Electronic Structure of Mn-Doped ZnO Studied by Using X-ray Absorption Spectroscopy

P. Thakur,K. H. Chae,M. Subramanain,R. Jayavel,K. Asokan 한국물리학회 2008 THE JOURNAL OF THE KOREAN PHYSICAL SOCIETY Vol.53 No.5

Mn-doped ZnO thin films that showed ferromagnetism at room temperature were synthesized with nominal compositions Zn1-xMnxO (x = 0.03, 0.05, 0.07, 0.10 and 0.15) by using a spray pyrolysis technique. High-resolution X-ray diffraction studies suggested that the doped Mn ions occupied Zn sites and that all the samples exhibited a wurtzite hexagonal-like crystal structure similar to that of the parent compound, ZnO. The near-edge X-ray absorption fine structure (NEXAFS) measurements at the O K-edge clearly exhibited a pre-edge spectral feature, which evolved with Mn doping, similar to one observed in hole-doped cuprates and manganites. The Mn L3;2-edge NEXAFS spectra exhibited divalent Mn apart from mixed valent Mn3+ / Mn4+ states, which were well supported by Mn K-edge spectra.

X-ray Absorption and Emission Studies of Mn-doped ZnO Thin Films

P. Thakur,S. Gautam,K. H. Chae,M. Subramanain,R. Jayavel,K. Asokan 한국물리학회 2009 THE JOURNAL OF THE KOREAN PHYSICAL SOCIETY Vol.55 No.1

The electronic structure of Mn-doped ZnO thin films, a dilute magnetic semiconductor (DMS) having possible room temperature (RT) ferromagnetism, synthesized with nominal compositions of Zn1−xMnxO (x = 0.03, 0.05, 0.07, 0.10, and 0.15) by using the spray pyrolysis method are investigated using soft X-ray absorption and emission spectroscopy. The intensity of the pre-edge spectral feature at the O K-edge increases with Mn concentration, which clearly reveals that there is a strong hybridization of Mn ions with the ZnO matrix. The near-edge X-ray absorption fine structure (NEXAFS) measurements at the Mn K- and L3,2-edges show a mixed valence nature for the Mn ions, with Mn2+ and Mn3+/Mn4+ states, and the Mn3+/Mn4+ states are observed to increase with the Mn-concentration. Mn L2,3 resonant inelastic X-ray scattering (RIXS) measurements show that the excess Mn interstitials appear in the sample and that direct exchange interactions with substitutional Mn atoms may explain the magnetic interaction in Mn-doped ZnO. The electronic structure of Mn-doped ZnO thin films, a dilute magnetic semiconductor (DMS) having possible room temperature (RT) ferromagnetism, synthesized with nominal compositions of Zn1−xMnxO (x = 0.03, 0.05, 0.07, 0.10, and 0.15) by using the spray pyrolysis method are investigated using soft X-ray absorption and emission spectroscopy. The intensity of the pre-edge spectral feature at the O K-edge increases with Mn concentration, which clearly reveals that there is a strong hybridization of Mn ions with the ZnO matrix. The near-edge X-ray absorption fine structure (NEXAFS) measurements at the Mn K- and L3,2-edges show a mixed valence nature for the Mn ions, with Mn2+ and Mn3+/Mn4+ states, and the Mn3+/Mn4+ states are observed to increase with the Mn-concentration. Mn L2,3 resonant inelastic X-ray scattering (RIXS) measurements show that the excess Mn interstitials appear in the sample and that direct exchange interactions with substitutional Mn atoms may explain the magnetic interaction in Mn-doped ZnO.

Electronic Structure of Co-doped ZnO Thin Films by X-ray Absorption and Emission Spectroscopy

S. Gautam,P. Thakur,K. H. Chae,G. S. Chang,M. Subramanain,R. Jayavel,K. Asokan 한국물리학회 2009 THE JOURNAL OF THE KOREAN PHYSICAL SOCIETY Vol.55 No.1

