significant flexoelectric polarization induced also facilitates efficient photocarrier separation, leading to a 41-fold enhancement in short-circuit photocurrent under a strain gradient of . Furthermore, the flexoelectric-engineered photodetector can be dynamically tuned via air pressure, enabling multilevel photoconductance and achieving a responsivity of 191 mA/W. This performance surpasses existing self-powered MoS2-based photodetectors reported in literature, offering a strategy for enhanced photodetection.
{"title":"Self-powered tunable photodetection via flexoelectric engineering of single-phase 2HMoS2","authors":"Junxi Yu , Yuan Zhang , Songjie Yang , Chunlin Song , Shiyao Xu , Boyuan Huang , Qingyuan Wang , Jiangyu Li","doi":"10.1016/j.jmat.2025.101103","DOIUrl":"10.1016/j.jmat.2025.101103","url":null,"abstract":"<div><div>Two-dimensional (2D) molybdenum disulfide (MoS<sub>2</sub>) has shown considerable potential for photodetection, yet existing MoS<sub>2</sub>-based photodetectors require either external voltage bias or complex heterojunctions. In this work, we present a new device concept based on flexoelectric engineering of bulk photovoltaic effect (BPVE) of 2H<img>MoS<sub>2</sub>, simplifying the device configuration considerably while enhancing its self-powered photodetection performance. By introducing a strain gradient in the suspended 2H<img>MoS<sub>2</sub>, we break its inversion symmetry, resulting in BPVE in the otherwise centrosymmetric system. The significant flexoelectric polarization induced also facilitates efficient photocarrier separation, leading to a 41-fold enhancement in short-circuit photocurrent under a strain gradient of <span><math><mn>0.95</mn><mspace></mspace><msup><mi>μm</mi><mrow><mo>−</mo><mn>1</mn></mrow></msup></math></span>. Furthermore, the flexoelectric-engineered photodetector can be dynamically tuned <em>via</em> air pressure, enabling multilevel photoconductance and achieving a responsivity of 191 mA/W. This performance surpasses existing self-powered MoS<sub>2</sub>-based photodetectors reported in literature, offering a strategy for enhanced photodetection.</div></div>","PeriodicalId":16173,"journal":{"name":"Journal of Materiomics","volume":"11 6","pages":"Article 101103"},"PeriodicalIF":8.4,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144311736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-30DOI: 10.1016/j.jmat.2025.101089
Sitong Luo , Yujin Wang , Jingxuan Liang , Yuntian Jiang , Zhibo Wei , Yifan Du , Liang Lv , Shuqi Zheng , Weiyu Song
CuGaTe2 is p-type thermoelectric material with high thermoelectric potential. However, its performance is hindered by its intrinsic high resistivity and thermal conductivity. In this study, a synergistic strategy combining band engineering and chemical bonding modulation is employed to simultaneously optimize the electrical and thermal transport properties of CuGaTe2. First-principles calculations reveal that Cd preferentially occupy Ga sites, leading to bandgap narrowing and increasing density of states near Fermi level. Consequently, both carrier concentration and density-of-states effective mass are simultaneously optimized, ultimately power factor reaches 1359 μW·m−1·K−2. Phonon dispersion analysis reveals that Cd doping induces acoustic-optical phonon avoided crossing behavior, decelerating phonon velocity. Combined with the increase of Grüneisen parameter and weakened chemical bonding, which significantly enhances lattice anharmonicity, leading to effectively reduce in lattice thermal conductivity. Microstructural characterization further reveals that CdTe doping leads to the formation of three-dimensional defect network consisting of point defects, dislocations, and stacking faults enhances phonon scattering. Ultimately, lattice thermal conductivity of doped sample is reduced to 0.81 W·m−1·K−1. Consequently, (CuGaTe2)0.9975(2CdTe)0.0025 sample achieves enhanced zT of 1.05 at 823 K. This work provides insights into the synergistic effects of band engineering and chemical bonding modulation, offering pathway for the design of thermoelectric materials.
