Spin-induced transition metal (TM) doped SnO2 a dilute magnetic semiconductor (DMS): A first principles study

Accepted Manuscript Spin-induced transition metal (TM) doped SnO2 a dilute magnetic semiconductor (DMS): A first principles study D.P. Rai, Amel Laref, A. Shankar, Sandeep, Anup P. Sakhya, R. Khenata, R.K. Thapa PII:

S0022-3697(17)31886-3

DOI:

10.1016/j.jpcs.2018.04.006

Reference:

PCS 8522

To appear in:

Journal of Physics and Chemistry of Solids

Received Date: 6 October 2017 Revised Date:

22 March 2018

Accepted Date: 7 April 2018

Please cite this article as: D.P. Rai, A. Laref, A. Shankar, Sandeep, A.P. Sakhya, R. Khenata, R.K. Thapa, Spin-induced transition metal (TM) doped SnO2 a dilute magnetic semiconductor (DMS): A first principles study, Journal of Physics and Chemistry of Solids (2018), doi: 10.1016/j.jpcs.2018.04.006. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT Spin-induced transition metal (TM) doped SnO2 a dilute magnetic semiconductor (DMS): A first principles study D. P. Rai,1, ∗ Amel Laref,2 A. Shankar,3 Sandeep,4 Anup P. Sakhya,5 R. Khenata,6 and R. K. Thapa7 1

Department of Physics, Pachhunga University College, Aizawl, 796001, India Department of Physics,College of Science, King Saud University, Riyadh,Saudi Arabia 3 Department of Physics, Kurseong College, Darjeeling, India-734203 4 Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education, Guangdong Province, Shenzhen University, China-518060 5 Department of Physics, Bose Institute, 93/1 Acharya Prafulla Chandra Road, Kolkata, 700009, India 6 Laboratoire de Physique Quantique de la matiere et de Modelisation Mathematique, Universitede Mascara, Mascara, 29000, Algeria 7 Department of Physics, Mizoram University, Aizawl, 796009, India

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I.

INTRODUCTION

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A density functional theory (DFT) employing generalized gradient approximation (GGA) has been used to study the electronic and magnetic properties of Mo doped SnO2 . The presence of symmetric density of states (DOS) and direct band gap in Sn1−x Mox O2 (at x=0.00) predicts this material to be a direct band gap semiconductor. The substitution of Mo atoms on the Sn sites induced a spin functionality on the DOS. The Mo impurities played an important role in facilitating the hybridization between Mo-d and O-p orbitals. The p − d hybridization gives an antisymmetric DOS at the EF by creating an exchange splitting at Mo-d states. The higher value of energy exchange splitting is responsible for the of partial magnetic moment at Mo site. In all composition except at x=0.0, the a wide band gaps are preserved at the spin down region and a metallic characteristic at the spin up region, confirm it’s metal-semiconductor hybrid property. These type of materials exhibit 100% spin polarization at the EF , which can be a potential candidate for electron-spin based futuristic devices.

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Recently, metal oxides like TiO2 , SnO2 , ZnO, In2 O3 , CdO, Al2 O3 etc., have gained immense interest due to their multifunctional properties like optical, electrical and ability to function as catalysts1–4 . These properties can be utilized in manufacturing many important electronic devices such as solar cells and other optoelectronic devices. Among the widely used metal-oxides, SnO2 has emerged as the suitable one due to its flexibility in fabrication of devices. It has now becoming the most commonly used gas sensing material due to comparatively high sensitivity of grain surface oxygen when exposed to atmosphere. Exposure to atmosphere immediately results in resistance change, which can be easly measured5,6 . Other properties like high chemical and high physical stability, absense of hysteresis loss, excellent repeatability and high sensitivity to humidity fluctuation are also found to be very useful when SnO2 is used as gas sensors. Recent reports have also shown that SnO2 is a potential candidate for humidity sensors in automotive and construction industries, medical sectors, meteorological and food processing industries7–13 . However, it also has limitations in certain practical application due to poor selectivity of specific gases. This problem can be fixed by doping with other elements such as Fe, Os, Ni, Pd, Ru, Pt, etc., as recently reported. Especially, doping of Mo atoms enhances its chemical sensitivity and transparency thus providing additional advantages in device application14–17 . SnO2 in its rutile phase possess an n-type charge carriers and indirect band gap of about 3.6 eV at room temperature18–21 . On the other hand, MoO itself is a good gas sensor material, and Mo also exhibit an excellent catalytic property which accelerate the redox reactions of some gases like alkanes, ammonia, hy-

