Article(id=1319726317667463526, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319726260922728931, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20250289, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1744560000000, receivedDateStr=2025-04-14, revisedDate=1747324800000, revisedDateStr=2025-05-16, acceptedDate=null, acceptedDateStr=null, onlineDate=1792576873460, onlineDateStr=2026-10-21, pubDate=1758297600000, pubDateStr=2025-09-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792576873460, onlineIssueDateStr=2026-10-21, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792576873460, creator=13701087609, updateTime=1792576873460, 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=2441, endPage=2451, ext={EN=ArticleExt(id=1319726317885567335, articleId=1319726317667463526, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Texture-Induced Self-Polarization of Flexible BiFeO
3 Thin Films, 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 Conventional poling methods, such as contact poling and corona poling, are frequently hampered by susceptibility to dielectric breakdown and film failure. Achieving self-poling without external poling procedure required in lead-free ferroelectric thin films is critical for advancing flexible piezoelectric devices. Here, we introduce a LaNiO3 seed layer on flexible mica substrates to induce (001)-textured BiFeO3 films for self-poling, while systematically evaluating the impact of Mn doping on film properties. The resulting self-poled BiFeO3 films achieve a piezoelectric coefficient d33, d≈50 pC/N and demonstrate exceptional bending stability, retaining over 90% of their initial d33, d after more than 5000 bending cycles. This work presents a compelling new pathway for the development of high-performance lead-free flexible ferroelectric devices.
Methods Mica substrates were prepared via blade-cleaving, followed by sequential 3-minute ultrasonic cleaning in anhydrous ethanol, acetone, and anhydrous ethanol to remove contaminants. LaNiO3 solution was synthesized by sol-gel processing: stoichiometric lanthanum nitrate and nickel acetate (La: Ni = 1∶1 mol ratio, 0.2 mol/L concentration) were dissolved in glacial acetic acid with stirring at 80 ℃ until complete dissolution, then stirred for 2 h at 25 ℃. The solution was aged for 48 h at 25 ℃. Subsequently, LaNiO3 solution was spin-coated onto mica substrates at 5000 rpm, dried on a hotplate at 150 ℃, and thermally processed in a rapid thermal annealing furnace under air atmosphere. This involved a pyrolysis step at 400 ℃ for 5 min, followed by crystallization at 700 ℃ for 1 min. Layer-by-layer spin-coating with intermediate annealing achieved the target LaNiO3 electrode thickness. Mn-doped BiFeO3 solutions (0, 1%, 3%, 5% Mn-doping) were prepared by dissolving bismuth nitrate (10% excess), iron nitrate, and manganese acetate in ethylene glycol monomethyl ether (0.4 mol/L concentration), adding citric acid (1∶1 molar ratio to metal ions) as a chelating agent, magnetically stirring for 4 h at 25 ℃, and aging for 48 h. These sols were spin-coated onto LaNiO3/mica substrates, followed by 10 iterative cycles of thermal treatment: drying at 200 ℃ (5 min), pyrolysis at 400 ℃ (5 min), and crystallization at 550 ℃ (5 min) per layer to attain the final film thickness.
Results and discussion The LaNiO3 seed layer promotes a dominant (001) texture in BiFe1-xMnxO3 (0%, 1%, 3%, 5% Mn) thin films. However, increasing Mn dopant concentration induces compressive stress relaxation, significantly degrading the film texture from 92.3% to 56.7%. Undoped and 0.01% Mn-doped films exhibit pronounced out-of-plane self-polarization, yielding piezoelectric coefficients d33, d = 48.6 pC/N and 47.4 pC/N. Internal bias in PFM voltage-phase/amplitude curves and unipolar conduction in I-V characteristics unequivocally confirm a built-in electric field. This field weakens at higher Mn concentrations (x = 0.03 and 0.05), concurrently diminishing self-polarization—A causal relationship demonstrating that self-polarization originates from this internal field. Although increased Mn doping reduces self-polarization, it, however, significantly improves electrical performance: leakage current decreases by 78% at x = 0.05 compared to undoped films. Therefore, optimal Mn doping (x = 0.01) synergistically preserves self-polarization while enhancing electrical performance. As flexible films, BiFe1-xMnxO3 demonstrates exceptional bending stability and mechanical fatigue resistance. P-E hysteresis loops remain invariant under compressive/tensile stresses compared to undeformed states. After 5000 bending cycles at tensile strain (r =10 mm), ferroelectric properties and piezoelectric coefficient d33, d degrade by<10%, confirming outstanding operational durability.
Conclusions This work demonstrates that LaNiO3 seed layers deposited on mica substrates induce a dominant (001) texture in BiFeO3-based thin films. Undoped and 0.01% Mn-doped compositions exhibit significant self-polarization driven by a built-in electric field, while increased Mn doping reduces texture degree from 92.3% to 56.7% and weakens self-polarization. The latter is evidenced by the decrease of piezoelectric coefficient, d33, d, from 48.6 pC/N to 14.6 pC/N. Crucially, despite diminishing self-polarization, Mn doping substantially enhances electrical properties (78% leakage reduction at x=0.05). All films endow exceptional mechanical resilience: after 5,000 bending cycles (r = 10 mm), d33, d degrades <10%, with P-E hysteresis loops remaining unaffected. By synergistically integrating texture engineering and doping optimization, we achieve self-poling with a d33, d≈50 pC/N, establishing a novel technological pathway for lead-free flexible ferroelectric devices.
, authors=Zhiqiang ZHOU, Shuo HUANG, Le DAI, Lisha LIU, authorsList=Zhiqiang ZHOU, Shuo HUANG, Le DAI, Lisha LIU, authorCompany=null, correspAuthors=Lisha LIU, authorNote=
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3薄膜自极化性能调控, columnId=1321945583783359132, journalTitle=硅酸盐学报, columnName=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, runingTitle=null, highlight=null, articleAbstract=
为在BiFeO3薄膜中诱导宏观自极化性能，引入晶种层LaNiO3，在具有高度柔性的云母衬底上制备了具有高度（001）取向的BiFe1-xMnxO3（x=0，0.01，0.03，0.05）织构薄膜。研究表明，未掺杂和低浓度（x≤0.01）掺杂的薄膜存在向下的自极化行为，并存在内置电场。随着Mn掺杂浓度的增加，薄膜的织构度从92.3%下降至56.7%，自极化程度逐渐减弱，自极化压电系数d33，d从48.6 pC/N下降到14.1 pC/N，由此推断衬底对薄膜产生的应力是产生自极化行为的原因。Mn掺杂虽弱化了自极化程度，但大大提高了薄膜的电学性能。此外，该柔性薄膜具有良好的弯曲稳定性以及耐机械疲劳特性，在5×103次弯曲（r=10 mm）后，正压电系数d33，d下降不超过10%。
, authors=周智强, 黄硕, 戴乐, 刘丽莎, authorsList=周智强, 黄硕, 戴乐, 刘丽莎, authorCompany=null, correspAuthors=刘丽莎, authorNote=
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刘丽莎（1989—），女，博士，教授。
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周智强（1998—），男，硕士研究生。
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