Ambipolar Half-Metallicity in One-Dimensional Metalâ(1,2,4,5

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Ambipolar Half-Metallicity in One-Dimensional Metal-(1,2,4,5benzenetetramine) Coordination Polymers via Carrier Doping Yangyang Wan, Yingjie Sun, Xiaojun Wu, and Jinlong Yang J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.7b12022 • Publication Date (Web): 20 Dec 2017 Downloaded from http://pubs.acs.org on December 21, 2017

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The Journal of Physical Chemistry

Ambipolar Half-Metallicity in One-Dimensional Metal-(1,2,4,5-Benzenetetramine) Coordination Polymers via Carrier Doping Yangyang Wan,a Yingjie Sun,a Xiaojun Wu,a,b,* and Jinlong Yanga,b a

School of Chemistry and Materials Sciences, CAS Key Lab of Materials for Energy

Conversion, Hefei National Laboratory of Physical Sciences at the Microscale, and CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, Anhui 230026, China b

Synergetic Innovation of Quantum Information & Quantum Technology, University of Science

and Technology of China, Hefei, Anhui 230026, China *Email: [email protected] Tel: (+86) 0551-63607915.

ACS Paragon Plus Environment

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ABSTRACT. A family of one-dimensional (1D) π-d conjugated coordination polymers (CPs) with diverse magnetic properties are reported on the basis of first-principles calculations and coordinative assembly of metal (TM=Cr, Mn, Fe, Co, Ni, and Cu) and 1,2,4,5-benzenetetramine (BTA). Our calculations show that 1D TM-BTA are semiconductors, and Mn-, Fe-, and Co-BTA have ferromagnetic ground states. In particular, Mn- and Fe-BTA are bipolar magnetic semiconductors, which can be turned into half metals with controlled spin-polarization orientation via carrier doping. The long range super-exchange interaction between metal’s d and BTA’s π orbitals is responsible for tunable ferromagnetism with large magnetic anisotropic energy. The Born-Oppenheimer molecular dynamic simulation demonstrates that TM-BTA retains their lattice structures at temperature of 800 K. The ambipolar half-metallicity and high Curie temperature endow TM-BTA potential applicability in nanoscale spintronics.

1. INTRODUCTION Spintronics, using spin freedom of electron for delivering and storing information, have gained great research attentions for advantages in low power consumption, high response speed and density memory, making them suitable for next-generation information technology.1 Half metals (HMs) with only one metallic spin channel are ideal materials to provide completely spinresolved carriers.2 So far, tremendous efforts have been devoted to exploring low-dimensional HMs, including one-dimensional (1D) nanowires, and various organic or inorganic twodimensional (2D) sheets.3-17 In addition, half metallicity with tunable spin-polarization orientations for carriers has been reported theoretically in carrier-doped bipolar magnetic semiconductors (BMSs), of which the valence band maximum (VBM) and conduction band minimum (CBM) possess opposite spin-polarization orientation.18-20 Nevertheless, it is still a


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challenge to develop experiment-feasible nanomaterials with tunable half metallicity partly due to low yield, small domains and numerous of defects, or difficult in obtaining crystalline structure with ordered spin arrangement.21,22 Coordination polymers (CPs), also known as metal-organic frameworks, are comprised of metal-organic units linked together at least in one dimension to form an infinity array via covalent or coordination interactions.23,24 Benefiting from the abundance of building blocks, CPs can be bottom-up and scalable synthesized with controlled morphologies by selecting metal centers and coordinating ligands, resulting in their versatile properties and broad applications in electronics, optics, and magnetic devices.

25-38

For instance, numbers of 1D and 2D CPs with

diverse properties, including photocatalytic and electrocatalytic activity,25-27 ambipolar electrical conductivity,28-30 and topological insulating,31,32 have been reported via interfacial reaction between metal ions and multidentate organic ligands with different symmetries, such as aromatic dithiols,25 tetrathiols,27,33 or hexathiols,28 triphenylenehexathiol,34 tetraazanaphthacene,35 and hexaaminobenzene.38 The isolated and regularly distributed metal atoms in low-dimensional CPs, in particular, are ideal prototypic templates for nanoscale spintronics applications as metal’s rich d electronic structure and their hybrid with the delocalized π-orbitals of conjugated organic ligands leads to their novel magnetic properties. However, low-dimensional CPs with tunable half metallicity are still rarely reported. Herein, on the basis of first-principles calculations, we report six 1D CPs by assembling transitional metal (TM = Cr, Mn, Fe, Co, Ni and Cu) and 1,2,4,5-benzenetetramine (BTA) via coordination interactions. Except nonmagnetic (NM) Ni-BTA, our results establish that other 1D TM-BTA CPs are magnetic semiconductors with high structural stability at the temperature up to 800 K, confirmed with Born-Oppenheimer molecular dynamic simulations (BOMD) and phonon


