Article(id=1320090117050581734, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320090116236882876, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20240694, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1730390400000, receivedDateStr=2024-11-01, revisedDate=1735315200000, revisedDateStr=2024-12-28, acceptedDate=null, acceptedDateStr=null, onlineDate=1792663609992, onlineDateStr=2026-10-22, pubDate=1745078400000, pubDateStr=2025-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792663609992, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792663609992, creator=13701087609, updateTime=1792663609992, updator=13701087609, issue=Issue{id=1320090116236882876, tenantId=1146029695717560320, journalId=1263187385517883426, year='2025', volume='53', issue='4', pageStart='733', pageEnd='1030', issueExtLink='null', onlineDate='null', pubDate='1745078400000', pubDateStr='2025-04-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792663609799, creator='13701087609', updateTime=1792663788359, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320090865276670951, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320090116236882876, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320090865276670952, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320090116236882876, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=759, endPage=768, ext={EN=ArticleExt(id=1320090117306434279, articleId=1320090117050581734, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Effect of Mn Doping on Pyroelectric Properties of 0.96NaNbO3-0.04BaTiO3 Ceramics, columnId=1321897768591937660, journalTitle=Journal of the Chinese Ceramic Society, columnName=Special Issue on the 14th Inorganic and Non-metallic Materials Conference—Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction

Pyroelectric materials are widely used in the field of infrared detection. With the development of miniaturization and integration of devices, it is particularly important to develop lead-free pyroelectric sensitive elements with superior pyroelectric properties and high depolarization temperature compatible with reflow soldering process. In this paper, different mass fractions of Mn ions were doped into 0.96NaNbO3-0.04BaTiO3 matrix materials via a component gradient design. The effect of doping amount on the microstructure, ferroelectric properties, dielectric and pyroelectric properties of 0.96NaNbO3-0.04BaTiO3 ceramics was systematically investigated. The results show that when the doping amount of Mn is 0.4%, the ceramics have the optimum pyroelectric properties, which has a practical prospect of uncooled infrared detection.

Methods

All the components of sodium niobate ceramics were prepared by a solid-phase sintering method. The series of components were weighed according to the stoichiometric ratio, and the raw materials with anhydrous ethanol were ground in a stirred bead mill with zirconia beads at 400 r/min for 6 h. After being dried and shaped, the ground material was was pre-sintered at 1000 ℃ for 4 h, and then subjected to milling and drying. Green wafers with a diameter of 12 mm were prepared by pressure cold isostatic pressing at 200 MPa for 5 min after adding 10% PVA. The wafers were degummed at 600 ℃ for 2 h to remove organic matter and other impurities. To prevent the volatilization of sodium at a high temperature, the padding with the same composition was used for burial treatment, and the padding was kept at the corresponding temperature for 3 h and then cooled naturally. The sintered ceramic wafers were ground to fine particles with the size of 300 μm, coated with silver electrodes on both sides, and polarized in silicone oil under an electric field of 8-10 kV/mm at 80 ℃ for 15 min. The electrical properties were tested after 24 h.

Results and discussion

The microstructural morphology, dielectric properties, temperature stability, and pyroelectric properties of 0.96NN-0.04BT ceramics doped with 0-0.6% Mn are investigated. The results show that doping Mn ions significantly improves the sintering characteristics of 0.96NN-0.04BT ceramics, enhances the density, and the relative densities of all components reach above 90%. The NN-BT ceramic grain size increases with the increase of the doping amount. The substitution position of Mn ions causes changes in the electrical properties of the ceramic as the Mn doping content increases gradually. The concentration of oxygen vacancies caused by Na+ evaporation decreases when Mn ions substitute for A-site vacancies, which is beneficial to reducing the ceramic dielectric constant and dielectric loss, thus significantly improving the detection sensitivity factor. However, as the Mn doping content further increases, the imbalance of charges is prone to attract oxygen vacancies to form defect dipoles due to the heterovalent substitution of Mn ions on the B-site, thereby producing domain wall pinning effects. Also, the defect dipoles cause the increasing coercive field of the doped material and make it difficult to fully polarize, resulting in the material that is unable to fully utilize its pyroelectric properties.

Conclusions

The ceramic could have more suitable characteristics for pyroelectric requirements via appropriately adjusting the Mn doping concentration. The ceramic with Mn ion doping mass fraction of 0.4% had the optimal pyroelectric performance (i.e., the pyroelectric coefficient of 2.11×10-8 C·cm-2·K-1, and the Fv value of 3.74×10-2 m2·C-1), which was greater than 1.3 times and 1.8 times of the un-doped component. The coercive field reduced from 4.04 kV/mm of the un-doped component to 3.17 kV/mm, which was decreased by 21.5%. The results of the thermal stability test proved that the depolarization temperature could be maintained at 310 ℃, which had a practical prospect for non-cooled infrared detection.

