Article(id=1319726323568849324, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319726260922728931, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20250225, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1743177600000, receivedDateStr=2025-03-29, revisedDate=1745251200000, revisedDateStr=2025-04-22, acceptedDate=null, acceptedDateStr=null, onlineDate=1792576874867, onlineDateStr=2026-10-21, pubDate=1758297600000, pubDateStr=2025-09-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792576874867, onlineIssueDateStr=2026-10-21, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792576874867, creator=13701087609, updateTime=1792576874867, updator=13701087609, issue=Issue{id=1319726260922728931, tenantId=1146029695717560320, journalId=1263187385517883426, year='2025', volume='53', issue='9', pageStart='2419', pageEnd='2752', issueExtLink='null', onlineDate='null', pubDate='1758297600000', pubDateStr='2025-09-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792576859932, creator='13701087609', updateTime=1792577418267, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1319728602791395512, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319726260922728931, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1319728602791395513, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319726260922728931, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=2469, endPage=2478, ext={EN=ArticleExt(id=1319726323875033517, articleId=1319726323568849324, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Electrical Properties of BiFeO3/Si Heterojunctions with SiOx Interface Layer, columnId=1321945583586226843, journalTitle=Journal of the Chinese Ceramic Society, columnName=Special Issue on Ferroelectric Thin Films and Devices Toward Next-Generation Information Technology Applications—Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction

As electronic technology and integrated circuits advance rapidly, the functional demands of devices are increasingly elevated. Ferroelectric/semiconductor heterostructures are significant in applications including memory, sensing, and optoelectronic devices because they combine the best qualities of both ferroelectric and semiconductor materials. In recent years, the variety and refinement of the preparation process have led to the successful direct integration of ferroelectric materials with semiconductor silicon. Nevertheless, constructing ferroelectric/semiconductor heterostructures devoid of any interface layers, particularly on silicon substrates, is exceedingly challenging. Due to thermal diffusion, there is usually a SiOx layer at the interface, which subsequently affects device performance. However, systematic researches are urgently need regarding the effect of the interface layer on the potential barriers, ferroelectric polarization, and carrier transport. This work develops SiOx layers of varying thicknesses and densities on the n-Si surface, followed by the fabrication of bismuth ferrite (BiFeO3) films on the pretreated substrate. When the substrate pretreatment temperature rises, the SiOx layer progressively thickens, thereby altering the interface barrier, polarization switching, and the transport of photogenerated carriers. This study presents a novel concept for the creation of ferroelectric/semiconductor heterostructures featuring several interface contact types and electrical transport pathways.

Methods

Oxygen was introduced into the tube furnace, which was later heated to 400-1000 ℃. Once the temperature stabilizes, the (100) oriented n-Si substrate (resistivity of approximately 10 Ω·cm) is put into the furnace. After heating for 1 h, the substrate is directly removed from the tube furnace and allowed to cool in a room temperature environment.

The raw materials Bi(NO3)3·5H2O and Fe(NO3)3·9H2O were dissolved in acetic acid and ethylene glycol methyl ether, respectively. Subsequently, these two solutions were mixed, stirred for 8 h, and filtered to obtain a BiFeO3 precursor solution at a concentration of 0.1 mol/L. The precursors were spin-coated onto the pretreated n-Si (100) substrate at 3500 r/min for 30 s and heated at 180 ℃ for 5 min. The spin-coating process was done three times to attain a film thickness of approximately 60 nm, afterwards, the samples were annealed in a nitrogen environment at 380 ℃ for 15 min, followed by 550 ℃ for 50 min, with a heating rate of 10 ℃/min.

Results and discussion

The n-Si substrate was pretreated at various temperatures in an oxygen environment. The cross-sectional high-resolution transmission electron microscopy indicates an increase in the thickness of the SiOx layer with increasing substrate pretreatment temperature. The dielectric measurements show that when the pretreatment temperature is above 600 ℃, the activation energy of the dielectric relaxation begins to decline, signifying a decrease in the oxygen vacancy content while the transition of the oxygen vacancies from divalent to monovalent. Subsequently, BiFeO3 films were fabricated on the pretreated substrate. X-ray diffraction studies demonstrated that all the BiFeO3 films exhibit R3c polycrystalline structure.