drogen, and liquefied petroleum gas22–24 . Other than gas sensing ability, TM-doped SnO2 also have diverse applications as heat reflector, catalyst, transparent electrodes, micro electro mechanical system (MEMS), etc. Interestingly, TM doped SnO2 induced a spin functionality which opens an opportunity in the field of electron spin based futuristic technologies25,26 . This kind of materials is often known as diluted magnetic semiconductors (DMS) or half-metal ferromagnet (HMF)27 . Diluted magnetic semiconductors (DMS) have been developed by doping TMs in semiconductos like GaAs, GaP, InAs, AlN, AlAs, etc., at a Curie temperature28 . However, the materials with lower Curie temperature are not suitable for technological applications. Therefore, materials having Curie temperatures higher than room temperature are necessary. In general, semiconductors with wide band gap like TiO2 , ZnO, SnO2 have high Curie temperature about (∼650K) and can be doped with TMs for making prospective candidates for spintronic devices29,30 . Spintronic is an emerging field of quantum electronics involving manipulation of electron-spin. In DMS electron spins are found in two orientations (up/down) in which one of them is conducting and the other is insulating31 . This peculiar behaviour of metal-semiconductor hybrid is pioneered by de Groot et al., in NiMnSb32 . After that, a tremendous research interest was deviated towards the designing of the solid-state materials for HMF33–35 . As a result, HMF can be exploited in many electron-spin based spintronic technologies such as GMR, TMR, MRAM, quantum qubits etc.36–39 . In TM doped metal oxides, the mechanism of electron-spin transfer and magnetic polaron are mediated on the basis of oxygen vacancies40–43 . A ferromagnetic behavior has been reported in Co-doped SnO2 thin film prepared using pulse laser deposition (PLD) with a large magnetic moment of ∼ 7.0 µB

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bility we have computed the formation energy of each system from the following formula58 :

Eb =

RESULT AND DISCUSSION

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III.

A.

Electronic properties

The first principles calculation proceed with the optimized latice constant to analyse the electronic structures. The electronic configuration of constituent atoms in Sn1−x Mox O2 is given as Sn:[Kr]5s2 3d10 4p2 , O:[He]2s2 2p4 and Mo:[Kr]5s1 4d5 . The description of electronic structure is obtain by calculating the density of the states (DOS) and the band structures. The calculated partial DOS of SnO2 is shown in Fig.2. SnO2 is a wide band gap semiconductor with a direct band gap of ∼ 1.41 eV, underestimated as compared to the experimenatl one (3.6 eV)18–20 but in consistent with 1.38 eV obtained from LDA calculation59 . The underestimation of band gap is due to the inefficiency of DFT-GGA which fails to treat the orbital independent potential due to the presence of free electrons in the interstitial region. It can be seen that the maximum contribution comes from the O-p (px , py and pz ) states in the valence region [see Fig.2]. However O-p and Snp have significant contribution in the conduction band. The lowest band due to pz states of O atom lies in the conduction band and the maxima in the valence band is due to py states. Both maxima and minima lies at Γ-point. The formation of band gap in SnO2 is a result of p − p hybridization, which gives a covalent bond between Sn-p and O-p orbitals. The p − p hybridization gives rise to two type of bondings that is σ and π, that lies below the Fermi energy (EF ). Corresponding antibonding states are formed above the EF . The measure of energy difference between the bonding and the antibonding states is a semiconductor band gap. A doping of TMs on SnO2 is an interesting phenomena as it mediate a non-magnetic to magnetic phase transition, induces spin functionality. The TM doped SnO2 results in a super exchange-type of interaction between the two doped Mo atoms that energetically favor the ferromagnetic (FM) configuration. MoO2 possesses the rutile-type structure belongs to D4h point group60 , therefore, the 4d energy level Splits into four levels: A1g (dz2 ), B1g (dx2 −y2 ), B2g (dxy ), and Eg (dyz , dzx ). A crystal field plays a major role in splitting Mo-d orbital into dz2 , dx2 −y2 , dxy , dyz and dzx states. However, the monoclinic structure of

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where Etot is the total energy of a system. E1 , E2 and E3 are the energies of first, second and third atoms, respectively. N = (n1 + n2 + n3 ), n1 , n2 and n3 are the number of constituent atoms in the system. The calculated values of formation energy per unit volume for each system is presented in Table I . The negative value of Eb represents the ground state structural stability of a system. The undoped (pure) system shows more stability as compared to doped ones with higher values of negative Eb .