{"title":"Realizing high thermoelectric performance of CuGaTe2 via CdTe-doping-driven band engineering and chemical bond modulation","authors":"Sitong Luo , Yujin Wang , Jingxuan Liang , Yuntian Jiang , Zhibo Wei , Yifan Du , Liang Lv , Shuqi Zheng , Weiyu Song","doi":"10.1016/j.jmat.2025.101089","DOIUrl":"10.1016/j.jmat.2025.101089","url":null,"abstract":"<div><div>CuGaTe<sub>2</sub> is p-type thermoelectric material with high thermoelectric potential. However, its performance is hindered by its intrinsic high resistivity and thermal conductivity. In this study, a synergistic strategy combining band engineering and chemical bonding modulation is employed to simultaneously optimize the electrical and thermal transport properties of CuGaTe<sub>2</sub>. First-principles calculations reveal that Cd preferentially occupy Ga sites, leading to bandgap narrowing and increasing density of states near Fermi level. Consequently, both carrier concentration and density-of-states effective mass are simultaneously optimized, ultimately power factor reaches 1359 μW·m<sup>−1</sup>·K<sup>−2</sup>. Phonon dispersion analysis reveals that Cd doping induces acoustic-optical phonon avoided crossing behavior, decelerating phonon velocity. Combined with the increase of Grüneisen parameter and weakened chemical bonding, which significantly enhances lattice anharmonicity, leading to effectively reduce in lattice thermal conductivity. Microstructural characterization further reveals that CdTe doping leads to the formation of three-dimensional defect network consisting of point defects, dislocations, and stacking faults enhances phonon scattering. Ultimately, lattice thermal conductivity of doped sample is reduced to 0.81 W·m<sup>−1</sup>·K<sup>−1</sup>. Consequently, (CuGaTe<sub>2</sub>)<sub>0.9975</sub>(2CdTe)<sub>0.0025</sub> sample achieves enhanced <em>zT</em> of 1.05 at 823 K. This work provides insights into the synergistic effects of band engineering and chemical bonding modulation, offering pathway for the design of thermoelectric materials.</div></div>","PeriodicalId":16173,"journal":{"name":"Journal of Materiomics","volume":"11 6","pages":"Article 101089"},"PeriodicalIF":8.4,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176969","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-30DOI: 10.1016/j.jmat.2025.101090
Qi Zhao , Zhen Fan , Yi Wang , Qiulin Liu , Xuejuan Dong , Xiaowei Wu , Zhicheng Shan , Hangtian Zhu , Zhiliang Li , Shufang Wang , Huaizhou Zhao
High-strength high-performance p-type (Bi,Sb)2Te3 are of pivotal importance for near-room-temperature thermoelectric conversions, the reliable synthesis and fabrication has been viewed of imperative priority. It is known that the energy-favorable formation of anti-site SbTe’ and vacancy vSb''' acceptor defects from high-temperature syntheses results in additional charge carriers and scattering centers for electrical and phonon transport. However, how p-type (Bi,Sb)2Te3 with minimal lattice defects function remains to be scrutinized. Herein, we present the synergistic enhancements of mechanical robustness and thermoelectric property in crystallographic-defect-suppressed pristine (Bi,Sb)2Te3 through a simple mechanical alloying combined with spark-plasma-sintering (SPS) process. The SbTe’ and vSb''' acceptor defects were efficiently restrained, contributing to markedly increased charge carrier mobilities. A slightly enlarged band gap of 0.24 eV underpinned enhanced thermoelectric performance for pristine Bi0.3Sb1.7Te3 over a wide temperature range, delivering high zT300 K of 1.16 and zTave of 1.21 over 300–473 K. Interestingly, the confined in-situ grain coarsening during SPS with uniform dispersive nanopores readily endowed an ultra-high compressive strength of 206 MPa, surpassing that of reported (Bi,Sb)2Te3 so far. A 7-pair module (coupled with n-Bi2Te3) was fabricated, demonstrating a competitive ΔT over 70 K at Thot = 300 K. Furthermore, a power-generation module coupled with n-Mg3SbBi registered a cutting-edge thermoelectric conversion efficiency of 9.5% at a temperature gradient of 250 K. The strategy eliminates the need of complex processing nor extrinsic doping for pristine (Bi,Sb)2Te3, demonstrating great potentials in thermoelectric power generation and cooling applications.
