High-throughput computational discovery of in2mn2o7 as a high curie temperature ferromagnetic semiconductor for spintronics

ABSTRACT Materials combining strong ferromagnetism and good semiconducting properties are highly desirable for spintronic applications (e.g., in spin-filtering devices). In this work, we

conduct a search for concentrated ferromagnetic semiconductors through high-throughput computational screening. Our screening reveals the limited availability of semiconductors combining

ferromagnetism and a low effective mass. We identify the manganese pyrochlore oxide In2Mn2O7 as especially promising for spin transport as it combines low electron effective mass (0.29 

_m_0), a large exchange splitting of the conduction band (1.1 eV), stability in air, and a Curie temperature (about 130 K) among the highest of concentrated ferromagnetic semiconductors. We

rationalise the high performance of In2Mn2O7 by the unique combination of a pyrochlore lattice favouring ferromagnetism with an adequate alignment of O–2_p_, Mn–3_d_, and In–5_s_ forming a

dispersive conduction band while enhancing the Curie temperature. SIMILAR CONTENT BEING VIEWED BY OTHERS HOLE-DOPING INDUCED FERROMAGNETISM IN 2D MATERIALS Article Open access 10 November

2022 HIGH-THROUGHPUT CALCULATIONS OF SPIN HALL CONDUCTIVITY IN NON-MAGNETIC 2D MATERIALS Article Open access 14 May 2025 DIFFERENT TYPES OF SPIN CURRENTS IN THE COMPREHENSIVE MATERIALS

DATABASE OF NONMAGNETIC SPIN HALL EFFECT Article Open access 12 October 2021 INTRODUCTION Materials combining semiconductivity and magnetism open up possibilities for novel electronic

devices that utilise electron spin in addition to charge degrees of freedom.1,2 Ferromagnetic semiconductors (FMSs) are in particular valued for their potential in spintronics for

spin-polarised transport. Compared to ferromagnetic metals, FMSs are more suited for injecting spin-polarised electrons into non-magnetic semiconductors.3,4,5,6,7,8 A closely related and

technologically important phenomenon is spin filtering, which can be realised through the use of FMSs as the tunneling barrier for generating highly spin-polarised current.9,10,11,12,13,14

FMSs used in spintronics are primarily based on magnetic impurities embedded into conventional non-magnetic semiconductors.15 The robustness of carrier-induced ferromagnetism is extremely

sensitive to the growth conditions and processing methods, and the origin of room-temperature ferromagnetism of such diluted magnetic semiconductors remains a subject of debate.2,16 In

contrast, concentrated magnetic semiconductors exhibit long-range magnetism without resorting to extrinsic doping. A few concentrated FMSs have been reported, including Cr halides CrBr317,18

and CrI3,19,20,21,22,23 Cr spinel selenides,6 Mn pyrochlore oxides,24 and perovskites such as BiMnO3,25 CuSeO3,26 and YTiO3.27 Among the most studied FMSs for spintronics are the Eu

chalcogenides Eu_X_ (_X_ = O,S,Se).10,11,12,14,28 While providing very good performances in spin-filter devices, the Eu_X_ exhibit very low Curie temperature (e.g., _T_C = 69 K for EuO29),

which is characteristic for most FMSs known to date. In addition, the electronic structure of FMSs needs to be tailored in the context of spin transport. For a barrierless electrical spin

injection depicted in Fig. 1a, the efficiency is determined by the exchange splitting of the conduction band while a low effective electron mass is appreciated for achieving high carrier

mobility. Analogously, the exchange splitting is critical for spin filtering as it gives rise to spin-dependent potential barriers for the tunneling current (cf. Fig. 1b), resulting in

spin-polarised current in favour of the spin with a lower potential barrier.13,30,31 As such, EuO is in particular attractive for spin injection32 and filtering12 because of its large

exchange splitting of the conduction band (0.6 eV) and highly dispersive conduction band.33 Nevertheless, its poor air stability34,35,36,37 along with the low _T_C present major obstacles

