Article(id=1320095748159558050, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320095743872971684, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20250885, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1764950400000, receivedDateStr=2025-12-06, revisedDate=1767456000000, revisedDateStr=2026-01-04, acceptedDate=null, acceptedDateStr=null, onlineDate=1792664952554, onlineDateStr=2026-10-22, pubDate=1778601600000, pubDateStr=2026-05-13, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792664952554, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792664952554, creator=13701087609, updateTime=1792664952554, updator=13701087609, issue=Issue{id=1320095743872971684, tenantId=1146029695717560320, journalId=1263187385517883426, year='2026', volume='54', issue='6', pageStart='1881', pageEnd='2170', issueExtLink='null', onlineDate='null', pubDate='1781884800000', pubDateStr='2026-06-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792664951531, creator='13701087609', updateTime=1792738533970, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320404371276411812, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320095743872971684, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320404371276411813, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320095743872971684, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1937, endPage=1944, ext={EN=ArticleExt(id=1320095748394439075, articleId=1320095748159558050, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Structure and Properties of Dy/Eu-Doped Potassium Sodium Niobate-Based Piezoelectric Ceramics, columnId=1263922769897599102, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Articles, runingTitle=null, highlight=null, articleAbstract=
Introduction

Piezoelectric ceramics are critical components in sensors, actuators, energy converters, and micro-electromechanical systems. The lead-based compositions dominate in the existing market. However, the release of lead during their lifecycle poses severe environmental and human-being health risks, which contradicts global sustainable development goals. Therefore, developing high-performance lead-free alternatives becomes a paramount research priority. Among lead-free alternatives, potassium sodium niobate ((K,Na)NbO3, KNN)-based ceramics stand out due to their low driving voltage, large electrostrain, and minimal hysteresis, making them performance-competitive with conventional PZT for precision actuators. Their performance is typically enhanced by constructing polymorphic phase boundaries and regulating microstructure. However, the existing doping strategies inadvertently degrade thermal stability, which remains a key bottleneck for practical applications. Rare-earth ions act as effective modifiers in KNN-based piezoceramics. They enhance a relaxor behavior, and improve thermal stability by shifting rhombohedral-tetragonal (R-T) phase transition below room temperature, and introduce photoluminescence due to their abundant energy levels. The integration of electrostrain and luminescence in KNN-based systems is thus significant, paving a way for developing novel bimodal functional materials for next-generation optoelectronic devices. In this work, the 0.96(K0.48Na0.52)(Nb0.95Sb0.05)O3-0.04Bi0.5(Na0.82K0.18)0.5ZrO3(0.96KNNS-0.04BNKZ) composition with a polymorphic phase transition characteristic was chosen as a matrix, and rare-earth oxides (Dy2O3 and Eu2O3) served as modifiers. The effect of rare-earth oxides doping on the microstructure, ferroelectric/electrostrain properties, and photoluminescence performance of the 0.96KNNS-0.04BNKZ ceramics was investigated.

Methods

0.96KNNS-0.04BNKZ-x%Dy/Eu (x = 0, 0.05, 0.10, 0.20, 0.40) lead-free ferroelectric ceramics were synthesized by a solid-state reaction method. The stoichiometric raw materials were weighed according to the formula. They were then ground in ethanol in a ball mill with zirconia balls for 24 h. The powders were calcined at 850 ℃ for 4 h, then ground again for 24 h. After drying, the powders were mixed with 10% polyvinyl alcohol (PVA) as a binder and then granulated. Subsequently, disc-shaped green compacts (with the sizes of 10 mm in diameter and 0.5 mm in thickness) were pressed and subjected to a debinding process at 550 ℃. The ceramics were obtained after sintering at 1130-1200 ℃ for 2 h. After polishing, silver electrodes were fired at 650 ℃ for electrical testing. The ceramics were sintered at at 1130 ℃ to 1200 ℃ for 2 h, depending on the doping levels. After polishing, silver electrodes were fired on the surfaces at 650 ℃ for electrical characterization. The phase structure was analyzed by an X-ray diffractometer (D8 advance). The surface morphology was determined by a field emission scanning electron microscope (Merlin compact, Carl Zeiss Co., Germany). The temperature-dependent dielectric constant was measured by a broadband dielectric spectrometer (Novocontrol concept 40). The ferroelectric and electric-field-induced strain were characterized by a ferroelectric analyzer (TF 2000) coupled with a laser interferometer (SP-S 120/500). The photoluminescence properties were evaluated by a fluorescence spectrometer (FLS920).