After substrate pretreatment, the clamping phenomenon of the BiFeO3/n-Si hysteresis loop disappears. As the pretreatment temperature increases, the loop becomes slimmer, and the coercive voltage decreases. The reason is that the increased thickness of the SiOx layer hinders the carrier migration between BiFeO3 and the n-Si substrate. At temperatures below and above 700 ℃, the SiOx can be considered as a tunneling layer and a resistive layer, respectively. I-V curves show that the BiFeO3/n-Si samples still exhibit rectification effects, but the cut-off voltage under negative bias and the conduction current under positive bias both decrease, which is consistent with the weakening of the interface barrier and the decrease in conductivity. Although the photocurrent and on-off ratio generally decline with the increasing pretreatment temperature, the on-off ratio of the sample on 700 ℃ pretreated substrate increases abnormally, attributed to the increased conductivity associated with the aggregation of monovalent oxygen vacancies.

Conclusions

BiFeO3 films are grown on n-Si substrates pretreated at different temperatures. As the pretreatment temperature increases, the SiOx layer on the n-Si surface became thicker and denser, accompanied by a reduction in oxygen vacancies and a transition from divalent to monovalent. The hysteresis loops are no longer clamped, with the coercive voltage deceased, and both the cut-off voltage of the I-V curves and the on-off ratio of the photocurrent reduce. The primary explanation is that the SiOx layer reduces the pn junction barrier and the built-in electric field at the BiFeO3/n-Si interface, facilitating the polarization switching of BiFeO3 and the transport of photogenerated carriers. The accumulation of oxygen vacancies at a particular temperature can result in an anomalous rise in photocurrent.

, authors=Zeyu XIAO, Lin LEI, Lin LIU, Xueli HU, Fengzhen HUANG, Xiaomei LU, authorsList=Zeyu XIAO, Lin LEI, Lin LIU, Xueli HU, Fengzhen HUANG, Xiaomei LU, authorCompany=null, correspAuthors=Fengzhen HUANG, Xiaomei LU, authorNote=

XIAO Zeyu (1999-), female, Doctoral Candidate. E-mail:

, correspAuthorsNote=
LU Xiaomei (1969-), female, Ph.D., Professor. E-mail: ;
HUANG Fengzhen (1979-), female, Ph.D., Associate Professor.
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构建铁电/半导体异质结构是现代多功能电子器件的重要发展方向。利用溶胶-凝胶方法在不同温度预处理后的n-Si衬底上制备了BiFeO3薄膜。结果表明,衬底预处理使得样品电滞回线细化变形,同时光电流变弱。结合介电-温度谱以及截面高分辨透射电子显微镜等分析表明,衬底预处理后,n-Si表面的SiOx层厚度增加,削弱了BFO与n-Si之间的pn结界面接触势垒以及相应的分压,有利于BFO的极化开关。势垒的降低伴随着界面内建电场的减小,对光生载流子分离运动的驱动力减弱。通过揭示不同SiOx厚度对铁电/半导体异质结界面及电荷迁移的影响,可为基于Si衬底的铁电集成器件的设计提供重要参考。

, authors=肖泽宇, 雷林, 刘琳, 胡雪莉, 黄凤珍, 吕笑梅, authorsList=肖泽宇, 雷林, 刘琳, 胡雪莉, 黄凤珍, 吕笑梅, authorCompany=null, correspAuthors=黄凤珍, 吕笑梅, authorNote=

肖泽宇(1999—),女,博士研究生。

, correspAuthorsNote=
吕笑梅(1969—),女,博士,教授;
黄凤珍(1979—),女,博士,副教授。
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界面SiOx层对BiFeO3/Si异质结电学性能的影响
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肖泽宇 , 雷林 , 刘琳 , 胡雪莉 , 黄凤珍 , 吕笑梅
硅酸盐学报 | 面向新一代信息技术应用的铁电薄膜与器件专题—研究论文 2025,53(9): 2469-2478
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硅酸盐学报 |面向新一代信息技术应用的铁电薄膜与器件专题—研究论文 2025 , 53 (9) : 2469 -2478
界面SiOx层对BiFeO3/Si异质结电学性能的影响
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肖泽宇 , 雷林, 刘琳, 胡雪莉, 黄凤珍 , 吕笑梅
作者信息
  • 南京大学物理学院,固体微结构物理国家重点实验室,人工微结构科学与技术协同创新中心,南京 210093
通讯作者:
吕笑梅(1969—),女,博士,教授;
黄凤珍(1979—),女,博士,副教授。
作者简介:

肖泽宇(1999—),女,博士研究生。

Electrical Properties of BiFeO3/Si Heterojunctions with SiOx Interface Layer
Zeyu XIAO , Lin LEI, Lin LIU, Xueli HU, Fengzhen HUANG , Xiaomei LU
Affiliations
  • National Laboratory of Solid State Microstructures and School of Physics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093
  • Corresponding Author:
    LU Xiaomei (1969-), female, Ph.D., Professor. E-mail: ;
    HUANG Fengzhen (1979-), female, Ph.D., Associate Professor.

    XIAO Zeyu (1999-), female, Doctoral Candidate. E-mail:

出版时间: 2025-09-20 doi: 10.14062/j.issn.0454-5648.20250225
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构建铁电/半导体异质结构是现代多功能电子器件的重要发展方向。利用溶胶-凝胶方法在不同温度预处理后的n-Si衬底上制备了BiFeO3薄膜。结果表明,衬底预处理使得样品电滞回线细化变形,同时光电流变弱。结合介电-温度谱以及截面高分辨透射电子显微镜等分析表明,衬底预处理后,n-Si表面的SiOx层厚度增加,削弱了BFO与n-Si之间的pn结界面接触势垒以及相应的分压,有利于BFO的极化开关。势垒的降低伴随着界面内建电场的减小,对光生载流子分离运动的驱动力减弱。通过揭示不同SiOx厚度对铁电/半导体异质结界面及电荷迁移的影响,可为基于Si衬底的铁电集成器件的设计提供重要参考。

铁电/半导体异质结  /  铁酸铋薄膜  /  硅衬底  /  氧化硅  /  电荷迁移
Introduction

As electronic technology and integrated circuits advance rapidly, the functional demands of devices are increasingly elevated. Ferroelectric/semiconductor heterostructures are significant in applications including memory, sensing, and optoelectronic devices because they combine the best qualities of both ferroelectric and semiconductor materials. In recent years, the variety and refinement of the preparation process have led to the successful direct integration of ferroelectric materials with semiconductor silicon. Nevertheless, constructing ferroelectric/semiconductor heterostructures devoid of any interface layers, particularly on silicon substrates, is exceedingly challenging. Due to thermal diffusion, there is usually a SiOx layer at the interface, which subsequently affects device performance. However, systematic researches are urgently need regarding the effect of the interface layer on the potential barriers, ferroelectric polarization, and carrier transport. This work develops SiOx layers of varying thicknesses and densities on the n-Si surface, followed by the fabrication of bismuth ferrite (BiFeO3) films on the pretreated substrate. When the substrate pretreatment temperature rises, the SiOx layer progressively thickens, thereby altering the interface barrier, polarization switching, and the transport of photogenerated carriers. This study presents a novel concept for the creation of ferroelectric/semiconductor heterostructures featuring several interface contact types and electrical transport pathways.

Methods

Oxygen was introduced into the tube furnace, which was later heated to 400-1000 ℃. Once the temperature stabilizes, the (100) oriented n-Si substrate (resistivity of approximately 10 Ω·cm) is put into the furnace. After heating for 1 h, the substrate is directly removed from the tube furnace and allowed to cool in a room temperature environment.

The raw materials Bi(NO3)3·5H2O and Fe(NO3)3·9H2O were dissolved in acetic acid and ethylene glycol methyl ether, respectively. Subsequently, these two solutions were mixed, stirred for 8 h, and filtered to obtain a BiFeO3 precursor solution at a concentration of 0.1 mol/L. The precursors were spin-coated onto the pretreated n-Si (100) substrate at 3500 r/min for 30 s and heated at 180 ℃ for 5 min. The spin-coating process was done three times to attain a film thickness of approximately 60 nm, afterwards, the samples were annealed in a nitrogen environment at 380 ℃ for 15 min, followed by 550 ℃ for 50 min, with a heating rate of 10 ℃/min.