for practical applications. Combining strong ferromagnetism and attractive semiconducting properties in one material is therefore desirable but remains an open problem. Here, we set out to

identify systematically concentrated FMSs through a large-scale computational screening of known compounds. We report on the materials identified and especially their semiconducting

properties, their Curie–Weiss temperatures, and their stabilities. In particular, we identify the Mn pyrochlore oxide In2Mn2O7 as a very promising material. We discuss its potential use for

spin transport and the inherent structural and chemical reasons for its high performances. RESULTS We consider a material to be a good FMS candidate if it offers a high ferromagnetic

transition temperature and good semiconducting properties. Because electrons have much longer spin lifetimes than holes,2 we focus on spin transport based on electrons as illustrated in Fig.

1, and hence look for FMSs with a large exchange splitting of the conduction band and a low electron effective mass. Starting from the materials project (MP) database comprising over 40,000

density-functional theory (DFT) calculations using the semilocal Perdew–Burke–Ernzerhof (PBE) functional38 and the Hubbard _U_ correction (PBE + _U_)39 (for transition-metal oxides), we

first screen the materials based on their thermodynamic stability (energy above convex hull at 0 K lower than 50 meV per atom) and electronic band gap (>100 meV). This step leads to about

15,300 semiconductors, out of which 3100 compounds show a finite magnetic moment (>0.5 _μ__B_) in the ground state (when the computation is initialised in a ferromagnetic state). Among

these magnetic materials, only about 1000 compounds exhibit an electron effective mass (\(m_e^ \ast\)) smaller than 1.5 _m_0. In comparison, typical semiconductors (e.g. GaAs, Si, and ZnO)

present \(m_e^ \ast\) ranging from 0.05 to 0.5 _m_0.40 Figure 2a shows the distribution of \(m_e^ \ast\) for materials exhibiting a finite magnetisation compared to non-magnetic materials.

It is clear that low \(m_e^ \ast\) is more easily achieved in non-magnetic compounds. The need for magnetism often implies partially filled _d_ bands. When the conduction-band character is

dominated by these orbitals, their localised nature leads to a high effective mass.41 Figure 2b confirms that low \(m_e^ \ast\) materials are mainly of _s_ character. The poor effective mass

and strong ferromagnetism are, for instance, present in CrBr3 and certain manganites such as LaMnO3, where a predominant 3_d_ character in the lowest conduction band leads to a high \(m_e^

\ast\) of over 10 _m_0. At variance, the low \(m_e^ \ast\) of EuO (0.4 _m_0) is remarkable in that the ferromagnetism arises from an indirect exchange between the localised Eu–4_f_ electrons

in the valence and the delocalised 5_d_/6_s_ electrons in the conduction band.33,42 The presence of a non-zero total magnetisation in the 0 K DFT computation with an initial ferromagnetic

ordering does not imply that the ground state is necessarily ferromagnetic and that this ferromagnetic configuration is sustained at high temperature. We thereby estimate the magnetic

ordering of the ~1000 compounds by comparing the total energies of the ferromagnetic ground state to the antiferromagnetic (AFM) or ferrimagnetic (FiM) one. The difference serves as an

indicator of whether the compound in question is dominated by ferromagnetic exchange interactions. To determine the magnetic ground state, we use supercells that contain at least four atoms

for each distinct magnetic species. An exhaustive search of the lowest-energy AFM (or FiM) configuration is carried out by enumerating all possible configurations in which half of the

magnetic sites are initialised with a positive magnetic moment whereas the other half with a negative magnetic moment. The absolute value of the initial magnetic moment follows the

calculated magnetic moment in the FM configuration. We consider only the collinear magnetic configurations as non-collinear calculations would be computationally prohibitive at this stage of

screening. We find that less than 30 compounds favour an FM ground state by over 10 meV per formula unit compared to the AFM or FiM configurations (see Table S1 of Supplementary