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spectrum. Cr- and Cu-BTA CPs are antiferromagnetic (AFM), while Mn-, Fe-, and Co-BTA are ferromagnetic (FM) at their ground states. In particular, Mn-BTA and Fe-BTA are 1D BMS, which can be tuned into half metals with tunable orientation of spin polarization via carrier doping. The long range super-exchange interaction through ligand’s π orbitals leads to the tunable magnetism in TM-BTA. 2. METHODS All calculations are performed with spin-polarized density functional theory method and projected augmented wave (PAW) scheme as implemented in Vienna ab initio simulation package (VASP).39-41 The energy cutoff of 500 eV for plane wave functions is used. A vacuum region of of 15 Å is used to eliminate inter-chain interaction for 1D TM-BTA nanowire. Brillouin zone is sampled with 1×1×9 Gamma-centered k-points. Both lattice constants along the periodic direction and atomic positions are optimized with the convergence of force less than 0.005 eV/Å. The screened hybrid HSE06 functional is employed in electronic and magnetic properties calculation to deal with strong-correlation effect of TM’s d electrons.42 BOMD simulations are performed in canonical ensemble with a Nosé thermostat method under the temperature of up to 1000 K for 5 ps with time step of 1 fs. 3. RESULTS AND DISCUSSIONS As illustrated in Figure 1a, BTA is a multidentate ligand with D2h symmetry. 1D TM-BTA CPs can be obtained by assembling TM ions and BTA along c-axis with TM coordinated by ligands in either planar quadrilateral or tetrahedral configuration (Figure 1b), leading to P-type or T-type 1D TM-BTA CP nanowires (Figure 1c and 1d), respectively. The calculated energies indicate that P-type TM-BTA are more stable than T-type with energy difference spanning from -0.47 to 2.31 eV (Table S1 in Supporting Information). Thus, the following calculations are performed on P-type TM-BTA.


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Figure 1. (a) is the structure of BTA. (b) Metal atom is coordinated in either planar quadrilateral (P-type) or tetrahedral (T-type) coordination. (c) and (d) are the optimized structures of TM-BTA with P-type or T-type coordination, respectively. As summarized in Table 1, the optimized lattice constants for TM-BTA range from 7.68 to 7.99 Å, consistent with the tendency of metal’s atomic radius. The formation energy of 1D TMBTA is defined as Ef = E(TM-BTA)-E(BTA)-E(TM)+2E(H2). Co-BTA has the largest formation energy of -3.88 eV per stoichiometric formula (s.f.), while Cu-BTA has the smallest value of 0.99 eV/s.f.. The negative values of formation energy suggest that the formation of 1D TM-BTA from BTA and metal is energetically favorable. The structural stability of 1D TM-BTA is further investigated with the calculated phonon spectrum and BOMD simulations. As shown in Figure S1, no imaginary vibration mode is observed in the calculated phonon dispersion spectra of TM-BTA, implying their lattice stability. BOMD simulations are performed on the temperature from 300 to 1000 K. A supercell containing 4 unit cells is used. Figure S2 displays the structural snapshots of 1D TM-BTA at time of 5 ps during BOMD simulations. It is evident that TM-BTAs retain their 1D lattice


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structures at the temperature up to 800 K, confirming their high structural stability for roomtemperature devices applications. Various magnetic orders of TM-BTA, including NM, AFM, and FM states, are considered to find their magnetic order at ground state. Only Ni-BTA is NM at ground state. Both Cr- and CuBTA CPs have AFM ground states with the energy difference between AFM and FM states of 0.09 and 0.006 eV per cell, respectively, as summarized in Table 1. The negligible energy difference implies that Cu-BTA is most likely to exhibit paramagnetic behavior at room temperature. Plus, Mn-, Fe-, and Co-BTA CPs have ferromagnetic ground states, which are more stable than FM state by energy difference of -0.27, -0.24, and -0.09 eV/cell, respectively. Table 1. Optimized lattice constant (L, Å), formation energy (Ef, eV/s.f.), bandgap (EG, eV), magnetic moment (M, µB) on metal, ground State (GS, S denotes semiconductor), energy difference between FM and AFM states (∆E = E(FM) - E(AFM), eV/cell), and charge on metal (C, e). TM L

