{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T21:11:40Z","timestamp":1760130700042,"version":"build-2065373602"},"reference-count":43,"publisher":"MDPI AG","issue":"9","license":[{"start":{"date-parts":[[2023,8,31]],"date-time":"2023-08-31T00:00:00Z","timestamp":1693440000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"national funds","doi-asserted-by":"publisher","award":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","ICT_2009_02_012_1890","UIDB\/04564\/2020","UIDP\/04564\/2020","UIDB\/00313\/2020","UIDP\/00313\/2020","FSFZ-2023-0005","LA\/P\/0056\/2020"],"award-info":[{"award-number":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","ICT_2009_02_012_1890","UIDB\/04564\/2020","UIDP\/04564\/2020","UIDB\/00313\/2020","UIDP\/00313\/2020","FSFZ-2023-0005","LA\/P\/0056\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"name":"TAIL-UC facility funded","award":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","ICT_2009_02_012_1890","UIDB\/04564\/2020","UIDP\/04564\/2020","UIDB\/00313\/2020","UIDP\/00313\/2020","FSFZ-2023-0005","LA\/P\/0056\/2020"],"award-info":[{"award-number":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","ICT_2009_02_012_1890","UIDB\/04564\/2020","UIDP\/04564\/2020","UIDB\/00313\/2020","UIDP\/00313\/2020","FSFZ-2023-0005","LA\/P\/0056\/2020"]}]},{"DOI":"10.13039\/501100001871","name":"FCT","doi-asserted-by":"publisher","award":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","ICT_2009_02_012_1890","UIDB\/04564\/2020","UIDP\/04564\/2020","UIDB\/00313\/2020","UIDP\/00313\/2020","FSFZ-2023-0005","LA\/P\/0056\/2020"],"award-info":[{"award-number":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","ICT_2009_02_012_1890","UIDB\/04564\/2020","UIDP\/04564\/2020","UIDB\/00313\/2020","UIDP\/00313\/2020","FSFZ-2023-0005","LA\/P\/0056\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"name":"government task project","award":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","ICT_2009_02_012_1890","UIDB\/04564\/2020","UIDP\/04564\/2020","UIDB\/00313\/2020","UIDP\/00313\/2020","FSFZ-2023-0005","LA\/P\/0056\/2020"],"award-info":[{"award-number":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","ICT_2009_02_012_1890","UIDB\/04564\/2020","UIDP\/04564\/2020","UIDB\/00313\/2020","UIDP\/00313\/2020","FSFZ-2023-0005","LA\/P\/0056\/2020"]}]},{"name":"IMS project","award":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","ICT_2009_02_012_1890","UIDB\/04564\/2020","UIDP\/04564\/2020","UIDB\/00313\/2020","UIDP\/00313\/2020","FSFZ-2023-0005","LA\/P\/0056\/2020"],"award-info":[{"award-number":["UIDB\/50011\/2020","UIDP\/50011\/2020","LA\/P\/0006\/2020","ICT_2009_02_012_1890","UIDB\/04564\/2020","UIDP\/04564\/2020","UIDB\/00313\/2020","UIDP\/00313\/2020","FSFZ-2023-0005","LA\/P\/0056\/2020"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Crystals"],"abstract":"<jats:p>We successfully synthesized millimeter-sized single crystals of the molecular erbium(III) complex Er(acac)3(cphen), where acac = acetylacetonate and cphen = 5-chloro-1,10-phenanthroline. The novelty of this work stems from the exhaustive examination of the polar and electronic properties of the obtained samples at the macro-, micro-, and nanoscale levels. The single crystal X-ray diffraction method demonstrates the monoclinic (noncentrosymmetric space group P21) crystallographic structure of the synthesized samples and scanning electron microscopy exhibits the terrace\u2013ledge morphology of the surface in erbium(III) crystals. By using the piezoelectric force microscopy mode, the origin of the polar properties and the hyperpolarizability in the synthesized samples were assigned to the internal domain structure framed by the characteristic terrace\u2013ledge topography. The direct piezoelectric coefficient (~d33) was found to be intensely dependent on the local area and was measured in the range of 4\u20138 pm\/V. A nanoscale study using the kelvin probe force and capacitance force (dC\/dz) microscopy modes exposed the effect of the Er ions clustering in the erbium(III) complex. The PFM method applied solely to the Er ion revealed the corresponding direct piezoelectric coefficient (~d33) of about 4 pm\/V. Given the maximum piezoelectric coefficient in the erbium(III) complex at 8 pm\/V, we highlight the significant importance of the spatial coordination between the lanthanide ion and the ligands. The polar coordination between the lanthanide ion and the nitrogen and oxygen atoms was also corroborated by Raman spectroscopy supported by the density functional theory calculations. The obtained results can be of paramount importance for the application of molecular erbium(III) complex crystals in low-magnitude magnetic or electric field devices, which would reduce the energy consumption and speed up the processing switching in nonvolatile memory devices.<\/jats:p>","DOI":"10.3390\/cryst13091331","type":"journal-article","created":{"date-parts":[[2023,8,31]],"date-time":"2023-08-31T11:31:18Z","timestamp":1693481478000},"page":"1331","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Nanoscale Study of the Polar and Electronic Properties of a Molecular Erbium(III) Complex Observed via Scanning Probe Microscopy"],"prefix":"10.3390","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9155-9288","authenticated-orcid":false,"given":"Maxim","family":"Ivanov","sequence":"first","affiliation":[{"name":"Department of Materials and Ceramic Engineering, CICECO\u2014Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]},{"given":"Arkadiusz","family":"Grempka","sequence":"additional","affiliation":[{"name":"Biological and Chemical Research Centre, Faculty of Chemistry, University of Warsaw, 02-089 Warsaw, Poland"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3347-9076","authenticated-orcid":false,"given":"Arseniy","family":"Buryakov","sequence":"additional","affiliation":[{"name":"Department of Nanoelectronics, MIREA\u2014Russian Technological University, 78 Vernadsky Avenue, 119454 Moscow, Russia"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0907-5936","authenticated-orcid":false,"given":"Timur","family":"Nikitin","sequence":"additional","affiliation":[{"name":"CQC-IMS, Department of Chemistry, University of Coimbra, Rua Larga s\/n, 3004-535 Coimbra, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8338-6441","authenticated-orcid":false,"given":"Lic\u00ednia L. G.","family":"Justino","sequence":"additional","affiliation":[{"name":"CQC-IMS, Department of Chemistry, University of Coimbra, Rua Larga s\/n, 3004-535 Coimbra, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8264-6854","authenticated-orcid":false,"given":"Rui","family":"Fausto","sequence":"additional","affiliation":[{"name":"CQC-IMS, Department of Chemistry, University of Coimbra, Rua Larga s\/n, 3004-535 Coimbra, Portugal"},{"name":"Department of Physics, Faculty Sciences and Letters, Istanbul Kultur University, Bakirkoy, 34158 Istanbul, Turkey"}]},{"given":"Paula M.","family":"Vilarinho","sequence":"additional","affiliation":[{"name":"Department of Materials and Ceramic Engineering, CICECO\u2014Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4634-7395","authenticated-orcid":false,"given":"Jos\u00e9 A.","family":"Paix\u00e3o","sequence":"additional","affiliation":[{"name":"CFisUC, Department of Physics, University of Coimbra, Rua Larga s\/n, 3004-516 Coimbra, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2023,8,31]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"590","DOI":"10.1039\/D0QI01191F","article-title":"Recent Progress in Lanthanide Metal-Organic Frameworks and Their Derivatives in Catalytic Applications","volume":"8","author":"Zhang","year":"2021","journal-title":"Inorg. Chem. Front."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"189","DOI":"10.1039\/B905604C","article-title":"Lanthanide Luminescence for Functional Materials and Bio-Sciences","volume":"39","author":"Eliseeva","year":"2010","journal-title":"Chem. Soc. Rev."