Information), manifesting already the difficulty of finding semiconductors with robust ferromagnetism. Our computational screening thus far relies on the PBE( + _U_) calculations. While

instrumental in determining the energetic stability among various magnetic orderings, PBE and PBE + _U_ with _U_ values calibrated for formation enthalpies do not warrant a faithful

description of the underlying electronic structure. For a higher accuracy and a better treatment, particularly of localised _d_ and _f_ electrons, hybrid functionals such as the

Heyd–Scuseria–Ernzerhof (HSE) functional43,44 should be used.45 We have thus performed HSE calculations on the candidates exhibiting the most favourable ferromagnetic ordering (The HSE

calculations exclude the pyrochlore oxides containing the lanthanide elements with partially filled _f_ electrons due to convergence issues. Nevertheless, these materials are expected to

exhibit more exotic magnetic properties than the simple ferromagnetic ordering24). We report in Table 1 the electron effective mass as well as the Curie–Weiss temperature _θ_CW obtained from

HSE calculations. The latter is defined from the paramagnetic response at high temperature, and is estimated with the random-phase approximation46 as described in Supplementary Information.

When known, we also report on their experimental Curie temperature _T_C. The difference between _θ_CW and _T_C indicates the degree of geometrical frustration in a magnetic system.24

Notably, the FMSs listed in Table 1 can be classified into five categories: Eu chalcogenides, Cr spinel chalcogenides, Bi manganites, Mn pyrochlore oxides, and Mn double perovskites. Figure

3 shows the HSE band structure for a representative compound in each category. Our screening recovers the well-known FMSs in the context of spintronics such as EuO, CdCr2Se4, and BiMnO3.

Less traditionally associated to spintronics are the Mn pyrochlores (e.g., In2Mn2O7). To compare the performances of these different compounds, we plot in Fig. 4 \(m_e^ \ast\) vs _θ_CW

obtained from HSE calculations. We further indicate the stability of the materials against oxidation by showing the maximum oxygen chemical potential reachable while keeping the material

thermodynamically stable. This provides a measure of air sensitivity: the higher oxygen chemical potential, the greater stability. The highest _θ_CW is clearly obtained among the double

perovskites La_B_MnO6 (_B_ = Ni, Co). In particular, La2NiMnO6 shows near room-temperature ferromagnetism arising from the strong ferromagnetic superexchange interactions between the Mn4+

and Ni2+.47 However, the large \(m_e^ \ast\) of over 1.1 _m_0 could be a limiting factor for high mobility applications. Following La2NiMnO6, the sulfide and selenide spinels _A_Cr2_X_4 (_A_

 = Hg, Cd, Zn, and Mg; _X_ = S, Se) show _θ_CW up to 200 K. The prevalence of Cr3+ can be related to the high magnetic moment of its _d_3 configuration. The strongest ferromagnetism is

observed in CdCr2Se4 in accordance with experiment.48 MgCr2Se4, which has been overlooked as a ferromagnetic spinel in literature, shows comparable ferromagnetism as CdCr2Se4 according to

our computational screening. In any case, all these spinel chalcogenides show poor stability in air due to their sulfide or selenide chemistry. The air stability is also an issue for Eu

chalcogenides. In fact, EuO is known for the difficulty in growing high-quality thin films since Eu2+ is easily oxidised to Eu3+.34,35,36,37 The remaining oxides are the pyrochlores and

BiMnO3. Among the pyrochlores, In2Mn2O7 is especially noteworthy as it shows the highest _θ_CW and the lowest \(m_e^ \ast\). While showing similar electronic and magnetic properties as

BiMnO3, In2Mn2O7 exhibits a higher air stability thanks to their high stability of the oxidation states of its cations: In3+ and Mn4+. In comparison with EuO, it offers an even lower \(m_e^