The electronic structure of Co-doped ZnO thin films, synthesized with a nominal composition of Zn1−xCoxO (x = 0.03, 0.05, 0.7, 0.10, and 0.15) by using spray pyrolysis method, has been investigated using near edge X-ray absorption fine structure (NEXAFS) measurements at the O K- and the Co L3,2-edges and using resonant inelastic X-ray scattering (RIXS) measurements at Co L3,2-edge. All the prepared Zn1−xCoxO thin films showed ferromagnetic behavior at room temperature, as measured by using an alternating gradient force magnetometer (AGFM). The intensity of the pre-edge spectral feature at the O K-edge increases with the Co concentration, which clearly reveals that there is strong hybridization of O 2p − Co 3d atoms in the ZnO matrix. Spectral features of the Co L3,2-edge NEXAFS exhibit multiple absorption peaks and are similar to those of Co2+ ions coordinated in tetrahedral symmetry by four oxygen atoms. These results clearly demonstrate that Co is in a 2+ state, substituting at the Zn site. Co L3,2-edge RIXS measurements show that the substitution by Co atoms can explain the magnetic interaction in Co-doped ZnO. The electronic structure of Co-doped ZnO thin films, synthesized with a nominal composition of Zn1−xCoxO (x = 0.03, 0.05, 0.7, 0.10, and 0.15) by using spray pyrolysis method, has been investigated using near edge X-ray absorption fine structure (NEXAFS) measurements at the O K- and the Co L3,2-edges and using resonant inelastic X-ray scattering (RIXS) measurements at Co L3,2-edge. All the prepared Zn1−xCoxO thin films showed ferromagnetic behavior at room temperature, as measured by using an alternating gradient force magnetometer (AGFM). The intensity of the pre-edge spectral feature at the O K-edge increases with the Co concentration, which clearly reveals that there is strong hybridization of O 2p − Co 3d atoms in the ZnO matrix. Spectral features of the Co L3,2-edge NEXAFS exhibit multiple absorption peaks and are similar to those of Co2+ ions coordinated in tetrahedral symmetry by four oxygen atoms. These results clearly demonstrate that Co is in a 2+ state, substituting at the Zn site. Co L3,2-edge RIXS measurements show that the substitution by Co atoms can explain the magnetic interaction in Co-doped ZnO.

Crystallite size induced crossover from paramagnetism to superparamagnetism in zinc ferrite nanoparticles

Singh, J.P.,Gautam, S.,Srivastava, R.C.,Asokan, K.,Kanjilal, D.,Chae, K.H. Academic Press 2015 Superlattices and microstructures Vol.86 No.-

Present work investigates the crossover from paramagnetism to superparamagnetism as a function of crystallite size in zinc ferrite nanoparticles using near edge X-ray absorption spectroscopy. Synthesized paramagnetic and superparamagnetic nanoparticles exhibit presence of Fe<SUP>2+</SUP> and Fe<SUP>3+</SUP> ions with dominant concentration of Fe<SUP>3+</SUP> ions. Fe L- and O K-edges spectra of paramagnetic nanoparticles consist of more intense spectral features compared to that of superparamagnetic nanoparticles. This reflects enhanced t<SUB>2g</SUB> and e<SUB>g</SUB> symmetry states of Fe-O hybridized states in paramagnetic nanoparticles induced by increased degree of crystallization.

Electronic structure studies of nanoferrite Cu(x)Co(1-x)Fe2O4 by X-ray absorption spectroscopy.

Gautam, S,Muthurani, S,Balaji, M,Thakur, P,Padiyan, D Pathinettam,Chae, K H,Kim, S S,Asokan, K American Scientific Publishers 2011 Journal of Nanoscience and Nanotechnology Vol.11 No.1

<P>Pure and mixed cobalt copper ferrites are of great interest due to their widespread application in electronics and medicine. We report on the electronic structure of a nanoferrite Cu(x)Co(1-x)Fe2O4 (0.0 < or = x < or = 1.0) system studied by X-ray absorption spectroscopy. These magnetic nanoferrites (average crystallite size approximately 31-43 nm) were synthesized by an auto combustion method and are characterized by high resolution X-ray diffraction and near edge X-ray absorption fine structure measurements at the O K and Co, Cu, and Fe L-edges. The O K-edge spectra suggest that there is a strong hybridization between O 2p and 3d electrons of Co, Cu and Fe cations and Fe L3,2-edge spectra indicate that Fe ions coexist in mixed valence states (Fe3+ and Fe2+) at tetrahedral and octahedral sites of the spinel structure. Copper and cobalt ions are distributed in the divalent state in octahedral sites of the spinel structure. The origin of high saturation magnetization and coercivity in cobalt-copper ferrites are explained in light of these results.</P>

Investigations on magnetic and electrical properties of Zn doped Fe₂O₃ nanoparticles and their correlation with local electronic structures

Kumar, Parmod,Sharma, Vikas,Singh, Jitendra P.,Kumar, Ashish,Chahal, Surjeet,Sachdev, K.,Chae, K.H.,Kumar, Ashok,Asokan, K.,Kanjilal, D. Elsevier 2019 Journal of magnetism and magnetic materials Vol.489 No.-

