Abstract：Nanosized Ni1-xRxTiO3 (R=Nd, Sm and Eu; x=0, 0.05 and 0.1) powders were synthesized by sol-gel method. The effects of Nd, Sm, and Eu doping on the microstructure and optical, electrical, and magnetic properties of NiTiO3 were systematically studied using characterization techniques such as X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and physical property measurement system. The results show that all samples exhibit charge transfer of O—Ti bonds and O—Ni bonds (200-365 nm), spin-allowed transition of Ni2+ from 3A2g(3F) to 3T1g(3P) (450 nm), spin-forbidden transitions of 1T2g(1D) and 1A1g(1G) (490-520 nm), and spin-forbidden transition of 1Eg(1D) (743 nm). Absorption spectra of Nd- doped samples exhibit an absorption peak near 588 nm correlated with the electronic transition of Nb3+ at the octahedral position, which change the samples color from yellow to green. All samples exhibit antiferromagnetism and ferroelectricity at room temperature, and Nd, Sm, and Eu doping at the Ni site significantly enhance the ferroelectricity of NiTiO3. Doping elements with larger ionic radii cause lattice distortion, promote the rotation of ferroelectric domains, and enhancc the ferroelectricity.
[1] LEUNG C M, LI J, VIEHLAND D, et al.A review on applications of magnetoelectric composites: from heterostructural uncooled magnetic sensors, energy harvesters to highly efficient power converters[J]. Journal of Physics D-Applied Physics, 2018, 51: 263002. [2] SUN H Y, WANG J R, WANG Y S, et al.Nonvolatile ferroelectric domain wall memory integrated on silicon[J]. Nature Communications, 2022, 13(1): 4332. [3] ZHANG X Y, WANG Y, GAO X Y, et al.High-temperature and flexible piezoelectric sensors for lamb-wave-based structural health monitoring[J]. ACS Applied Materials & Interfaces, 2021, 13(40): 47764-47772. [4] ASTAFEV P, PAVELKO A, LERER A, et al.Microwave- absorbing properties of PbMg1/3Nb2/3O3-PbZrO3-PbTiO3- PbGeO3 (PMN-PZT-PG) solid solutions on a microstrip line in the microwave range[J]. Crystals, 2022, 12(4): 551. [5] XIN C, WANG Y, SUI Y, et al.Electronic, magnetic and multiferroic properties of magnetoelectric NiTiO3[J]. Journal of Alloys and Compounds, 2014, 613: 401-406. [6] RUIZ-PRECIADO M A, BULOU A, MAKOWSKA- JANUSIK M, et al. Nickel titanate (NiTiO3) thin films: RF-sputtering synthesis and investigation of related features for photocatalysis[J]. Crystengcomm, 2016, 18(18): 3229-3236. [7] YAMAMOTO O, TAKEDA Y, KANNO R, et al.Perovskite-type oxides as oxygen electrodes for high temperature oxide fuel cells[J]. Solid State Ionics, 1987, 22: 241-246. [8] SOBHANI-NASAB A, HOSSEINPOUR-MASHKAIN S M, SALAVATI-NIASARI M, et al. Synthesis, characterization, and photovoltaic application of NiTiO3 nanostructures via two-step sol-gel method[J]. Journal of Materials Science- Materials in Electronics, 2015, 26(8): 5735-5742. [9] SUBRAMANIAN S, GANAPATHY S, DHARMALINGAM S, et al.Enhanced charge carrier transfer process in nickel titanate nanostructures for environmental remediation of industrial dye[J]. Environmental Science and Pollution Research, 2023, 30(27): 70011-70021. [10] MAAFA I M, ALI M A.Enhanced organic pollutant removal efficiency of electrospun NiTiO3/TiO2-decorated carbon nanofibers[J]. Polymers, 