#
Doping Effects on the Multiferroic Properties of KNbO_{3} Nanoparticles

^{1}

^{2}

^{3}

^{*}

## Abstract

**:**

## 1. Introduction

## 2. Model and Method

## 3. Numerical Results and Discussion

#### 3.1. Ion-Doping Dependence of the Magnetization of Bulk KNO

#### 3.2. Ion-Doping Dependence of the Polarization of Bulk KNO

#### 3.3. Magnetic and Electric Properties of KNO Nanoparticles

#### 3.4. Magnetic Field Dependence of the Polarization of KNO Bulk and NPs

#### 3.5. Ion-Doping Dependence of the Band Gap of Bulk KNO

## 4. Conclusions

## Author Contributions

## Funding

## Institutional Review Board Statement

## Informed Consent Statement

## Data Availability Statement

## Conflicts of Interest

## References

- Min, K.; Huang, F.; Lu, X.; Kan, Y.; Zhang, J.; Peng, S.; Liu, Y.; Su, J.; Zhang, C.; Liu, Z.; et al. Room-temperature multiferroic properties of Co-doped KNbO
_{3}ceramics. Solid State Commun.**2012**, 152, 304–306. [Google Scholar] [CrossRef] - Li, H.; Hao, Y.; Lin, Z.; He, X.; Cai, J.; Gong, X.; Gu, Y.; Zhang, R.; Cheng, H.; Zhang, B. (K, Na)NbO
_{3}lead-free piezoceramics prepared by microwave sintering and solvothermal powder synthesis. Solid State Commun.**2022**, 353, 114871. [Google Scholar] [CrossRef] - Yoneda, Y.; Ohara, K.; Nagata, H. Local structure and phase transitions of KNbO
_{3}. Jpn. J. Appl. Phys.**2018**, 57, 11UB07. [Google Scholar] [CrossRef] - Song, G.; Chen, L.; Xing, L.; Zhang, K.; Wu, Z.; Yang, H.; Zhang, N. Effect of Fe
^{3+}doping on the ferrielectric and magnetic properties of KNbO_{3}ceramics. Physica B**2021**, 621, 413308. [Google Scholar] [CrossRef] - Sakthivel, R.; Ramraj, R.B.; Ramamurthi, K.; Raman, S. Influence of Cr-doping on structural, morphological, optical, dielectric and magnetic properties of KNbO
_{3}ceramics. Mater. Chem. Phys.**2018**, 213, 130–139. [Google Scholar] [CrossRef] - Manikandan, M.; Venkateswaran, C. Observation of ferromagnetism in Mn doped KNbO
_{3}. AIP Conf. Proc.**2015**, 1665, 130036. [Google Scholar] [CrossRef] - Astudillo, J.A.; Izquierdo, J.L.; Gomez, A.; Bolanos, G.; Moran, O. Ferromagnetism at room temperature in Co-doped KNbO
_{3}bulk samples. J. Magn. Magn. Mater.**2014**, 373, 86–89. [Google Scholar] [CrossRef] - Astudillo, J.A.; Dionizio, S.A.; Izquierdo, J.L.; Moran, O.; Heiras, J.; Bolanos, G. Magnetic and electrical properties in Co-doped KNbO
_{3}bulk samples. AIP Adv.**2018**, 8, 055817. [Google Scholar] [CrossRef] - Korde, V.; Patil, N.; Shamkuwar, S. A critical field study of ferroelectric domain in Al-doped KNbO
_{3}single crystal. Ceram. Intern.**2022**, 48, 9172–9179. [Google Scholar] [CrossRef] - Golovina, I.S.; Shanina, B.D.; Kolesnik, S.P.; Geifman, I.N.; Andriiko, A.A. Magnetic properties of nanocrystalline KNbO
_{3}. J. Appl. Phys.**2013**, 114, 174106. [Google Scholar] [CrossRef] - Jameel, M.H.; Rehman, A.; Roslan, M.S.; Agam, M.A. To investigate the structural, electronic, optical and magnetic properties of Sr-doped KNbO
_{3}for perovskite solar cell applications: A DFT study. Phys. Scr.**2023**, 98, 055802. [Google Scholar] [CrossRef] - Zhang, X.; Qi, R.; Dong, S.; Yang, S.; Jing, C.; Sun, L.; Chen, Y.; Hong, X.; Yang, P.; Yue, F.; et al. Modulation of Ferroelectric and Optical Properties of La/Co-Doped KNbO
_{3}Ceramics. Nanomater**2021**, 11, 2273. [Google Scholar] [CrossRef] [PubMed] - Wang, P.; Shen, H.; Xia, K.; Zong, W.; Tan, R. Ferroelectric Properties of KNbO
_{3}Doped with Na: First-Principles Calculations. J. Phys. Conf. Ser.**2011**, 2209, 012003. [Google Scholar] [CrossRef] - Wang, P.; Shen, H.; Xia, K.; Tan, R.; Zong, W. First-principles study of the ferrielectric of X-doped KNbO
_{3}(X = Na, Rb, and Cs). Ferroelectrics**2023**, 603, 267–275. [Google Scholar] [CrossRef] - Trepakov, V.A.; Savinov, M.L.; Zelezny, V.; Syrnikov, P.P.; Deyneka, A.G.; Jastrabik, L. Li doping effect on properties and phase transfomations of KNbO
_{3}. J. Eur. Ceram. Soc.**2007**, 27, 4071–4073. [Google Scholar] [CrossRef] - Cucatti, S.; Gularte, L.T.; Fernandes, C.D.; Carvalho, R.D.; Ferrer, M.M.; Jardim, P.L.G.; Raubach, C.W.; Cavaac, S.S.; Moreira, M.L. KNbO