COMPUTATIONAL DETAILS

For calculation of he electronic properties we have used a computational package called WIEN2K52 , based on the KohnSham density functional theory (KS-DFT). The KS-DFT adopted the full potential linearized augmented plane wave (FPLAPW) method. An ordinary generalized gradient approximation (GGA) based on Perdew-Burke-Ernzerhof (PBE) scheme53 has been used to describe the electron exchangecorrelation. Nonspherical contributions to the charge density and potential within the muffin tin (MT) spheres are considered up to lmax = 10 (the highest value of angular momentum functions). The cut-off parameter is RM T ×Kmax =7 where Kmax is the maximum value of the reciprocal lattice vector in the plane wave expansion and RM T is the smallest atomic sphere radii of all atomic spheres. In the interstitial region the charge density and potential are expanded as a Fourier series with wave vectors up to Gmax =12 a.u−1 . A dense kmesh of 10×10×10 is considered in the first Brillouin, out of which 286 k-points in the irreducible Brillouin zone were used for the selfconsistent DFT calculation. The convergence criteria for the selfconsistency is set to be 0.0001 Ry. The core states were treated relativistically, the semicore states are treated semi-relativistically by neglecting the spin-orbit (SO) coupling. SnO2 crystallizes in rutile-type structure with the space group P 4− 2/mnm. The experimental lattice constants ˚ and c = 3.186454 used for structural opare a = 4.737 A timization based on Murnaghan’s equation of states55 . The optimized lattice constant is obtained from the energy versus volume curve [see Fig. 1]. The calculated lattice constant ˚ and c = 3.129 A, ˚ overestimated within GGA are a = 4.767 A as usual56 . The number of atoms has been increased by supercell method, derived from the 2 × 2 × 2 unit cell along [x,y,z] axis in which 8 Sn atoms are generated. We have considered the Mo concentration in Sn1−x Mox O2 as x=0.00, 0.25, 0.50, 0.75, and 1.00, as shown in Fig. 1. The compositions in terms of percentage are taken as x = 0.25 (2/8), 0.50(4/8), 0.75(6/8) and 1.00(8/8). The crystal structures of each composition of Sn1−x Mox O2 are shown in Fig.1. MoO2 takes up the simple monoclinic structure with space group P 21 /c (C52h )57 . The minimum energy as a function of Mo concentration has been presented in Fig. 1(f). For further confirmation structural sta-

Etot − (n1 E1 + n2 E2 + n3 E3 ) N ∗ V ol

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at room temperature29,30,44 . A huge magnetic moment has also been reported in Fe-doped SnO2 film43 and in bulk ceramic material from Mossbauer Spectroscopy45 . An enhanced saturated magnetization has been reported in Fe-doped SnO2 with the increase in Fe3+ ions, suggesting an increase in carrier density that initiates ferromagnetism40 . All experimental and theoretical reports sow similar mechanism of ferromagnetism in TM-doped SnO2 46–50 . Zhang et al.,51 carried out similar experiments in nanoscale. Most of the previous works are confined to analyse the gas sensing ability of SnO2 using various experimental tools. A systematic theoretical study of TM doped SnO2 is very limited. Therefore, we are encouraged to carry out first principles calculation of Mo doped SnO2 due to its potential applications.

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FIG. 1. Energy versus Volume curve of Sn1−x Mox O2 and the crystal structures (a) x=0.00 (Sn-red, O-blue), (b) x=0.25, (c) x=0.50 (Snred, Mo-green, O-blue), (d) x=0.75(Sn-blue, Mo-green and O-red),(e) x=1.00(Mo-blue and O-red) and (f) Minimum energy as a function of x-concentraion

FIG. 2. Partial DOS of SnO2 , displaying partial DOS of Sn-p(px ,py and pz ) and O-p (px ,py and pz )

MoO2 is derived from the hypothetical rutile structure. The distortion along the c-axis of rutile structure alter the atomic positions as well which can be viewed as a structural phase transition from rutile to monoclinic structure. The comparative study of electronic structures for both rutile and monoclinic MoO2 have been reported earlier57 . The cubic part of the crystal-field splitting of Mo-d orbital comprises of eg and t2g states57 . The eg state is a result of dz2 +dx2 −y2 whereas the t2g states consist of dxy +dyz +dzx . The interaction of Mo-d with the O-(px , py , pz ) orbitals giving rise to p-d hybridiza-

tion and expecting a semiconductor band gap. However the partial DOS displayed in Fig.3(d) shows metallic behaviour. In Fig.3(d) the energy range from 2.52 eV to -7 eV is completely dominated by O-2p states but the contribution due to the Mo 4d states are significantly viable above -2.0 eV. The contribution of t2g states are more prominent in the range from -2.0 eV to 3.0 eV , whereas eg states dominate the bands mostly above 3 eV. A finite amount of t2g − eg mixing has also been observed in an energy range from -1.0 eV to 2.5 eV. Mo-d states extended from -2.0 eV up to 6.0 eV dispersing around Fermi level which gives metallic behaviour. The presence of metallic behaviour of can be attributed to the fact that the increase in Mo-O bond length consequently diminishes the bonding-nonbonding effect of the σ and π bonded Mo-d and O-p orbitals57 . The calculated partial DOS of Mo and O in MoO2 are presented in Fig.3(d) which is in close agreement with the previous result of augmented spherical wave (ASW) method [see Fig.7]57 .