Results and discussion

Dy/Eu-doped 0.96KNNS-0.04BNKZ ceramics exhibit a single perovskite structure. At low doping levels (i.e., x ≤ 0.10%), the rhombohedral-tetragonal (R-T) coexisting phase maintains, while a higher doping (i.e., x ≥ 0.20%) induces a transition to the pseudocubic (Pc) phase, with no secondary phases appears in all the samples. All the ceramics present dense and uniform microstructures. The average grain size gradually decreases with increasing Dy/Eu doping, indicating that rare-earth ions effectively inhibit grain growth. In terms of electrical properties, a moderate Dy/Eu doping (i.e., Dy: x=0.10%; Eu: x=0.05%) enhances ferroelectricity, as reflected by improved P-E loop squareness and increased saturated polarization (Pmax). The 0.10%Dy and 0.05%Eu samples achieve an optimal electrostrain performance, delivering unipolar strains (Suni) of 0.257% and 0.241% at 70 kV/cm, which are accompanied by large piezoelectric strain coefficients (d33*) of 367 pm/V and 344 pm/V, respectively. An appropriate doping optimizes the domain structure and facilitates domain switching in an external electric field, thereby improving both ferroelectric and electrostrain properties. In contrast, excessive doping leads to a severe lattice distortion, notably octahedral tilting, which pins domain walls and hinders their reorientation in response to the electric field, ultimately compromising ferroelectric and electrostrain performance. Furthermore, the 0.05% Dy- and 0.05% Eu-doped ceramics exhibit excellent thermal stability, showing less than 10% variation in electrostrain at 25-100 ℃, which demonstrates their great potential for use in piezoelectric actuators. In addition, Dy/Eu doping introduces a pronounced photoluminescence to the ceramics. Under blue-light excitation, Dy3+-doped samples yield an intense yellow emission, whereas Eu3+-doped samples produce a bright orange-red emission.

Conclusions

The introduction of Dy/Eu could promote a phase transition from a mixed R-T phase to a Pc phase. An appropriate doping effectively enhanced the ferroelectric and electrostrain properties of the materials. Specifically, the 0.10% Dy- and 0.05% Eu-doped ceramics achieved unipolar strains (Suni) of 0.257% and 0.241% at an electric field of 70 kV/cm, with corresponding piezoelectric strain coefficients (d33*) of 367 pm/V and 344 pm/V, respectively. Furthermore, the 0.05% Dy- and 0.05% Eu-doped samples exhibited excellent thermal stability, with a variation in electrostrain of less than 10% at 25-100 ℃, demonstrating a great potential for piezoelectric actuator applications. In addition, Dy/Eu doping imparted outstanding photoluminescence properties to the ceramics. Under blue-light excitation, Dy3+-doped samples exhibited an intense yellow emission, while Eu3+-doped samples displayed a bright orange-red emission. The combination of electrical and luminescent characteristics could make this material a promising candidate for optoelectronic coupling devices.

, authors=Jingwen SUN, Jiarui WANG, Ziyue WANG, Jigong HAO, Wei LI, authorsList=Jingwen SUN, Jiarui WANG, Ziyue WANG, Jigong HAO, Wei LI, authorCompany=null, correspAuthors=Jigong HAO, Wei LI, authorNote=

SUN Jingwen (2002-), female, Master candidate. E-mail:

, correspAuthorsNote=
HAO Jigong (1984-), male, Ph.D., Associate Professor. E-mail: ;
LI Wei (1981-), male, Ph.D., Professor.
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采用传统固相合成法制备了稀土(Dy/Eu)掺杂的0.96(K0.48Na0.52)(Nb0.95Sb0.05)O3-0.04Bi0.5(Na0.82K0.18)0.5ZrO3无铅压电陶瓷,系统研究了Dy/Eu对其结构和电学性能的影响。结果表明,Dy/Eu的引入促使陶瓷的相结构由菱方-四方共存相逐步向赝立方相结构转变。适量的掺杂有效提升材料的铁电性能与电致应变性能,其中:0.10%(摩尔分数)Dy和0.05%Eu掺杂的样品在70 kV/cm电场下的单向应变Suni分别达0.257%和0.241%,对应的压电应变系数d33*分别为367 pm/V和344 pm/V。同时,0.05%Dy和0.05%Eu掺杂样品在25~100 ℃温度区间的电致应变波动幅度小于10%,表现出优异的温度稳定性,在压电驱动器方面展现出良好应用前景。此外,稀土Dy/Eu掺杂还使陶瓷具备优异的光致发光特性;在蓝光激发下,Dy3+掺杂样品呈现强黄光发射,而Eu3+掺杂样品则发出明亮的橙红色光。该材料兼具电学性能与发光特性,在光电耦合器件中具有潜在的应用价值。

, authors=孙静雯, 王佳蕊, 王子玥, 郝继功, 李伟, authorsList=孙静雯, 王佳蕊, 王子玥, 郝继功, 李伟, authorCompany=null, correspAuthors=郝继功, 李伟, authorNote=

孙静雯(2002—),女,硕士研究生。

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郝继功(1984—),男,博士,副教授;
李伟(1981—),男,博士,教授。
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稀土Dy/Eu掺杂对铌酸钾钠基压电陶瓷结构与性能的影响
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孙静雯 , 王佳蕊 , 王子玥 , 郝继功 , 李伟
硅酸盐学报 | 研究论文 2026,54(6): 1937-1944
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硅酸盐学报 |研究论文 2026 , 54 (6) : 1937 -1944
稀土Dy/Eu掺杂对铌酸钾钠基压电陶瓷结构与性能的影响
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孙静雯 , 王佳蕊, 王子玥, 郝继功 , 李伟
作者信息
  • 聊城大学材料科学与工程学院,山东省教育厅敏感材料与器件实验室,山东 聊城 25205
通讯作者:
郝继功(1984—),男,博士,副教授;
李伟(1981—),男,博士,教授。
作者简介:

孙静雯(2002—),女,硕士研究生。

Structure and Properties of Dy/Eu-Doped Potassium Sodium Niobate-Based Piezoelectric Ceramics
Jingwen SUN , Jiarui WANG, Ziyue WANG, Jigong HAO , Wei LI
Affiliations
  • School of Materials Science and Engineering, Laboratory of Sensitive Materials and Devices Shandong Department of Education, Liaocheng University, Liaocheng 252059, Shandong, China
  • Corresponding Author:
    HAO Jigong (1984-), male, Ph.D., Associate Professor. E-mail: ;
    LI Wei (1981-), male, Ph.D., Professor.

    SUN Jingwen (2002-), female, Master candidate. E-mail:

出版时间: 2026-05-13 doi: 10.14062/j.issn.0454-5648.20250885
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采用传统固相合成法制备了稀土(Dy/Eu)掺杂的0.96(K0.48Na0.52)(Nb0.95Sb0.05)O3-0.04Bi0.5(Na0.82K0.18)0.5ZrO3无铅压电陶瓷,系统研究了Dy/Eu对其结构和电学性能的影响。结果表明,Dy/Eu的引入促使陶瓷的相结构由菱方-四方共存相逐步向赝立方相结构转变。适量的掺杂有效提升材料的铁电性能与电致应变性能,其中:0.10%(摩尔分数)Dy和0.05%Eu掺杂的样品在70 kV/cm电场下的单向应变Suni分别达0.257%和0.241%,对应的压电应变系数d33*分别为367 pm/V和344 pm/V。同时,0.05%Dy和0.05%Eu掺杂样品在25~100 ℃温度区间的电致应变波动幅度小于10%,表现出优异的温度稳定性,在压电驱动器方面展现出良好应用前景。此外,稀土Dy/Eu掺杂还使陶瓷具备优异的光致发光特性;在蓝光激发下,Dy3+掺杂样品呈现强黄光发射,而Eu3+掺杂样品则发出明亮的橙红色光。该材料兼具电学性能与发光特性,在光电耦合器件中具有潜在的应用价值。