_{3}photoelectrode for DSSC: A structural, optical and electrical approach. Dalton Trans.**2023**, 52, 5976–5982. [Google Scholar] [CrossRef] [PubMed] - Dudhe, C.; Khambadkar, S.; Koinkar, P.M. Ferroelectric behavior in nanocrystalline KNbO
_{3}synthesized by a modified polymerized complex method. Ferroelectrics**2018**, 531, 157–166. [Google Scholar] [CrossRef] - Ge, H.H.; Huang, Y.; Hou, Y.; Xiao, H.; Zhu, M. Size dependence of the polarization and dielectric properties of KNbO
_{3}nanoparticles. RSC Adv.**2014**, 4, 23344–23350. [Google Scholar] [CrossRef] - Lee, G.; Shin, Y.-H.; Son, J.Y. Strain-Induced High Polarization of a KNbO
_{3}Thin Film on a Single Crystalline Rh Substrate. J. Amer. Ceram. Soc.**2012**, 95, 2773–2776. [Google Scholar] [CrossRef] - Golovina, I.S.; Lemishko, S.V.; Morozovska, A.N. Percolation Magnetism in Ferroelectric Nanoparticles. Nanoscale Res. Lett.
**2017**, 12, 382. [Google Scholar] [CrossRef] - Diao, C.L.; Zheng, H.W. The preparation and surface photovoltage characterization of KNbO
_{3}powder. J. Mater. Sci. Mater. Electr.**2015**, 26, 3108–3111. [Google Scholar] [CrossRef] - Liang, Y.; Shao, G. First principles study for band engineering of KNbO
_{3}with 3d transition metal substitution. RSC Adv.**2019**, 9, 7551. [Google Scholar] [CrossRef] [PubMed] - Gilyazov, L.R.; Eremin, M.V.; Nikitin, S.I.; Yusupov, R.V.; Dejnek, A.; Trepakov, V.A. Selective Laser Spectroscopy of Mn
^{4+}Mn^{4+}Pair Centers in SrTiO_{3}Crystal. Opt. Spectr.**2014**, 116, 811–817. [Google Scholar] [CrossRef] - Gutowski, M. Antisymmetric exchange interactions in Cr
^{3+}Cr^{3+}pairs in the inverse spinel LiGa_{5}O_{8}. Phys. Rev. B**1978**, 18, 5984. [Google Scholar] [CrossRef] - Orlov, Y.S.; Nikolaev, S.; Gavrichkov, V.A.; Ovchinnikov, S.G. Exchange interaction between the high spin Co
^{3+}states in LaCoO_{3}. Comp. Mater. Sci.**2022**, 204, 111134. [Google Scholar] [CrossRef] - Kizaki, Y.; Noguchi, Y.; Miyayama, M. Defect control for low leakage current in K
_{0.5}Na_{0.5}NbO_{3}single crystals. Appl. Phys. Lett.**2006**, 89, 142910. [Google Scholar] [CrossRef] - Lin, D.; Li, Z.; Zhang, S.; Xu, Z.; Yao, X. Influence of MnO
_{2}Doping on the Dielectric and Piezoelectric Properties and the Domain Structure in (K_{0.5}Na_{0.5})NbO_{3}Single Crystals. J. Am. Ceram. Soc.**2010**, 93, 941–944. [Google Scholar] [CrossRef] - Wesselinowa, J.M.; Apostolova, I. Impact of defects on the properties of ferromagnetic nanoparticles. J. Appl. Phys.
**2008**, 103, 073910. [Google Scholar] [CrossRef] - Vikhnin, V.S.; Asatryan, H.R.; Zakharchenya, R.I.; Kutsenko, A.B.; Kapphan, S.E. Magnetic resonance in Pb
_{x}Nb_{y}O_{z}-ceramics as a system containing chemical fluctuation regions. Solid State Phys.**2005**, 47, 1535–1539. [Google Scholar] [CrossRef] - Diaz-Moreno, C.; Farias, R.; Hurtado-Macias, A.; Elizalde-Galindo, J.; Hernandez-Paz, J. Multiferroic response of nanocrystalline lithium niobate. J. Appl. Phys.
**2012**, 111, 07D907. [Google Scholar] [CrossRef] - Zeng, F.; Sheng, P.; Tang, G.S.; Pan, F.; Yan, W.S.; Hu, F.C.; Zou, Y.; Huang, Y.; Jiang, Z.; Guo, D. Electronic structure and magnetism of Fe-doped LiNbO
_{3}. Mater. Chem. Phys.**2012**, 136, 783–788. [Google Scholar] [CrossRef] - Lin, L.; Hu, C.; Huang, J.; Yan, L.; Zhang, M.; Chen, R.; Tao, H.; Zhang, Z. Magnetism and optical properties of LiNbO
_{3}doped with (Fe,Ni,Ga): First-principles calculations. J. Appl. Phys.**2021**, 130, 053901. [Google Scholar] [CrossRef] - Lin, L.; Huang, J.; Yu, W.; Zhu, L.; Wang, P.; Xu, Y.; Tao, H.; Zhang, Z. First principles study of the electronic and magnetic properties of (Co,Ga) co-doped LiNbO
_{3}. J. Appl. Phys.**2019**, 125, 073901. [Google Scholar] [CrossRef] - Zamarron-Montes, L.; Espinosa-Gonzalez, D.; Espinosa-Magana, F. Study of electronic and magnetic properties of Mn-doped KNbO
_{3}: A first-principles approach. Solid State Commun.**2004**, 377, 115394. [Google Scholar] [CrossRef]