Results and discussion

The n-Si substrate was pretreated at various temperatures in an oxygen environment. The cross-sectional high-resolution transmission electron microscopy indicates an increase in the thickness of the SiOx layer with increasing substrate pretreatment temperature. The dielectric measurements show that when the pretreatment temperature is above 600 ℃, the activation energy of the dielectric relaxation begins to decline, signifying a decrease in the oxygen vacancy content while the transition of the oxygen vacancies from divalent to monovalent. Subsequently, BiFeO3 films were fabricated on the pretreated substrate. X-ray diffraction studies demonstrated that all the BiFeO3 films exhibit R3c polycrystalline structure.

After substrate pretreatment, the clamping phenomenon of the BiFeO3/n-Si hysteresis loop disappears. As the pretreatment temperature increases, the loop becomes slimmer, and the coercive voltage decreases. The reason is that the increased thickness of the SiOx layer hinders the carrier migration between BiFeO3 and the n-Si substrate. At temperatures below and above 700 ℃, the SiOx can be considered as a tunneling layer and a resistive layer, respectively. I-V curves show that the BiFeO3/n-Si samples still exhibit rectification effects, but the cut-off voltage under negative bias and the conduction current under positive bias both decrease, which is consistent with the weakening of the interface barrier and the decrease in conductivity. Although the photocurrent and on-off ratio generally decline with the increasing pretreatment temperature, the on-off ratio of the sample on 700 ℃ pretreated substrate increases abnormally, attributed to the increased conductivity associated with the aggregation of monovalent oxygen vacancies.

Conclusions

BiFeO3 films are grown on n-Si substrates pretreated at different temperatures. As the pretreatment temperature increases, the SiOx layer on the n-Si surface became thicker and denser, accompanied by a reduction in oxygen vacancies and a transition from divalent to monovalent. The hysteresis loops are no longer clamped, with the coercive voltage deceased, and both the cut-off voltage of the I-V curves and the on-off ratio of the photocurrent reduce. The primary explanation is that the SiOx layer reduces the pn junction barrier and the built-in electric field at the BiFeO3/n-Si interface, facilitating the polarization switching of BiFeO3 and the transport of photogenerated carriers. The accumulation of oxygen vacancies at a particular temperature can result in an anomalous rise in photocurrent.

ferroelectric/semiconductor heterojunction  /  bismuth ferrite thin film  /  silicon substrate  /  silicon dioxide  /  charge migration
肖泽宇, 雷林, 刘琳, 胡雪莉, 黄凤珍, 吕笑梅. 界面SiOx层对BiFeO3/Si异质结电学性能的影响. 硅酸盐学报, 2025 , 53 (9) : 2469 -2478 . DOI: 10.14062/j.issn.0454-5648.20250225
Zeyu XIAO, Lin LEI, Lin LIU, Xueli HU, Fengzhen HUANG, Xiaomei LU. Electrical Properties of BiFeO3/Si Heterojunctions with SiOx Interface Layer[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (9) : 2469 -2478 . DOI: 10.14062/j.issn.0454-5648.20250225
  • 国家重点研发计划(2022YFA1402903)
  • 国家自然科学基金(52172116; 62171214)
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doi: 10.14062/j.issn.0454-5648.20250225
  • 接收时间:2025-03-29
  • 首发时间:2026-10-21
  • 出版时间:2025-09-20
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  • 收稿日期:2025-03-29
  • 修回日期:2025-04-22
基金
国家重点研发计划(2022YFA1402903)
国家自然科学基金(52172116; 62171214)
作者信息
    南京大学物理学院,固体微结构物理国家重点实验室,人工微结构科学与技术协同创新中心,南京 210093

通讯作者:

吕笑梅(1969—),女,博士,教授;
黄凤珍(1979—),女,博士,副教授。
参考文献
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