, authors=Yiyang LIU, Fangjie CEN, Mingzhi FAN, Fangyuan LUO, Shenglin JIANG, Kanghua LI, Guangzu ZHANG, authorsList=Yiyang LIU, Fangjie CEN, Mingzhi FAN, Fangyuan LUO, Shenglin JIANG, Kanghua LI, Guangzu ZHANG, authorCompany=null, correspAuthors=Kanghua LI, Guangzu ZHANG, authorNote=

LIU Yiyang (2000-), male, Master candidate; E-mail: ;

CEN Fangjie (1997-), male, Doctoral candidate.

, correspAuthorsNote=
ZHANG Guangzu (1984-), male, Ph.D., Professor; E-mail: ;
LI Kanghua (1993-), male, Ph.D., Associate Professor.
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热释电材料在红外探测领域应用广泛,随着器件不断向小型化、集成化方向发展,开发兼具优异热释电性能和高退极化温度的无铅热释电材料显得尤为重要。通过组分梯度设计,向0.96NaNbO3-0.04BaTiO3基体材料中掺杂不同质量分数的Mn离子,系统研究了掺杂量对0.96NaNbO3-0.04BaTiO3陶瓷的显微结构、铁电性能、介电和热释电性能的影响。研究结果表明,当Mn掺杂为0.4%(质量分数)时,陶瓷在该组分下具有最佳热释电性能,其中热释电系数为2.11×10-8 C·cm-2·K-1,电压优值因子为3.74×10-2 m2·C-1,且通过250 ℃高温处理5 min后,热释电系数没有明显下降,表明该组分具有非制冷红外探测应用前景。

, authors=刘亦扬, 岑方杰, 范明智, 罗方苑, 姜胜林, 李康华, 张光祖, authorsList=刘亦扬, 岑方杰, 范明智, 罗方苑, 姜胜林, 李康华, 张光祖, authorCompany=null, correspAuthors=李康华, 张光祖, authorNote=

刘亦扬(2000—),男,硕士研究生;

岑方杰(1997—),男,博士研究生。

, correspAuthorsNote=
张光祖(1984—),男,博士,教授;
李康华(1993—)男,博士,副教授。
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锰掺杂对0.96NaNbO3-0.04BaTiO3陶瓷热释电性能的影响
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刘亦扬 , 岑方杰 , 范明智 , 罗方苑 , 姜胜林 , 李康华 , 张光祖
硅酸盐学报 | 第14届无机非金属材料专题研讨会专题—研究论文 2025,53(4): 759-768
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硅酸盐学报 |第14届无机非金属材料专题研讨会专题—研究论文 2025 , 53 (4) : 759 -768
锰掺杂对0.96NaNbO3-0.04BaTiO3陶瓷热释电性能的影响
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刘亦扬 , 岑方杰 , 范明智, 罗方苑, 姜胜林, 李康华 , 张光祖
作者信息
  • 华中科技大学集成电路学院,武汉 430074
通讯作者:
张光祖(1984—),男,博士,教授;
李康华(1993—)男,博士,副教授。
作者简介:

刘亦扬(2000—),男,硕士研究生;

岑方杰(1997—),男,博士研究生。

Effect of Mn Doping on Pyroelectric Properties of 0.96NaNbO3-0.04BaTiO3 Ceramics
Yiyang LIU , Fangjie CEN , Mingzhi FAN, Fangyuan LUO, Shenglin JIANG, Kanghua LI , Guangzu ZHANG
Affiliations
  • School of Integrated Circuits, Huazhong University of Science and Technology, Wuhan 430074, China
  • Corresponding Author:
    ZHANG Guangzu (1984-), male, Ph.D., Professor; E-mail: ;
    LI Kanghua (1993-), male, Ph.D., Associate Professor.

    LIU Yiyang (2000-), male, Master candidate; E-mail: ;

    CEN Fangjie (1997-), male, Doctoral candidate.

出版时间: 2025-04-20 doi: 10.14062/j.issn.0454-5648.20240694
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热释电材料在红外探测领域应用广泛,随着器件不断向小型化、集成化方向发展,开发兼具优异热释电性能和高退极化温度的无铅热释电材料显得尤为重要。通过组分梯度设计,向0.96NaNbO3-0.04BaTiO3基体材料中掺杂不同质量分数的Mn离子,系统研究了掺杂量对0.96NaNbO3-0.04BaTiO3陶瓷的显微结构、铁电性能、介电和热释电性能的影响。研究结果表明,当Mn掺杂为0.4%(质量分数)时,陶瓷在该组分下具有最佳热释电性能,其中热释电系数为2.11×10-8 C·cm-2·K-1,电压优值因子为3.74×10-2 m2·C-1,且通过250 ℃高温处理5 min后,热释电系数没有明显下降,表明该组分具有非制冷红外探测应用前景。

铌酸钠陶瓷  /  热释电陶瓷  /  锰掺杂  /  高退极化温度
Introduction

Pyroelectric materials are widely used in the field of infrared detection. With the development of miniaturization and integration of devices, it is particularly important to develop lead-free pyroelectric sensitive elements with superior pyroelectric properties and high depolarization temperature compatible with reflow soldering process. In this paper, different mass fractions of Mn ions were doped into 0.96NaNbO3-0.04BaTiO3 matrix materials via a component gradient design. The effect of doping amount on the microstructure, ferroelectric properties, dielectric and pyroelectric properties of 0.96NaNbO3-0.04BaTiO3 ceramics was systematically investigated. The results show that when the doping amount of Mn is 0.4%, the ceramics have the optimum pyroelectric properties, which has a practical prospect of uncooled infrared detection.