<P><B>Abstract</B></P> <P>Present work aims at investigating the structural, magnetic and dielectric properties of zinc doped Fe<SUB>2</SUB>O<SUB>3</SUB> nanoparticles (pure, 10%, 20% & 30%) and correlated with their local electronic structures using X-ray absorption near-edge structure (XANES) spectroscopy. X-ray diffraction and Raman measurements infer that doping of Zn cations lead to the formation of secondary phases corresponding to ZnFe<SUB>2</SUB>O<SUB>4</SUB> along with the hematite phase of Fe<SUB>2</SUB>O<SUB>3</SUB>. Magnetic measurements show that magnetization vs magnetic field curve for 10% Zn doping exhibit maximum saturation magnetization (~2.93 × 10<SUP>−3</SUP> emu/g) as well as the coercivity (~956 Oe). The values of these parameters decrease for higher content of Zn. The temperature dependence of dielectric behaviour follows the same trend as that of the lattice parameter and magnetic measurements. The XANES spectra at Fe L- and Fe K-edges indicate partial reduction of Fe<SUP>3+</SUP> ions into Fe<SUP>2+</SUP> upon Zn doping in the Fe<SUB>2</SUB>O<SUB>3</SUB> lattice. However, divalent state is favourable for Zn (i.e. Zn<SUP>2+</SUP>) within the doping range reported in this study.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Zn doped Fe<SUB>2</SUB>O<SUB>3</SUB> nanoparticles. </LI> <LI> Study of magnetic and electrical properties. </LI> <LI> Correlation of magnetic and electrical properties with local electronic structure. </LI> </UL> </P>

Role of low energy transition metal ions in interface formation in ZnO thin films and their effect on magnetic properties for spintronic applications

Bhardwaj, Richa,Kaur, Baljeet,Singh, Jitendra Pal,Kumar, Manish,Lee, H.H.,Kumar, Parmod,Meena, R.C.,Asokan, K.,Hwa Chae, Keun,Goyal, Navdeep,Gautam, Sanjeev Elsevier 2019 APPLIED SURFACE SCIENCE - Vol.479 No.-

<P><B>Abstract</B></P> <P>In this study, X-ZnO/ZnO/Si(100) (X = Co, Ni and Cu) bilayer structure is fabricated using low energy ion implantation technique. Five different fluences 1 × 10<SUP>15</SUP>, 5 × 10<SUP>15</SUP>, 1 × 10<SUP>16</SUP>, 2.5 × 10<SUP>16</SUP> and 5 × 10<SUP>16</SUP> ions/cm<SUP>2</SUP> with 100 keV ion-beam energy were selected in order to implant the ions up to the depth of ≈44 nm as calculated through Stopping Range of Ion in Matter and Transport Range of Ions in Matter software. Structural modification was investigated by high resolution X-ray diffraction measurements in ZnO bilayer system. An observed systematic 2<I>θ</I> shift in (002) peak with increasing fluence implies increased density of implanted metal ions in ZnO matrix revealing the substitution of implanted ion at Zn-site. The mechanism of bilayer formation by ion-beam implantation technique has been discussed for metal-ions by investigating their interface properties. Atomic force microscopy reveals the morphological modification after ion implantation. Near-edge X-ray absorption fine-structure (NEXAFS) measurements at metal <I>K</I>- and <I>L</I> <SUB>3,2</SUB>-edges have been used to investigate the nature of implanted ions in terms of their valance state and local electronic environment. Further, O <I>K</I>-edge NEXAFS measurement for Ni-ZnO/ZnO/Si bilayer is highly sensitive to incident beam angles whereas no spectral change is seen for Zn <I>L</I>-edge measurements. The magnetic measurements were performed via vibrating sample magnetometer that showed the films are ferromagnetic at room temperature. The origin of ferromagnetism has been understood through defect mediated bound magnetic polaron model. Further, perpendicular magnetic anisotropy is also observed for Ni-ZnO/ZnO/Si bilayer structure at room temperature, which is correlated with the angle dependent O K-edge NEXAFS measurements. Fabrication of ZnO bilayer via ion implantation and investigation of above properties may prove useful in spin related and optoelectronic applications.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Observance of RTFM in metal ion-implanted Ni-ZnO/ZnO/Si bilayer </LI> <LI> HRXRD and NEXAFS measurements confirms the wurtzite phase and Zn<SUP>2+</SUP> substitution in ZnO matrix. </LI> <LI> Angle dependent NEXAFS measurements provides the evidence of observed PMA. </LI> </UL> </P> <P><B>Graphical Abstract</B></P> <P>Mechanism of ion beam interaction X (X = Co, Ni and Cu) with ZnO lattice forming X-ZnO/ZnO/Si(100) bilayer structure. Films were implanted using a multi cathode source of negative-ions by cesium sputtering (MC-SNICS) and with the increasing ion flux, X can undergo one of two mechanisms of either substituting the Zn-site or occupy interstitial position in ZnO matrix. Angle dependent O K-edge NEXAFS measurements provides the evidence of perpendicular magnetic anisotropy in ZnO bilayer. </P> <P>[DISPLAY OMISSION]</P>

Mechanistic insights into the interaction between energetic oxygen ions and nanosized ZnFe₂O₄: XAS-XMCD investigations