无铅压电陶瓷  /  铌酸钾钠  /  电致应变性能  /  温度稳定性
Introduction

Piezoelectric ceramics are critical components in sensors, actuators, energy converters, and micro-electromechanical systems. The lead-based compositions dominate in the existing market. However, the release of lead during their lifecycle poses severe environmental and human-being health risks, which contradicts global sustainable development goals. Therefore, developing high-performance lead-free alternatives becomes a paramount research priority. Among lead-free alternatives, potassium sodium niobate ((K,Na)NbO3, KNN)-based ceramics stand out due to their low driving voltage, large electrostrain, and minimal hysteresis, making them performance-competitive with conventional PZT for precision actuators. Their performance is typically enhanced by constructing polymorphic phase boundaries and regulating microstructure. However, the existing doping strategies inadvertently degrade thermal stability, which remains a key bottleneck for practical applications. Rare-earth ions act as effective modifiers in KNN-based piezoceramics. They enhance a relaxor behavior, and improve thermal stability by shifting rhombohedral-tetragonal (R-T) phase transition below room temperature, and introduce photoluminescence due to their abundant energy levels. The integration of electrostrain and luminescence in KNN-based systems is thus significant, paving a way for developing novel bimodal functional materials for next-generation optoelectronic devices. In this work, the 0.96(K0.48Na0.52)(Nb0.95Sb0.05)O3-0.04Bi0.5(Na0.82K0.18)0.5ZrO3(0.96KNNS-0.04BNKZ) composition with a polymorphic phase transition characteristic was chosen as a matrix, and rare-earth oxides (Dy2O3 and Eu2O3) served as modifiers. The effect of rare-earth oxides doping on the microstructure, ferroelectric/electrostrain properties, and photoluminescence performance of the 0.96KNNS-0.04BNKZ ceramics was investigated.

Methods

0.96KNNS-0.04BNKZ-x%Dy/Eu (x = 0, 0.05, 0.10, 0.20, 0.40) lead-free ferroelectric ceramics were synthesized by a solid-state reaction method. The stoichiometric raw materials were weighed according to the formula. They were then ground in ethanol in a ball mill with zirconia balls for 24 h. The powders were calcined at 850 ℃ for 4 h, then ground again for 24 h. After drying, the powders were mixed with 10% polyvinyl alcohol (PVA) as a binder and then granulated. Subsequently, disc-shaped green compacts (with the sizes of 10 mm in diameter and 0.5 mm in thickness) were pressed and subjected to a debinding process at 550 ℃. The ceramics were obtained after sintering at 1130-1200 ℃ for 2 h. After polishing, silver electrodes were fired at 650 ℃ for electrical testing. The ceramics were sintered at at 1130 ℃ to 1200 ℃ for 2 h, depending on the doping levels. After polishing, silver electrodes were fired on the surfaces at 650 ℃ for electrical characterization. The phase structure was analyzed by an X-ray diffractometer (D8 advance). The surface morphology was determined by a field emission scanning electron microscope (Merlin compact, Carl Zeiss Co., Germany). The temperature-dependent dielectric constant was measured by a broadband dielectric spectrometer (Novocontrol concept 40). The ferroelectric and electric-field-induced strain were characterized by a ferroelectric analyzer (TF 2000) coupled with a laser interferometer (SP-S 120/500). The photoluminescence properties were evaluated by a fluorescence spectrometer (FLS920).