2023, 15(1): 109. [11] CHUNG K H, LAM S S, PARK Y K, et al.Preparation of nickel-bismuth titanates enhanced visible-light photosensitivity and their photocatalytic properties for hydrogen generation by plasma cracking[J]. Molecular Catalysis, 2023, 545: 113239. [12] PISHCH I V, RADION E V.Production of pigments with a perovskite-like structure based on nickel titante by the precitation method[J]. Glass and Ceramics, 2003, 60(5/6): 154-157. [13] ASLAN E, TOY E, GUNER Z, et al.The effect of various nickel oxide ratios on the color and reflectivity of PY53 nickel-titanate yellow pigment[J]. Results in Chemistry, 2022, 4: 100662. [14] KASHANI F Z, GHOREISHI S M, KHOOBI A, et al.A carbon paste electrode modified with a nickel titanate nanoceramic for simultaneous voltammetric determination of ortho- and para-hydroxybenzoic acids[J]. Microchimica Acta, 2018, 186(1): 12. [15] OBAYASHI H, SAKURAI Y, GEJO T.Perovskite-type oxides as ethanol sensors[J]. Journal of Solid State Chemistry, 1976, 17(3): 299-303. [16] VARGA T, DROUBAY T C, BOWDEN M E, et al.Epitaxial growth of NiTiO3 with a distorted ilmenite structure[J]. Thin Solid Films, 2012, 520(17): 5534-5541. [17] TURSUN R B, SU Y C, YU Q S, et al.Room-temperature coexistence of electric and magnetic orders in NiTiO3 and effect of ethylene glycol[J]. Materials Science and Engineering B, 2018, 228: 96-102. [18] YUVARAJ S, NITHYA V D, FATHIMA K S, et al.Investigations on the temperature dependent electrical and magnetic properties of NiTiO3 by molten salt synthesis[J]. Materials Research Bulletin, 2013, 48(3): 1110-1116. [19] HACHIMI A G, ZAARI H, HAMEDOUN M, et al.Experimental and theoretical investigation of Nd doped ZnO[J]. Journal of Magnetism and Magnetic Materials, 2017, 444: 416-420. [20] KUMARI A, KUMARI K, AHMED F, et al.Influence of Sm doping on structural, ferroelectric, electrical, optical and magnetic properties of BaTiO3[J]. Vacuum, 2021, 184: 109872. [21] ZAFAR A, RAHMAN A, SHAHZADA S, et al.Electrical and magnetic properties of nano-sized Eu doped barium hexaferrites[J]. Journal of Alloys and Compounds, 2017, 727(15): 683-690. [22] TONG Y P, CHEN Z, WANG H X, et al.Fabrication and characterization of environmental-friendly Ni1-xRxTiO3 nanopigments with high NIR reflectance[J]. Functional Materials Letters, 2015, 8(5): 1550050. [23] SADJADI M S, ZARE K, KHANAHMADZADEH S, et al.Structural characterization of NiTiO3 nanopowders prepared by stearic acid gel method[J]. Materials Letters, 2008, 62(21/22): 3679-3681. [24] RUIZ-PRECIADO M A, KASSIBA A, GIBAUD A, et al. Comparison of nickel titanate (NiTiO3) powders synthesized by sol-gel and solid state reaction[J]. Materials Science in Semiconductor Processing, 2015, 37: 171-178. [25] GUIET A, HUAN T N, PAYEN C, et al.Copper-substituted NiTiO3 ilmenite-type materials for oxygen evolution reaction[J]. ACS Applied Materials & Interfaces, 2019, 11(34): 31038-31048. [26] NITHYA V D, SELVAN R K, KARTHIKEYAN K, et al.Impact of Si4+ ions doping on the electrochemical cycling performance of NiTiO3 as anodes for Li-ion batteries[J]. Journal of Nanoscience and Nanotechnology, 2015, 15(1): 694-702. [27] IMANI M, RADMANESH L, TADJARODI A.Synthesis and study of the pseudocapacitive behavior of