\ast\) (0.29 _m_0), better air stability, and a significantly higher _θ_CW (155 K vs 76 K). The calculated exchange splitting of the conduction band shown in Table 1 for the candidates

confirms the good performance in spin filtering with EuO12 and BiMnO3.25 Table 1 implies that In2Mn2O7 should also present an excellent spin-filter effect. But as uncertainty remains in the

exchange splitting with the HSE calculations and little is known from experiment, we resort to the self-consistent quasiparticle _GW_ calculations (QS_GW_) with vertex corrections49 to

calculate the electronic structure of In2Mn2O7. The QS_GW_ method does not depend on any adjustable parameter and starting point, and it has been shown to provide a reasonable description of

the electronic structure for correlated transition-metal oxides.50 As shown in the QS_GW_ band structure in Fig. 5a, the exchange splitting further opens up to 1.1 eV, in support of using

In2Mn2O7 for efficient spin filtering. DISCUSSION Our large-scale computational screening shows that the viable routes toward ferromagnetism in semiconducting materials involve either the

partially filled Eu–4_f_ electrons or the partially filled 3_d_ electrons of transition metals such as Cr, Mn, and to some extent, V. Indeed, the identified FMSs are mostly Cr spinels and Mn

pyrochlores. They are commonly characterised by the high-spin _S_ = 3/2 state in the 3_d_3 configuration, which in the (pseudo)cubic crystal field results in an occupied _t_2_g_ and an

unoccupied _e__g_ manifold of states. For Cr spinels, the strength of ferromagnetism reduces from selenides to sulfides, and eventually inverts to antiferromagnetism for oxides as the

ferromagnetic _t_2_g_–_e__g_ exchange interaction is outweighed by the AFM _t_2_g_–_t_2_g_ interaction.51 While the same competing mechanism is also at play for the pyrochlores, the larger

lattice constant stabilises the ferromagnetic configuration for a series of Mn and V pyrochlore oxides. The double perovskites, on the other hand, offer significantly higher _T_C than the

simple perovskite counterparts such as BiMnO3 and LaMnO3. The anomalously strong ferromagnetism of La2NiMnO6 stems from the fully occupied _e__g_ state of Ni2+, which is unique to this type

of material. In comparison, the _e__g_ state is either partially occupied for the Mn3+ in BiMnO3, or simply empty for the Mn4+ and Cr3+ in the case of pyrochlores and spinels. Our results

confirm the challenge in combining adequate air stability, effective mass, and Curie temperature. In2Mn2O7 offers an exceptional compromise between these three metrics. Among the

ferromagnetic pyrochlore materials, In2Mn2O7 shows a very low \(m_e^ \ast\) of 0.29 _m_0, which is among the lowest for all identified FMSs. Such a low effective mass is the result of the

prominent In–5_s_ character of the conduction band minimum (CBM) in the minority spin channel, as clearly shown by the element-resolved band structure in Fig. 5a. In contrast, most

pyrochlore oxides, such as Y2Mn2O7, exhibit much less dispersive CBM in both spin channels (cf. Fig. 5b) as the Y–5_s_ states do not mix in the lower conduction band. In–5_s_ states are

known to lead to dispersive conduction band in binary and ternary oxides:41 one of the highest electron mobility oxide being doped In2O3. The _s_ character in the conduction band is also at

the origin of the strong ferromagnetism present in In2Mn2O7, leading to the highest _T_C among all pyrochlore oxides. Apparently, the semi-empirical Goodenough–Kanamori rules of

superexchange52,53 do not fully account for such strong ferromagnetism as all the pyrochlore oxides considered in Table 1 show Mn–O–Mn bond angles between 130° and 133°. Longer Mn–O bond

lengths reduce the AFM _t_2_g_–_t_2_g_ interactions among neighbouring Mn atoms, yet this does not explain the higher _T_C of In2Mn2O7 (_d_Mn−O = 1.89 Å) compared to Y2Mn2O7 (_d_Mn−O = 1.91 

Å). Indeed, the hybridisation among Mn(_t_2_g_)–O(_p_)–In(_s_) states is key to the strong ferromagnetism of In2Mn2O7. Specifically, the In–O covalency mixes with the Mn-_t_2_g_–O-_p_

states, stabilising the ferromagnetic configuration by shifting the In–O states upward (downward) in the majority (minority) channel.54 This is supported by the band-resolved crystal orbital