{"title":"Atomic-defect-suppressed pristine p-type Bi0.3Sb1.7Te3 as robust high-performance thermoelectrics for power generation and cooling","authors":"Qi Zhao , Zhen Fan , Yi Wang , Qiulin Liu , Xuejuan Dong , Xiaowei Wu , Zhicheng Shan , Hangtian Zhu , Zhiliang Li , Shufang Wang , Huaizhou Zhao","doi":"10.1016/j.jmat.2025.101090","DOIUrl":"10.1016/j.jmat.2025.101090","url":null,"abstract":"<div><div>High-strength high-performance p-type (Bi,Sb)<sub>2</sub>Te<sub>3</sub> are of pivotal importance for near-room-temperature thermoelectric conversions, the reliable synthesis and fabrication has been viewed of imperative priority. It is known that the energy-favorable formation of anti-site Sb<sub>Te</sub><sup>’</sup> and vacancy v<sub>Sb</sub><sup>'''</sup> acceptor defects from high-temperature syntheses results in additional charge carriers and scattering centers for electrical and phonon transport. However, how p-type (Bi,Sb)<sub>2</sub>Te<sub>3</sub> with minimal lattice defects function remains to be scrutinized. Herein, we present the synergistic enhancements of mechanical robustness and thermoelectric property in crystallographic-defect-suppressed pristine (Bi,Sb)<sub>2</sub>Te<sub>3</sub> through a simple mechanical alloying combined with spark-plasma-sintering (SPS) process. The Sb<sub>Te</sub><sup>’</sup> and v<sub>Sb</sub><sup>'''</sup> acceptor defects were efficiently restrained, contributing to markedly increased charge carrier mobilities. A slightly enlarged band gap of 0.24 eV underpinned enhanced thermoelectric performance for pristine Bi<sub>0.3</sub>Sb<sub>1.7</sub>Te<sub>3</sub> over a wide temperature range, delivering high <em>zT</em><sub>300 K</sub> of 1.16 and <em>zT</em><sub>ave</sub> of 1.21 over 300–473 K. Interestingly, the confined <em>in-situ</em> grain coarsening during SPS with uniform dispersive nanopores readily endowed an ultra-high compressive strength of 206 MPa, surpassing that of reported (Bi,Sb)<sub>2</sub>Te<sub>3</sub> so far. A 7-pair module (coupled with n-Bi<sub>2</sub>Te<sub>3</sub>) was fabricated, demonstrating a competitive Δ<em>T</em> over 70 K at <em>T</em><sub>hot</sub> = 300 K. Furthermore, a power-generation module coupled with n-Mg<sub>3</sub>SbBi registered a cutting-edge thermoelectric conversion efficiency of 9.5% at a temperature gradient of 250 K. The strategy eliminates the need of complex processing nor extrinsic doping for pristine (Bi,Sb)<sub>2</sub>Te<sub>3</sub>, demonstrating great potentials in thermoelectric power generation and cooling applications.</div></div>","PeriodicalId":16173,"journal":{"name":"Journal of Materiomics","volume":"11 6","pages":"Article 101090"},"PeriodicalIF":8.4,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144183760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-29DOI: 10.1016/j.jmat.2025.101091
Zhixing Wan , Shuo Wang , Yahao Mu , Ruihua Zhou , Hang Liu , Tingwu Jin , Di Wu , Jianlong Xia , Ce-Wen Nan
Organic cathode materials have garnered significant attention for their potential application in lithium-ion batteries due to their lightweight nature, tunable structures, high energy density, and environmental friendliness. However, the dissolution of organic cathodes in liquid electrolytes often leads to poor cycling stability, which limits their practical application. In this study, a composite cathode was prepared by ball milling the PTCDA/CuS (perylene-3,4,9,10-tetracarboxylic dianhydride, PTCDA) with a sulfide-based electrolyte and carbon nanotubes. By optimizing the component ratios, the assembled all-solid-state batteries (ASSBs) show a high discharge capacity of 210 mA⸱h/g after 200 cycles without any capacity degradation at a current density of 33.0 mA/g. Through comprehensive characterization techniques including X-ray diffraction (XRD), Raman spectroscopy, Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), the coordination of Cu2+ and the formation of sulfur-linked polymers during the charge-discharge processes are elucidated, and the reversibility of the electrochemical reactions has been confirmed. This work highlights the excellent compatibility between organic cathodes and sulfide-based electrolytes, providing a new way for the development of high-performance ASSBs with high energy density and extended lifespan.