Results and discussion

Dy/Eu-doped 0.96KNNS-0.04BNKZ ceramics exhibit a single perovskite structure. At low doping levels (i.e., x ≤ 0.10%), the rhombohedral-tetragonal (R-T) coexisting phase maintains, while a higher doping (i.e., x ≥ 0.20%) induces a transition to the pseudocubic (Pc) phase, with no secondary phases appears in all the samples. All the ceramics present dense and uniform microstructures. The average grain size gradually decreases with increasing Dy/Eu doping, indicating that rare-earth ions effectively inhibit grain growth. In terms of electrical properties, a moderate Dy/Eu doping (i.e., Dy: x=0.10%; Eu: x=0.05%) enhances ferroelectricity, as reflected by improved P-E loop squareness and increased saturated polarization (Pmax). The 0.10%Dy and 0.05%Eu samples achieve an optimal electrostrain performance, delivering unipolar strains (Suni) of 0.257% and 0.241% at 70 kV/cm, which are accompanied by large piezoelectric strain coefficients (d33*) of 367 pm/V and 344 pm/V, respectively. An appropriate doping optimizes the domain structure and facilitates domain switching in an external electric field, thereby improving both ferroelectric and electrostrain properties. In contrast, excessive doping leads to a severe lattice distortion, notably octahedral tilting, which pins domain walls and hinders their reorientation in response to the electric field, ultimately compromising ferroelectric and electrostrain performance. Furthermore, the 0.05% Dy- and 0.05% Eu-doped ceramics exhibit excellent thermal stability, showing less than 10% variation in electrostrain at 25-100 ℃, which demonstrates their great potential for use in piezoelectric actuators. In addition, Dy/Eu doping introduces a pronounced photoluminescence to the ceramics. Under blue-light excitation, Dy3+-doped samples yield an intense yellow emission, whereas Eu3+-doped samples produce a bright orange-red emission.

Conclusions

The introduction of Dy/Eu could promote a phase transition from a mixed R-T phase to a Pc phase. An appropriate doping effectively enhanced the ferroelectric and electrostrain properties of the materials. Specifically, the 0.10% Dy- and 0.05% Eu-doped ceramics achieved unipolar strains (Suni) of 0.257% and 0.241% at an electric field of 70 kV/cm, with corresponding piezoelectric strain coefficients (d33*) of 367 pm/V and 344 pm/V, respectively. Furthermore, the 0.05% Dy- and 0.05% Eu-doped samples exhibited excellent thermal stability, with a variation in electrostrain of less than 10% at 25-100 ℃, demonstrating a great potential for piezoelectric actuator applications. In addition, Dy/Eu doping imparted outstanding photoluminescence properties to the ceramics. Under blue-light excitation, Dy3+-doped samples exhibited an intense yellow emission, while Eu3+-doped samples displayed a bright orange-red emission. The combination of electrical and luminescent characteristics could make this material a promising candidate for optoelectronic coupling devices.

lead-free piezoelectric ceramics  /  potassium sodium niobate  /  electrostrain  /  thermal stability
孙静雯, 王佳蕊, 王子玥, 郝继功, 李伟. 稀土Dy/Eu掺杂对铌酸钾钠基压电陶瓷结构与性能的影响. 硅酸盐学报, 2026 , 54 (6) : 1937 -1944 . DOI: 10.14062/j.issn.0454-5648.20250885
Jingwen SUN, Jiarui WANG, Ziyue WANG, Jigong HAO, Wei LI. Structure and Properties of Dy/Eu-Doped Potassium Sodium Niobate-Based Piezoelectric Ceramics[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (6) : 1937 -1944 . DOI: 10.14062/j.issn.0454-5648.20250885
  • 山东省自然科学基金(ZR2025MS781; ZR2024ME2013)
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doi: 10.14062/j.issn.0454-5648.20250885
  • 接收时间:2025-12-06
  • 首发时间:2026-10-22
  • 出版时间:2026-05-13
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  • 收稿日期:2025-12-06
  • 修回日期:2026-01-04
基金
山东省自然科学基金(ZR2025MS781; ZR2024ME2013)
作者信息
    聊城大学材料科学与工程学院,山东省教育厅敏感材料与器件实验室,山东 聊城 25205

通讯作者:

郝继功(1984—),男,博士,副教授;
李伟(1981—),男,博士,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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Family
属数
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genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
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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