Hamilton population (COHP) analysis,55,56,57,58,59 showing the antibonding nature of In(5_s_)–O and Mn–O interactions at the CBM of the minority spin channel (see Table S2 and Fig. S2 of

Supplementary Information). More intuitively, the enhanced ferromagnetism can be understood by the indirect-exchange mechanism60 involving virtual electron hopping from the O–_p_ to the

In–_s_ states in the conduction band. This leaves the O–_p_ state effectively spin polarised and enhances the ferromagnetic superexchange through the O atom. For this mechanism to take

effect, the atomic valence _s_ state needs to be in a reasonable proximity to the O–_p_ state, which is exactly the case of the group 13 elements such as In and Tl, although Tl2Mn2O7 is a

half-metal.54,60,61,62,63 While pyrochlore oxides comprising other group 13 elements (such as B, Al, and Ga) do not appear as a candidate because of their instability, they indeed exhibit a

highly dispersive _s_-like CBM from the minority channel and a high _θ_CW comparable to In2Mn2O7 (see Table S3 of Supplementary Information for the properties of these hypothetical

pyrochlore oxides). Finally, the FMSs need to be _n_-type to facilitate the transport of spin-polarised electrons. To this end, we assess several dopants in In2Mn2O7, among which Sn and Mo

are found to incorporate on the In site while acting as shallow donors, analogous to that in In2O3.64,65 The computational details of defect calculations are described in Supplementary

Information, whereas the formation energies of the dopants in various charge states are given in Fig. S1. We additionally find no evidence of favourable self-trapping of electrons as small

polarons in this material and a general unfavourability of native compensating centers like cation vacancies, which suggests that In2Mn2O7 can be effectively _n_-type doped. In conclusion,

we have carried out a large-scale computational screening in quest of concentrated FMSs. Among the very few identified materials, the pyrochlore oxide In2Mn2O7 emerges as a particularly

interesting candidate that exhibits robust ferromagnetism, good air stability, and a low electron effective mass, an uncommon combination that is of great promise for high mobility spin

transport. While In2Mn2O7 does not yet fulfill the requirement of room-temperature ferromagnetism, its Curie temperature could be potentially increased with epitaxial strain.66,67,68 Indeed,

as shown in Supplementary Information, we find that tensile stress due to the lattice mismatch to some semiconductor substrates (such as Si and GaAs) can effectively increase the Curie

temperature of In2Mn2O7, but it needs to be practiced with caution as it has adverse effects on the effective mass (see Fig. S3). Other routes, such as doping, can also be explored to

enhance the Curie temperature as it has been demonstrated for EuO and BiMnO3.68,69,70,71,72 METHODS FIRST-PRINCIPLES CALCULATIONS Collinear spin-polarised semilocal DFT–PBE and hybrid

functional HSE calculations are performed with the Vienna ab initio simulation package (VASP).73,74 Electron–ion interactions are described by the projector-augmented-wave (PAW) method.75,76

We use the Pymatgen package77 to generate VASP input files based on the structures retrieved from the MP database. Throughout the calculations, the kinetic energy cut-off is set to 520 eV,

and a regular Γ-centered K-point mesh is used with a grid density of 1600 K points per atom. For transition-metal oxides, the PBE calculation is carried out with the Hubbard _U_ correction

(PBE + _U_), for which the _U_ parameters take the values adopted by the MP following the approach described by Wang et al.78 Quasiparticle self-consistent _GW_ calculations are performed

with the ABINIT code79,80 using the PseudoDojo optimised norm-conserving pseudopotentials.81,82 Vertex corrections in the dielectric screening are accounted for through the use of the

bootstrap exchange-correlation kernel.49,83 The dielectric function is evaluated through the contour deformation method84 including unoccupied states up to 150 eV above the Fermi level in

the summations. The dielectric matrix is represented by a plane-wave basis set with an energy cut-off of 160 eV. The self-consistent iteration of the wavefunctions is restricted to the