**Figure 1.**Ion-doping dependence of the magnetization M in bulk KNO for T = 300 K and different doping ions at the Nb site: (1) Co; (2) Mn; (3) Cr. Curve 2a represents Mn doping in a KNO NP with d = 40 nm.

**Figure 2.**Ion-doping dependence of the polarization P in bulk KNO for T = 300 K and different doping ions at the Nb site: (1) Co; (2) Cr; and at the K site (3) Na. Curve 1a represents Co-doped KNO NP with d = 40 nm.

**Figure 3.**Size dependence of the magnetization M (1) and the polarization P (2) for KNO for T = 300 K.

**Figure 4.**Magnetic field dependence of the polarization P of Co-doped (1) bulk KNO and (2) KNO NP (40 nm) for x = 0.4, T = 300 K.

**Figure 5.**Ion-doping dependence of the band-gap energy ${E}_{g}$ in KNO for T = 300 K and different doping ions at the Nb site: (1) Cr; (2) Mn; (3) Co; (4) Zn.

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content. |

© 2024 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).

## Share and Cite

**MDPI and ACS Style**

Apostolov, A.T.; Apostolova, I.N.; Wesselinowa, J.M.
Doping Effects on the Multiferroic Properties of KNbO_{3} Nanoparticles. *Magnetochemistry* **2024**, *10*, 19.
https://doi.org/10.3390/magnetochemistry10030019

**AMA Style**

Apostolov AT, Apostolova IN, Wesselinowa JM.
Doping Effects on the Multiferroic Properties of KNbO_{3} Nanoparticles. *Magnetochemistry*. 2024; 10(3):19.
https://doi.org/10.3390/magnetochemistry10030019

**Chicago/Turabian Style**

Apostolov, A. T., I. N. Apostolova, and J. M. Wesselinowa.
2024. "Doping Effects on the Multiferroic Properties of KNbO_{3} Nanoparticles" *Magnetochemistry* 10, no. 3: 19.
https://doi.org/10.3390/magnetochemistry10030019