heterojunctional NiTiO3-based chitosan nanocomposite[J]. Journal of Physics and Chemistry of Solids, 2020, 139: 109309. [28] HUANG Z D, ZHANG T T, LU H, et al.Grain- boundary- rich mesoporous NiTiO3 micro-prism as high tap-density, super rate and long life anode for sodium and lithium ion batteries[J]. Energy Storage Materials, 2018, 13: 329-339. [29] NUNE S V K. NiTiO3 nanocomposite: solvo-thermal synthesis and its application in environmental remediation[J]. Materials Today: Proceedings, 2019, 19: 2697-2701. [30] INCEESUNGVORN B, TEERANUNPONG T, NUNKAEW J, et al.Novel NiTiO3/Ag3VO4 composite with enhanced photocatalytic performance under visible light[J]. Catalysis Communications, 2014, 54: 35-38. [31] SIDDAIAH T, GOPAL N O.Doping Na+ into polyvinyl alcohol: nethacrylic acid-ethyl acrylate (PVA/MAA:EA) polymer blend electrolytes; a way to improve the blend’s thermal, structural, optical and electrical properties[J]. Journal of Macromolecular Science. Physics, 2023, 61(10/11): 1451-1462. [32] LIU X, HONG R, TIAN C.Tolerance factor and the stability discussion of ABO3-type ilmenite[J]. Journal of Materials Science-Materials in Electronics, 2008, 20(4): 323-327. [33] ZHAO Z T, GUO R F, MAO H R, et al.Effect of components on the microstructures and properties of rare-earth zirconate ceramics prepared by ultrafast high-throughput sintering[J]. Journal of the European Ceramic Society, 2021, 41(11): 5768-5773. [34] INCEESUNGVORN B, TEERANUNPONG T, NUNKAEW J, et al.Novel NiTiO3/Ag3VO4 composite with enhanced photocatalytic performance under visible light[J]. Catalysis Communications, 2014, 54: 35-38. [35] YANG G R, CHANG W, YAN W.Fabrication and characterization of NiTiO3 nanofibers by sol-gel assisted electrospinning[J]. Journal of Sol-Gel Science and Technology, 2014, 69(3): 473-479. [36] SAKAMOTO K, HAYASHI F, SATO K, et al.XPS spectral analysis for a multiple oxide comprising NiO2, TiO2, and NiTiO3[J]. Applied Surface Science, 2020, 526: 146729. [37] MOMOSE Y, TSURUYA K, SAKURAI T, et al.Photoelectron emission and XPS studies of real iron surfaces subjected to scratching in air, water, and organic liquids[J]. Surface and Interface Analysis, 2016, 48(4): 202-211. [38] TZENG B C, SELVAM T, TSAI M H.M(II)- dipyridylamide-based coordination frameworks (M=Mn, Co, Ni): structural transformation[J]. Journal of Solid State Chemistry, 2016, 243: 70-76. [39] CUMMINS T R, EGDELL R G.Electron energy in Nd2-xCexCuO4: a study by valence and core-level photoemission spectroscopy[J]. Physical Review B, 1993, 48(9): 6556-6568. [40] KOMPA A, MURARI M S, KEKUDA D, et al.Low concentration rare earth doping (Nd) and its effect on structural properties of titania thin films[J]. Ceramics International, 2021, 47(10): 13480-13487. [41] WEI L G, YANG Y L, XIA X, et al.Band edge movement in dye sensitized Sm-doped TiO2 solar cells: a study by variable temperature spectroelectrochemistry[J]. RSC Advances, 2015, 5(86): 70512-70521. [42] MERCIER F, ALLIOT C, BION L, et al.XPS study of Eu (III) coordination compounds: core levels binding energies in solid mixed-oxo-compounds EumXxOy[J]. Journal of Electron Spectroscopy and Related Phenomena, 2006, 150(1): 21-26. [43] BELLAM J B, RUIZ-PRECIADO M A, EDELY M, et al. Visible-light