lowest 2_N__v_ states where _N__v_ is the number of the valence bands. Band-resolved COHP calculations are carried out with a development version of the LOBSTER package.55,56,57,58,59 The

pbeVaspFit2015 basis is used with the following basis functions: O: 2_s_, 2_p_; In: 5_s_, 5_p_, and 4_d_; Mn: 4_s_, 3_p_, and 3_d_. The wavefunctions are obtained using the PBE + _U_

functional. EFFECTIVE MASS CALCULATION The reported effective mass is defined as the conductivity effective mass $$(m^ \ast )^{ - 1} = \frac{{\sigma (T,\mu )}}{{n(T,\mu )e^2\tau }},$$ (1)

where the electrical conductivity _σ_ and the charge carrier concentration _n_ are computed directly from the Boltztrap calculations85 with _T_ = 300 K and a chemical potential _μ_ leading

to _n_ = 1018 cm−3. The relaxation time _τ_ is assumed to be independent of _T_ and _μ_ following previous high-throughput works.41,86 DATA AVAILABILITY All data generated or analysed during

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ACKNOWLEDGEMENTS G.-M.R. acknowledges the F.R.S.-FNRS for funding. G.H., G.-M.R. and J.G. acknowledge the F.R.S.-FNRS project HTBaSE (Contract no. PDR-T.1071.15) for financial support. W.C.

and G.-M.R. acknowledge support from the Communaté française de Belgique through the BATTAB project (Project no. RC 14/19-057). The work by J.B.V. has been performed under the auspices of

the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract no. DE-AC52-07NA27344. Computational resources have been provided by the supercomputing facilities of

the Université catholique de Louvain (CISM/UCL) and the Consortium des Euipements de Calcul Intensif en Fédération Wallonie Bruxelles (CECI) funded by the Fonds de la Recherche Scientifique

de Belgique (F.R.S.-FNRS) under Grant no. 2.5020.11. The present research has also benefited from computational resources made available on the Tier-1 supercomputer of the Fédération

Wallonie-Bruxelles, infrastructure funded by the Walloon Region under Grant no. 1117545. We thank Darrel Schlom for useful discussions, and Richard Dronskowski and Ryky Nelson for a

development version of Lobster. The MP is funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Science, Materials Sciences and Engineering Division under

Contract no. DE-AC02-05-CH11231: Materials Project program KC23MP. AUTHOR INFORMATION AUTHORS AND AFFILIATIONS * Institute of Condensed Matter and Nanoscicence (IMCN), Université catholique

de Louvain, 1348, Louvain-la-Neuve, Belgium Wei Chen, Janine George, Gian-Marco Rignanese & Geoffroy Hautier * Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA Joel B.

Varley Authors * Wei Chen View author publications You can also search for this author inPubMed Google Scholar * Janine George View author publications You can also search for this author

inPubMed Google Scholar * Joel B. Varley View author publications You can also search for this author inPubMed Google Scholar * Gian-Marco Rignanese View author publications You can also

search for this author inPubMed Google Scholar * Geoffroy Hautier View author publications You can also search for this author inPubMed Google Scholar CONTRIBUTIONS G.H. and W.C. conceived

the study. W.C. carried out the high-throughput computational screening and calculated the electronic and magnetic properties of the compounds. J.G. did the COHP analysis and J.B.V.

performed the defect calculation for In2Mn2O7. All authors analysed the results. The manuscript is written by W.C. with inputs from J.G. and J.B.V. and is approved by all authors.

CORRESPONDING AUTHOR Correspondence to Geoffroy Hautier. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. ADDITIONAL INFORMATION PUBLISHER’S NOTE: Springer

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_et al._ High-throughput computational discovery of In2Mn2O7 as a high Curie temperature ferromagnetic semiconductor for spintronics. _npj Comput Mater_ 5, 72 (2019).

https://doi.org/10.1038/s41524-019-0208-x Download citation * Received: 26 February 2019 * Accepted: 20 June 2019 * Published: 11 July 2019 * DOI: https://doi.org/10.1038/s41524-019-0208-x

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