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"109","DOI":"10.1016\/j.jphotochemrev.2017.11.001","article-title":"Lanthanide Complex-Derived White-Light Emitting Solids: A Survey on Design Strategies","volume":"33","author":"SeethaLekshmi","year":"2017","journal-title":"J. Photochem. Photobiol. C Photochem. Rev."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"353","DOI":"10.1016\/j.pmatsci.2009.10.001","article-title":"Recent Progress in Quantum Cutting Phosphors","volume":"55","author":"Zhang","year":"2010","journal-title":"Prog. Mater. Sci."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"7589","DOI":"10.1063\/1.373027","article-title":"1.54 \u039cm Infrared Photoluminescence and Electroluminescence from an Erbium Organic Compound","volume":"87","author":"Sun","year":"2000","journal-title":"J. Appl. Phys."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"6466","DOI":"10.1039\/c0dt00132e","article-title":"Hybridization of Near-Infrared Emitting Erbium(Iii) and Ytterbium(Iii) Monoporphyrinate Complexes with Silica Xerogel: Synthesis, Structure and Photophysics","volume":"39","author":"He","year":"2010","journal-title":"Dalt. Trans."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"4766","DOI":"10.1039\/b822364e","article-title":"Monoporphyrinate Ytterbium(Iii) Complexes with New Ancillary Ligands: Synthesis, Structural Analysis and Photophysical Investigation","volume":"24","author":"He","year":"2009","journal-title":"Dalt. Trans."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"14440","DOI":"10.1021\/acs.inorgchem.9b01831","article-title":"Photochemically Tuned Magnetic Properties in an Erbium(III)-Based Easy-Plane Single-Molecule Magnet","volume":"58","author":"Li","year":"2019","journal-title":"Inorg. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"61","DOI":"10.1038\/s41535-020-00263-9","article-title":"Unusual Magnetoelectric Effect in Paramagnetic Rare-Earth Langasite","volume":"5","author":"Weymann","year":"2020","journal-title":"Npj Quantum Mater."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2236","DOI":"10.1002\/anie.201410523","article-title":"A High-Temperature Molecular Ferroelectric Zn\/Dy Complex Exhibiting Single-Ion-Magnet Behavior and Lanthanide Luminescence","volume":"54","author":"Long","year":"2015","journal-title":"Angew. Chem.-Int. Ed."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"8857","DOI":"10.1002\/anie.201904305","article-title":"A Nickel(II) Nitrite Based Molecular Perovskite Ferroelectric","volume":"58","author":"Xiong","year":"2019","journal-title":"Angew. Chem.-Int. Ed."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"4598","DOI":"10.1002\/chem.201305029","article-title":"Efficient Luminescence from Fluorene- and Spirobifluorene-Based Lanthanide Complexes upon Near-Visible Irradiation","volume":"20","author":"Bottaro","year":"2014","journal-title":"Chem.-A Eur. J."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"321","DOI":"10.1080\/00018730902920554","article-title":"Multiferroicity: The Coupling between Magnetic and Polarization Orders","volume":"58","author":"Wang","year":"2009","journal-title":"Adv. Phys."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"44","DOI":"10.32362\/2500-316X-2020-8-5-44-67","article-title":"Ferroelectric Memory: State-of-the-Art Manufacturing and Research","volume":"8","author":"Abdullaev","year":"2020","journal-title":"Russ. Technol. J."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"20","DOI":"10.1103\/Physics.2.20","article-title":"Classifying Multiferroics: Mechanisms and Effects","volume":"2","author":"Khomskii","year":"2009","journal-title":"Physics"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"16046","DOI":"10.1038\/natrevmats.2016.46","article-title":"The Evolution of Multiferroics","volume":"1","author":"Fiebig","year":"2016","journal-title":"Nat. Rev. Mater."