{"title":"PTCDA/CuS cathode enabling stable sulfide-based all-solid-state batteries","authors":"Zhixing Wan , Shuo Wang , Yahao Mu , Ruihua Zhou , Hang Liu , Tingwu Jin , Di Wu , Jianlong Xia , Ce-Wen Nan","doi":"10.1016/j.jmat.2025.101091","DOIUrl":"10.1016/j.jmat.2025.101091","url":null,"abstract":"<div><div>Organic cathode materials have garnered significant attention for their potential application in lithium-ion batteries due to their lightweight nature, tunable structures, high energy density, and environmental friendliness. However, the dissolution of organic cathodes in liquid electrolytes often leads to poor cycling stability, which limits their practical application. In this study, a composite cathode was prepared by ball milling the PTCDA/CuS (perylene-3,4,9,10-tetracarboxylic dianhydride, PTCDA) with a sulfide-based electrolyte and carbon nanotubes. By optimizing the component ratios, the assembled all-solid-state batteries (ASSBs) show a high discharge capacity of 210 mA⸱h/g after 200 cycles without any capacity degradation at a current density of 33.0 mA/g. Through comprehensive characterization techniques including X-ray diffraction (XRD), Raman spectroscopy, Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), the coordination of Cu<sup>2+</sup> and the formation of sulfur-linked polymers during the charge-discharge processes are elucidated, and the reversibility of the electrochemical reactions has been confirmed. This work highlights the excellent compatibility between organic cathodes and sulfide-based electrolytes, providing a new way for the development of high-performance ASSBs with high energy density and extended lifespan.</div></div>","PeriodicalId":16173,"journal":{"name":"Journal of Materiomics","volume":"12 1","pages":"Article 101091"},"PeriodicalIF":9.6,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144176964","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-24DOI: 10.1016/j.jmat.2025.101077
Cangjin Li, Manwen Yao, Xi Yao, Chunyu Li
For multilayer ceramic capacitors, co-sintering of ceramics with inner electrodes is a crucial issue. This requires ceramic materials to have a low sintering temperature. In response to this criterion, a hybrid processing technology is proposed in this study. This technology involves mixing of calcined ceramic powders with sol solutions to obtain composite powders. Eventually, sintering temperature of the obtained composite material is reduced from 1300 °C to 1120 °C. This is originated from the introduction of more specific surface areas and more oxygen vacancies by sol solutions, leading to an enhancement of chemical reaction activity. The ceramic powders and the sol solutions used in this work are (Pb0.94La0.04)(Zr0.51Sn0.47Hf0.01Ti0.01)O3 and (Pb0.97La0.02)(Zr0.6Sn0.4)O3, respectively. Such composition design helps improve the dielectric constant and polarization intensity. While in the meantime, because of the strong interfacial resistance caused by sol solutions, interfacial insulation as well as electrical breakdown strength can be significantly improved. Consequently, a high energy storage density up to 12.4 J/cm3 and an efficiency of 92.4% is obtained in this work. Overall, this technology is applicable to a wide range of ceramic material systems, and provides an innovative design and manufacture of ceramics.