Methods

All the components of sodium niobate ceramics were prepared by a solid-phase sintering method. The series of components were weighed according to the stoichiometric ratio, and the raw materials with anhydrous ethanol were ground in a stirred bead mill with zirconia beads at 400 r/min for 6 h. After being dried and shaped, the ground material was was pre-sintered at 1000 ℃ for 4 h, and then subjected to milling and drying. Green wafers with a diameter of 12 mm were prepared by pressure cold isostatic pressing at 200 MPa for 5 min after adding 10% PVA. The wafers were degummed at 600 ℃ for 2 h to remove organic matter and other impurities. To prevent the volatilization of sodium at a high temperature, the padding with the same composition was used for burial treatment, and the padding was kept at the corresponding temperature for 3 h and then cooled naturally. The sintered ceramic wafers were ground to fine particles with the size of 300 μm, coated with silver electrodes on both sides, and polarized in silicone oil under an electric field of 8-10 kV/mm at 80 ℃ for 15 min. The electrical properties were tested after 24 h.

Results and discussion

The microstructural morphology, dielectric properties, temperature stability, and pyroelectric properties of 0.96NN-0.04BT ceramics doped with 0-0.6% Mn are investigated. The results show that doping Mn ions significantly improves the sintering characteristics of 0.96NN-0.04BT ceramics, enhances the density, and the relative densities of all components reach above 90%. The NN-BT ceramic grain size increases with the increase of the doping amount. The substitution position of Mn ions causes changes in the electrical properties of the ceramic as the Mn doping content increases gradually. The concentration of oxygen vacancies caused by Na+ evaporation decreases when Mn ions substitute for A-site vacancies, which is beneficial to reducing the ceramic dielectric constant and dielectric loss, thus significantly improving the detection sensitivity factor. However, as the Mn doping content further increases, the imbalance of charges is prone to attract oxygen vacancies to form defect dipoles due to the heterovalent substitution of Mn ions on the B-site, thereby producing domain wall pinning effects. Also, the defect dipoles cause the increasing coercive field of the doped material and make it difficult to fully polarize, resulting in the material that is unable to fully utilize its pyroelectric properties.

Conclusions

The ceramic could have more suitable characteristics for pyroelectric requirements via appropriately adjusting the Mn doping concentration. The ceramic with Mn ion doping mass fraction of 0.4% had the optimal pyroelectric performance (i.e., the pyroelectric coefficient of 2.11×10-8 C·cm-2·K-1, and the Fv value of 3.74×10-2 m2·C-1), which was greater than 1.3 times and 1.8 times of the un-doped component. The coercive field reduced from 4.04 kV/mm of the un-doped component to 3.17 kV/mm, which was decreased by 21.5%. The results of the thermal stability test proved that the depolarization temperature could be maintained at 310 ℃, which had a practical prospect for non-cooled infrared detection.

sodium niobate ceramics  /  pyroelectric ceramics  /  manganese doping  /  high depolarization temperature
刘亦扬, 岑方杰, 范明智, 罗方苑, 姜胜林, 李康华, 张光祖. 锰掺杂对0.96NaNbO3-0.04BaTiO3陶瓷热释电性能的影响. 硅酸盐学报, 2025 , 53 (4) : 759 -768 . DOI: 10.14062/j.issn.0454-5648.20240694
Yiyang LIU, Fangjie CEN, Mingzhi FAN, Fangyuan LUO, Shenglin JIANG, Kanghua LI, Guangzu ZHANG. Effect of Mn Doping on Pyroelectric Properties of 0.96NaNbO3-0.04BaTiO3 Ceramics[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (4) : 759 -768 . DOI: 10.14062/j.issn.0454-5648.20240694
  • 国家重点研发计划(2022YFA1204603)
  • 国家自然科学基金(52172114; 52372108; 52272110; 62105110; 523B2011)
  • 湖北省自然科学基金创新群体项目(2024AFA012)
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doi: 10.14062/j.issn.0454-5648.20240694
  • 接收时间:2024-11-01
  • 首发时间:2026-10-22
  • 出版时间:2025-04-20
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  • 收稿日期:2024-11-01
  • 修回日期:2024-12-28
基金
国家重点研发计划(2022YFA1204603)
国家自然科学基金(52172114; 52372108; 52272110; 62105110; 523B2011)
湖北省自然科学基金创新群体项目(2024AFA012)
作者信息
    华中科技大学集成电路学院,武汉 430074

通讯作者:

张光祖(1984—),男,博士,教授;
李康华(1993—)男,博士,副教授。
参考文献
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2种不同金属材料的力学参数
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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