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"021304","DOI":"10.1063\/1.4921545","article-title":"Multiferroic Oxide Thin Films and Heterostructures","volume":"2","author":"Lu","year":"2015","journal-title":"Appl. Phys. Rev."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"593","DOI":"10.3367\/UFNr.0182.201206b.0593","article-title":"Magnetoelectric and Multiferroic Media","volume":"182","author":"Pyatakov","year":"2012","journal-title":"Uspekhi Fiz. Nauk"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"299","DOI":"10.1140\/epjb\/e2009-00336-7","article-title":"A Short Review of the Magnetoelectric Effect and Related Experimental Techniques on Single Phase (Multi-) Ferroics","volume":"71","author":"Rivera","year":"2009","journal-title":"Eur. Phys. J. B"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"759","DOI":"10.1038\/nature05023","article-title":"Multiferroic and Magnetoelectric Materials","volume":"442","author":"Eerenstein","year":"2006","journal-title":"Nature"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"671","DOI":"10.1126\/science.aaz2795","article-title":"Room Temperature Magnetoelectric Coupling in a Molecular Ferroelectric Ytterbium(III) Complex","volume":"367","author":"Long","year":"2020","journal-title":"Science"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"3098","DOI":"10.1103\/PhysRevA.38.3098","article-title":"Density-Functional Exchange-Energy Approximation with Correct Asymptotic Behavior","volume":"38","author":"Becke","year":"1988","journal-title":"Phys. Rev. A"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"8822","DOI":"10.1103\/PhysRevB.33.8822","article-title":"Density-Functional Approximation for the Correlation Energy of the Inhomogeneous Electron Gas","volume":"33","author":"Perdew","year":"1986","journal-title":"Phys. Rev. B"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"464003","DOI":"10.1088\/0022-3727\/44\/46\/464003","article-title":"Piezoresponse Force Microscopy (PFM)","volume":"44","author":"Soergel","year":"2011","journal-title":"J. Phys. D Appl. Phys."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"173","DOI":"10.1007\/BF00528565","article-title":"Energy-Adjusted Pseudopotentials for the Rare Earth Elements","volume":"75","author":"Dolg","year":"1989","journal-title":"Theor. Chim. Acta"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"134222","DOI":"10.1016\/j.molstruc.2022.134222","article-title":"Octa-Coordination in Complexes of Lanthanides with N2 Confirmed by Matrix-Isolation IR Spectroscopy and DFT Calculations","volume":"1272","year":"2023","journal-title":"J. Mol. Struct."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"377","DOI":"10.1063\/1.1595651","article-title":"Structure and Vibrations of Lanthanide Trihalides: An Assessment of Experimental and Theoretical Data","volume":"33","author":"Konings","year":"2004","journal-title":"J. Phys. Chem. Ref. Data"},{"unstructured":"(2023, June 01). Chemcraft-Graphical Software for Visualization of Quantum Chemistry Computations. Version 1.8, Build 654. Available online: https:\/\/www.chemcraftprog.com.","key":"ref_28"},{"unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Petersson, G.A., and Nakatsuji, H. (2016). Gaussian 16, Revision B.01, Gaussian, Inc.","key":"ref_29"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"7269","DOI":"10.1021\/acs.cgd.1c01123","article-title":"2,4,6-Trinitro-N-(m-Tolyl)Aniline: A New Polymorphic Material Exhibiting Different Colors","volume":"21","author":"Nogueira","year":"2021","journal-title":"Cryst. Growth Des."