Singh, Jitendra Pal,Kaur, Baljeet,Sharma, Aditya,Kim, So Hee,Gautam, Sanjeev,Srivastava, Ramesh Chandra,Goyal, Navdeep,Lim, Weol Cheol,Lin, H.-J.,Chen, J. M.,Asokan, K.,Kanjilal, D.,Won, Sung Ok,Lee, The Royal Society of Chemistry 2018 Physical Chemistry Chemical Physics Vol.20 No.17

<P>The interactions of energetic ions with multi-cation compounds and their consequences in terms of changes in the local electronic structure, which may facilitate intriguing hybridization between O 2p and metal d orbitals and magnetic ordering, are the subject of debate and require a deep understanding of energy transfer processes and magnetic exchange mechanisms. In this study, nanocrystals of ZnFe2O4 were exposed to O<SUP>7+</SUP> ions with an energy of 100 MeV to understand, qualitatively and quantitatively, the metal-ligand field interactions, cation migration and magnetic exchange interactions by employing X-ray absorption fine structure measurements and X-ray magnetic circular dichroism to get deeper mechanistic insights. Nanosized zinc ferrite nanoparticles (NPs) with a size of ∼16 nm synthesized in the cubic spinel phase exhibited deterioration of the crystalline phase when 100 MeV O<SUP>7+</SUP> ions passed through them. However, the size of these NPs remained almost the same. The behaviour of crystal deterioration is associated with the confinement of heat in this interaction. The energy confined inside the nanoparticles promotes cation redistribution as well as the modification of the local electronic structure. Prior to this interaction, almost 42% of Zn<SUP>2+</SUP> ions occupied AO4 tetrahedra; however, this value increased to 63% after the interaction. An inverse effect was observed for metal ion occupancies in BO6 octahedra. The L-edge spectra of Fe and Zn reveal that the spin and valence states of the metal ions were not affected by this interaction. This effect is also supported by K-edge measurements for Fe and Zn. The t2g/eg intensity ratio in the O K-edge spectra decreased after this interaction, which is associated with detachment of Zn<SUP>2+</SUP> ions from the lattice. The extent of hybridization, as estimated from the ratio of the post-edge to the pre-edge region of the O K-edge spectra, decreased after this interaction. The metal-oxygen and metal-metal bond lengths were modified as a result of this interaction, as determined from extended X-ray absorption fine structure measurements. These measurements further support the observation of cation migration from AO4 tetrahedra to AO6 octahedra and <I>vice versa</I>. The Fe L-edge magnetic circular dichroism spectra indicate that Fe<SUP>3+</SUP> ions occupying sites in AO4 tetrahedra and BO6 octahedra exhibited antiferromagnetic-like ordering prior to this interaction. The NPs that interacted with energetic O ions displayed a different kind of magnetic ordering.</P>

Electronic structure of Ln₂O₂Te (Ln=La, Sm and Gd) by X-ray absorption spectroscopy

Gautam, Sanjeev,Chae, Keun Hwa,Llanos, Jaime,Peñ,a, Octavio,Asokan, K. Elsevier 2018 Vacuum Vol.158 No.-

<P><B>Abstract</B></P> <P>The oxytellurides are layered structure material which shows low lattice thermal conductivity and hence making them suitable for high temperature thermoelectric applications. We report the electronic structural properties of rare-earth doped oxytellurides [Ln<SUB>2</SUB>O<SUB>2</SUB>Te (Ln = La, Sm and Gd)] prepared by solid state reaction method. This research is focused on the suitability of rare-earth oxychalcogenide as a thermoelectric material using the electronic structure investigations. The X-ray absorption spectra at O K-edge show the O 2<I>p</I> bonding with Ln 5<I>d</I> and 4<I>f</I> and Te 5s states and the Ln M-edges show that the valences of Ln are to be trivalent or mixed states. The Ln M-edges are also simulated with Cowan code, and electronic structures of these oxytellurides are discussed. The substitution of different rare earth metals at the Ln-site, may enhance the thermoelectric property and stability of the material.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Oxytellurides Ln<SUB>2</SUB>O<SUB>2</SUB>Te (Ln = La, Sm and Gd) synthesized by the solid state reaction. </LI> <LI> NEXAFS shows the O 2<I>p</I> bonding with Ln 5d and, 4f and Te 5s states. </LI> <LI> Ln M-edge NEXAFS confirm the valences of Ln are to be trivalent and mixed. </LI> <LI> Cowan code and Thole et al. hypothesis are used to discuss the electronic structure. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

X-ray Absorption and Emission Study of Co-doped ZnO Thin Films

K. H. Chae,S. Gautam,J. H. Song,M. Subramanian,R.Jayavel,K. Asokan 한국진공학회 2009 한국진공학회 학술발표회초록집 Vol.37 No.-