{"title":"A hybrid processing technology for fabricating lead zirconate-based ceramics with high energy storage density, high efficiency, and low sintering temperature","authors":"Cangjin Li, Manwen Yao, Xi Yao, Chunyu Li","doi":"10.1016/j.jmat.2025.101077","DOIUrl":"10.1016/j.jmat.2025.101077","url":null,"abstract":"<div><div>For multilayer ceramic capacitors, co-sintering of ceramics with inner electrodes is a crucial issue. This requires ceramic materials to have a low sintering temperature. In response to this criterion, a hybrid processing technology is proposed in this study. This technology involves mixing of calcined ceramic powders with sol solutions to obtain composite powders. Eventually, sintering temperature of the obtained composite material is reduced from 1300 °C to 1120 °C. This is originated from the introduction of more specific surface areas and more oxygen vacancies by sol solutions, leading to an enhancement of chemical reaction activity. The ceramic powders and the sol solutions used in this work are (Pb<sub>0.94</sub>La<sub>0.04</sub>)(Zr<sub>0.51</sub>Sn<sub>0.47</sub>Hf<sub>0.01</sub>Ti<sub>0.01</sub>)O<sub>3</sub> and (Pb<sub>0.97</sub>La<sub>0.02</sub>)(Zr<sub>0.6</sub>Sn<sub>0.4</sub>)O<sub>3</sub>, respectively. Such composition design helps improve the dielectric constant and polarization intensity. While in the meantime, because of the strong interfacial resistance caused by sol solutions, interfacial insulation as well as electrical breakdown strength can be significantly improved. Consequently, a high energy storage density up to 12.4 J/cm<sup>3</sup> and an efficiency of 92.4% is obtained in this work. Overall, this technology is applicable to a wide range of ceramic material systems, and provides an innovative design and manufacture of ceramics.</div></div>","PeriodicalId":16173,"journal":{"name":"Journal of Materiomics","volume":"11 6","pages":"Article 101077"},"PeriodicalIF":8.4,"publicationDate":"2025-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144130452","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, the inequivalent substitution of Ca2+ by Li+ in the Ca3Co2SiV2O12 compound was designed to modulate its sintering characteristics and microwave dielectric properties. The corresponding Ca3–xLi2xCo2SiV2O12 (CCSV-xLi, 0.01≤ x ≤ 0.07) ceramics were prepared via the conventional solid-state phase method, which could be densely sintered at a temperature below 1140 °C. Rietveld refinement results suggested that all the doped Li occupied the Ca-site as x ≤ 0.05 while superfluous Li positioned at the Co-site of CCSV when x = 0.07. This atomic occupancy had a remarkable effect on the degree of “rattling effect” and thus modulated the relative permittivity of ceramics, constantly increasing at x = 0.01–0.05 and slightly decreasing at x = 0.07. Raman spectra revealed that Q×f value was closely related to Raman shift and FWHM. Also, the Q×f value was partly influenced by oxygen vacancy concentration. The τf demonstrated an opposite tendency to the bond valence of the A-site and was affected by the “rattling effect”. The CCSV-0.05Li ceramic sintered at 1120 °C possessed excellent microwave dielectric properties: εr = 12.17, Q×f = 56,220 GHz, and τf = −8.5 × 10−6 °C−1.
{"title":"Modulation in sintering characteristics and microwave dielectric properties of Ca3Co2SiV2O12 via Li+ inequivalent substitution","authors":"Zhenli Tao, Jiamao Li, Junxian Wang, Yuxuan Ren, Yunfeng Guo, Qinghe Yang, Zhihao Yuan, Rui Tian, Wenbo Wang","doi":"10.1016/j.jmat.2025.101074","DOIUrl":"10.1016/j.jmat.2025.101074","url":null,"abstract":"<div><div>In this study, the inequivalent substitution of Ca<sup>2+</sup> by Li<sup>+</sup> in the Ca<sub>3</sub>Co<sub>2</sub>SiV<sub>2</sub>O<sub>12</sub> compound was designed to modulate its sintering characteristics and microwave dielectric properties. The corresponding Ca<sub>3–<em>x</em></sub>Li<sub>2<em>x</em></sub>Co<sub>2</sub>SiV<sub>2</sub>O<sub>12</sub> (CCSV-<em>x</em>Li, 0.01≤ <em>x</em> ≤ 0.07) ceramics were prepared <em>via</em> the conventional solid-state phase method, which could be densely sintered at a temperature below 1140 °C. Rietveld refinement results suggested that all the doped Li occupied the Ca-site as <em>x</em> ≤ 0.05 while superfluous Li positioned at the Co-site of CCSV when <em>x</em> = 0.07. This