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"5701","DOI":"10.1039\/c3tc30686k","article-title":"Novel Erbium(Iii) Complexes with 2,6-Dimethyl-3,5-Heptanedione and Different N,N-Donor Ligands for Ormosil and PMMA Matrices Doping","volume":"1","author":"Lahoz","year":"2013","journal-title":"J. Mater. Chem. C"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"187","DOI":"10.1016\/j.poly.2013.08.035","article-title":"A New Near-IR Luminescent Erbium(III) Complex with Potential Application in OLED Devices","volume":"65","author":"Miranda","year":"2013","journal-title":"Polyhedron"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"485","DOI":"10.1016\/j.poly.2014.07.006","article-title":"X-Ray Analysis, Molecular Modeling and NIR-Luminescence of Erbium(III) 2,4-Octanedionate Complexes with N,N-Donors","volume":"81","author":"Silva","year":"2014","journal-title":"Polyhedron"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"1703","DOI":"10.1039\/C4NJ01828A","article-title":"Slow Magnetic Relaxation and Photoluminescent Properties of a Highly Coordinated Erbium (iii) Complex with Dibenzoylmethane and 2,2\u2032-Bipyridine","volume":"39","author":"Coutinho","year":"2015","journal-title":"New J. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"357","DOI":"10.1038\/nmat2137","article-title":"Organic Ferroelectrics","volume":"7","author":"Horiuchi","year":"2008","journal-title":"Nat. Mater."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"789","DOI":"10.1038\/nature08731","article-title":"Above-Room-Temperature Ferroelectricity in a Single-Component Molecular Crystal","volume":"463","author":"Horiuchi","year":"2010","journal-title":"Nature"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"6428","DOI":"10.1021\/ja5017393","article-title":"Design of Ferroelectric Organic Molecular Crystals with Ultrahigh Polarization","volume":"136","author":"Chen","year":"2014","journal-title":"J. Am. Chem. Soc."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"8051","DOI":"10.1021\/jacs.8b04600","article-title":"Multiaxial Molecular Ferroelectric Thin Films Bring Light to Practical Applications","volume":"140","author":"Tang","year":"2018","journal-title":"J. Am. Chem. Soc."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"1093","DOI":"10.1016\/j.apsusc.2018.11.213","article-title":"Strong Impact of LiNbO3 Fillers on Local Electromechanical and Electrochemical Properties of P(VDF-TrFe) Polymer Disclosed via Scanning Probe Microscopy","volume":"470","author":"Ivanov","year":"2019","journal-title":"Appl. Surf. Sci."},{"unstructured":"Magonov, S., and NT-MDT Development (2022, December 01). Magonov Single-Pass Measurements in Atomic Force Microscopy: Kelvin Probe Force Microscopy and Local Dielectric Studies. Available online: https:\/\/www.ntmdt-si.com\/resources\/applications\/single-pass-measurements-in-atomic-force-microscopy-kelvin-probe-force-microscopy-and-local-dielectric-studies.","key":"ref_40"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"2607","DOI":"10.1113\/jphysiol.2010.202580","article-title":"Non-Linear Relationship between Hyperpolarisation and Relaxation Enables Long Distance Propagation of Vasodilatation","volume":"589","author":"Chaston","year":"2011","journal-title":"J. Physiol."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"2084","DOI":"10.1002\/adma.201204237","article-title":"Self-Assembled Organic Microfibers for Nonlinear Optics","volume":"25","author":"Xu","year":"2013","journal-title":"Adv. Mater."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"948","DOI":"10.1002\/adom.201400637","article-title":"Controlling Microsized Polymorphic Architectures with Distinct Linear and Nonlinear Optical Properties","volume":"3","author":"Xu","year":"2015","journal-title":"Adv. Opt. Mater."}],"container-title":["Crystals"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4352\/13\/9\/1331\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T20:43:32Z","timestamp":1760129012000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4352\/13\/9\/1331"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,8,31]]},"references-count":43,"journal-issue":{"issue":"9","published-online":{"date-parts":[[2023,9]]}},"alternative-id":["cryst13091331"],"URL":"https:\/\/doi.org\/10.3390\/cryst13091331","relation":{},"ISSN":["2073-4352"],"issn-type":[{"type":"electronic","value":"2073-4352"}],"subject":[],"published":{"date-parts":[[2023,8,31]]}}}