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Magnetic properties

The origin of magnetism in SnO2 can be discussed in terms of Mo doping which induces a spin functionality. This may be look into as an exchange interaction of magnetic impurities that plays a crucial role in mediating the ferromagnetic characteristic of a DMS. It has also been reported that, a strong pd hybridization between the TM-d and O-p orbitals initiated a double-exchange type of interactions between the TM ions that creates a ferromagnetism61 . As shown in Fig.3 (a-d), the d-band width increases from 3.5 eV to 8.0 eV as Mo impu-

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FIG. 3. Partial DOS of Sn1−x Mox O2 (a) x=0.25, (b) x=0.50, (c) x=0.75 and (d) x=1.00 (Sn-p, Mo-d and O-p)

FIG. 4. Total DOS of Sn1−x Mox O2 (a) x=0.00, 0.25, 0.50, 0.75 and (b) Energy gap (Eg ) and partial magnetic moment of Mo (MM o ) with x composition

rity increases form 0.25 to 0.75. The presence of magnetic moment in Mo-doped SnO2 is a result of energy exchange splitting (∆xc ) of Mo-d states. The ∆xc originites form the assymetric partial DOS of Mo-d states. Along with the band witdh of Mo-d states, the ∆xc also increases with addition of

Mo impurities. The ∆xc is the energy difference between the spin splitting of Mo-d states. The two spin splitting states due to the d − eg (↑) and d − t2g (↓) states below and above the EF , respectively. The ∆xc varies from 1.5 eV to 2.2 eV as Mo impurity increases. As the partial magnetic moment of Mo atom

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is related to the ∆xc , it is obivious that the paritial moment increases inlearly from 1.26 µB to 1.375 µB [see Fig.4]. The partial moment of Mo atom is considereably smaller as compared to the magnetic moment of isolated Mo atom due to the exchange interactions between Mo-Mo ions. The doping of extra Mo atoms in SnO2 also induces a local moment at the Sn and O sites which aligned parallel to the moment of Mo atoms [see Table I].

IV.

ACKNOWLEDGMENTS

CONCLUSION

In summary, using DFT calculations, we have studied the electronic and magnetic properties of Mo doped SnO2 compound within FP-LAPW method. The electron exchange potential was considered by treating the electrons within PBEGGA scheme. The calculated lattice paremeters are in very close agreement with the experimental data. An analysis of

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electronic structure confirmed SnO2 is semiconductor. The calculated band gap is found to be ∼1.41 eV, underestimated as compared to the experimental one by around 2030 %. The underestimation of band gap is due to the inefficiency of DFT-GGA which fails to treat the orbital independent potential of the electrons in the interstitial region. In all composition, Sn1x Mox O2 is energetically stable in ferromagnetic configuration except for x=1.00. Also the doping of Mo in semiconducting SnO2 induces a peculiar transition, Semicondutor→Semiconductor-Metal→Metal. The metalsemiconductor hybrid arises along with a finite value of magnetic moment. The TM-doped semiconductors posessing a property of metal-semiconductor hybrid is also called a dilute magnetic semiconductor (DMS), due to the presence finite value of magnetic moment and the semiconducting band gap in one of the spin channels. The partial magnetic moment increases siginficantly with the increase in concentration of the impurities. Hence, SnO2 when doped with TMs gives HMF, favourable for practical application in spintronic devices. Our recent investigation predicts that SnO2 is not only a potential candidate for gas sensor but it also bears diverse functional properties which can be tuned by various techniques for technological application.

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TABLE I. Calculated Magnetic moment (µB ), Energy gap (eV) and Formation energy (Eb ) in Ry/a.u3 of Sn1−x Mox O2

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FIG. 5. Band structures of Sn1−x Mox O2 (a)x=0.00, (b) x=0.25, (c) x=0.50 & (d) x=0.75 (black-spin up, green-spin down)

E-mail:[email protected]

D. P. Rai acknowledges UGC Start-Up-Grant No.F.3052/2014/BSR (New Delhi, India). Author also acknowledging the Supercomputing resources from C-DAC National PARAM Supercomputing Facility (NPSF) Pune. One of the authors A. Laref acknowlegde the ”Research Center of Female Scientific and Medical Colleges, King Saud University” for financial support.

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Highlights (a) The lattice constant was optimized to get stable structure. (b) The electronic structure gives direct band gap. (c) With TM doped, SnO2 shows nonmagnetic-magnetuc phase transition. (d) TM-doped SnO2 shows halfmetallic behavoiour with integer value of magnetic moment. (e) The TM-doped SnO2 is dilute magnetic semiconductor, prospective for spintronic.