atomic occupancy had a remarkable effect on the degree of “rattling effect” and thus modulated the relative permittivity of ceramics, constantly increasing at <em>x</em> = 0.01–0.05 and slightly decreasing at <em>x</em> = 0.07. Raman spectra revealed that <em>Q</em>×<em>f</em> value was closely related to Raman shift and FWHM. Also, the <em>Q</em>×<em>f</em> value was partly influenced by oxygen vacancy concentration. The <em>τ</em><sub>f</sub> demonstrated an opposite tendency to the bond valence of the A-site and was affected by the “rattling effect”. The CCSV-0.05Li ceramic sintered at 1120 °C possessed excellent microwave dielectric properties: <em>ε</em><sub>r</sub> = 12.17, <em>Q</em>×<em>f</em> = 56,220 GHz, and <em>τ</em><sub>f</sub> = −8.5 × 10<sup>−6</sup> °C<sup>−1</sup>.</div></div>","PeriodicalId":16173,"journal":{"name":"Journal of Materiomics","volume":"11 6","pages":"Article 101074"},"PeriodicalIF":8.4,"publicationDate":"2025-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933325","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-10DOI: 10.1016/j.jmat.2025.101076
Peng Yan , Mingming Si , Yongping Liu, Yu Ren, Jie Min, Xu Wang, Qi Ding, Weizhong Jiang, Yuchi Fan, Wan Jiang
Cold-sintered ceramics typically exhibit inferior mechanical properties compared to high-temperature sintered counterparts. We demonstrate that introducing large internal stress through highly concentrated nanodiamonds (NDs) significantly enhances cold-sintered α-quartz composites to structural ceramic levels. At 500 MPa cold-sintering pressure, uniformly dispersed NDs generate 1.2 GPa local prestress via Young's modulus difference, while pressure-modulated internal stress is evidenced by dielectric property changes. The optimized composite achieves fracture toughness of (3.65 ± 0.21) MPa·m1/2 (180% increase) and Vickers hardness of 10.6 GPa (80% increase), matching some high-temperature-sintered ceramics. Toughening arises from prestress-driven crack deflection and crack tip bridging, while hardness enhancement stems from NDs' rigid constraint and high-pressure-induced dislocations in silica matrix. Compressive strength increases by 90% and fatigue life exceeds 1000 cycles, attributed to internal stress-strengthened grain boundaries and improved toughness. This work presents a transformative strategy for developing damage-resistant ceramics, meriting further exploration of scalability and engineering applications.
{"title":"Hard, strong, and tough cold-sintered α-quartz composites as high-performance structural ceramics","authors":"Peng Yan , Mingming Si , Yongping Liu, Yu Ren, Jie Min, Xu Wang, Qi Ding, Weizhong Jiang, Yuchi Fan, Wan Jiang","doi":"10.1016/j.jmat.2025.101076","DOIUrl":"10.1016/j.jmat.2025.101076","url":null,"abstract":"<div><div>Cold-sintered ceramics typically exhibit inferior mechanical properties compared to high-temperature sintered counterparts. We demonstrate that introducing large internal stress through highly concentrated nanodiamonds (NDs) significantly enhances cold-sintered α-quartz composites to structural ceramic levels. At 500 MPa cold-sintering pressure, uniformly dispersed NDs generate 1.2 GPa local prestress <em>via</em> Young's modulus difference, while pressure-modulated internal stress is evidenced by dielectric property changes. The optimized composite achieves fracture toughness of (3.65 ± 0.21) MPa·m<sup>1</sup>/<sup>2</sup> (180% increase) and Vickers hardness of 10.6 GPa (80% increase), matching some high-temperature-sintered ceramics. Toughening arises from prestress-driven crack deflection and crack tip bridging, while hardness enhancement stems from NDs' rigid constraint and high-pressure-induced dislocations in silica matrix. Compressive strength increases by 90% and fatigue life exceeds 1000 cycles, attributed to internal stress-strengthened grain boundaries and improved toughness. This work presents a transformative strategy for developing damage-resistant ceramics, meriting further exploration of scalability and engineering applications.</div></div>","PeriodicalId":16173,"journal":{"name":"Journal of Materiomics","volume":"11 6","pages":"Article 101076"},"PeriodicalIF":8.4,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143930994","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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