photocatalytic activity of nitrogen-doped NiTiO3 thin films prepared by a co-sputtering process[J]. RSC Advances, 2015, 5(14): 10551-10559. [44] LOPES K P, CAVALCANTE L S, SIMOES A Z, et al.NiTiO3 powders obtained by polymeric precursor method: synthesis and characterization[J]. Journal of Alloys and Compounds, 2009, 468(1/2): 327-332. [45] KARMAKAR S, MANNA A K, VARMA S, et al.Investigation of optical, electrical and magnetic properties of hexagonal NiTiO3 nanoparticles prepared via ultrasonic dispersion techniques for high power applications[J]. Materials Research Express, 2018, 5(5): 055037. [46] BARATON M I, BUSCA G, PRIETO M C, et al.On the vibrational spectra and structure of FeCrO3 and of the ilmenite-type compounds CoTiO3 and NiTiO3[J]. Journal of Solid State Chemisry, 1994, 122(1): 9-14. [47] CHELLASAMY V, THANGADURAI P.Structural and electrochemical investigations of nanostructured NiTiO3 in acidic environment[J]. Frontiers of Materials Science, 2017, 11(2): 162-170. [48] ZHU J, CHEN X B, SHEN J C.Lanthanum distribution in SrBi4-xLaxTi4O15[J]. Materials Letters, 2005, 59(12): 1581-1584. [49] MAMAT M H, PARIMON N, ISMAIL A S, et al.Structural, optical, and electrical evolution of sol-gel-immersion grown nickel oxide nanosheet array films on aluminium doping[J]. Journal of Materials Science-Materials in Electronics, 2019, 30(10): 9916-9930. [50] HE X M, WANG F, LIU H, et al.Fabrication of highly dispersed NiTiO3@TiO2 yellow pigments with enhanced NIR reflectance[J]. Materials Letters, 2017, 208(8): 82-85. [51] ACHER L, JI H, GARINO N, et al.Thermochromic properties of pure NiTiO3 and its Cu- or Co-doped derivatives[J]. Ceramics International, 2023, 49(8): 12267-12273. [52] RAHIMI-NASRABADI M, AHMADI F, EGHBALI- ARANI M.Novel route to synthesize nanocrystalline nickel titanate in the presence of amino acids as a capping agent[J]. Journal of Materials Science-Materials in Electronics, 2016, 27(11): 11873-11878. [53] TONG Y P, FU J, CHEN Z.Synthesis, characterization, and NIR reflectance of highly dispersed NiTiO3 and NiTiO3/TiO2 composite pigments[J]. Journal of Nanomaterials, 2016, 2016: 5464978. [54] WANG J, SUN J Y, HUANG J, et al.Synthesis and its characterization of silver sulfide/nickel titanate/chitosan nanocomposites for photocatalysis and water splitting under visible light, and antibacterial studies[J]. Materials Chemistry and Physics, 2021, 272: 124990. [55] CRAWFORD S E, OHODNICKI P R, BALTRUS J P.Materials for the photoluminescent sensing of rare earth elements: challenges and opportunities[J]. Journal of Materials Chemistry C, 2020, 8(24): 7975-8006. [56] DUNG N V, HAI N N, NGOC T V D, et al. Optical, ferroelectric, and magnetic properties of NiTiO3-CoFe2O4 composites prepared by one-step sol-gel method[J]. Journal of Materials Science-Materials in Electronics, 2022, 33(23): 18910-18921. [57] FENNIE C J.Ferroelectrically induced weak ferromagnetism by design[J]. Physical Review Letters, 2008, 100(16): 167203. [58] UEHARA M, AMANO Y, MIZUNO T, et al.Lattice distortion and piezoelectricity enhancement in GaN by alloying with group III and rare-earth elements: a comparative experimental study[J]. Physica Status Solidi- Rapid Research Letters, 2023: 2300087.
2023, Vol. 28 