Ef

EG

GS

M

∆E

3.59 0.09

C

Cr

7.99 -3.13 1.58 AFM S

Mn

7.86 -2.97 1.10 FM BMS 3.59 -0.27

1.53

Fe

7.78 -3.47 0.84 FM BMS 2.39 -0.24

1.36

Co

7.69 -3.88 0.79 FM S

1.08 -0.09

1.15

Ni

7.68 -3.80 1.50 NM S

0

0.95

Cu

7.86 -0.99 2.05 AFM S

0.67 0.006 1.08

/

1.35

The calculated electronic band structures with HSE06 functional indicate that six TM-BTAs are semiconductors with bandgap ranging from 0.79 and 2.05 eV (See Figure 2 and S3). Cr- and Ni-BTA are indirect-band-gap semiconductors, while others are direct-band-gap semiconductors. In particular, Mn- and Fe-BTA CPs are 1D BMS materials (Figure 2a and 2b), of which the


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VBM and CBM have opposite spin-polarization orientation.18 Therefore, it is most likely to shift the Fermi level into CB or VB via carrier doping, resulting in HMs with inverse spin-polarization direction for hole or electron doping.19

Figure 2. The spin-polarized band structures and PDOS of (a) Mn-BTA and (b) Fe-BTA are calculated with HSE06 method. The Fermi energy is set as zero. (c) and (d) are spin charge distributions for Mn- and Fe-BTA, respectively. The isovalue is 0.01 a.u.. To examine this concept, carrier doping was considered to manipulate the electronic and magnetic properties of Mn-BTA and Fe-BTA. The doping concentrations is up to 1.0 ×1014cm-2 (0.03 carriers/atom), which is experimentally feasible. Note that a charge density modulation of 1015cm-2 have been experimentally achieved in 2D systems by using ionic liquid as gate dielectric.43 Here, the width of TM-BTA is about 7.94 Å (Figure S4), considering van der Waals distance between two in-plane parallel CPs. As shown in Figure 3a, both Mn-BTA and Fe-BTA


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retain FM ground states, except that Mn-BTA with high electron doping (≥0.03 electrons/atom) has AFM ground state. Doping Mn-BTA with a small amount of holes increases the AFM-FM energy difference, while carries doping slightly reduces the AFM-FM energy difference for FeBTA. The positions of energy minimum in Figure 3a mainly originate from the different d electrons configuration in Mn (d5) and Fe (d6).

Figure 3. (a) Relative energy of AFM and FM states under the variation of carrier concentration. The positive and negative values are for electron and hole doping, respectively. (b) The band structures of Mn-BTA and Fe-BTA with carrier doping (0.01 carriers/atom). The fermi level is set as zero. As shown in Figure 3b, a small amount of carriers doping turn both Mn-BTA and Fe-BTA into HMs (0.01 carriers/atom). In particular, the spin-polarization orientation is tunable depending on the carrier types. Note that electron and hole doping can be realized via reversing the polarity of external gate voltage, the spin polarization orientation of Mn-BTA and Fe-BTA can be tuned by


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reversing the polarity of gate voltage, making it suitable for electrical-controlled spintronics applications. The spin charge density distribution (Figure 2c, 2d and S5) indicates that the magnetism in TM-BTA is mainly contributed by metal atoms. Cr-BTA and Mn-BTA CPs have the largest local magnetic moment of 3.59 µB on metal (Table 1). For Fe-, Co-, and Cu-BTA, the values are 2.16, 1.08, and 0.67 µB, respectively. Though metal atoms contribute major magnetism, the calculated atom projected density of states (PDOS) (Figure 2 and S6) shows that the electronic states around the Fermi energy level are mainly contributed by delocalized p orbitals of ligands and metal’s dxy orbitals. Figure S7 displays the partial charge distributions of VBM and CBM, and the delocalized π-type states around Fermi level makes TM-BTA applicable for longdistance spin transport.

Figure 4. (a) Schematic representation of TM-BTA. (b) The lowest unoccupied orbital of ligand (isovalue 0.03 a.u.) (c) d-electron configuration of Mn2+, Fe2+, and Co2+. (d) Schematic diagram for long range super-exchange interaction of Mn2+ via conjugated π* orbital in Mn-BTA. Crystalline field theory was used to understand the magnetism in TM-BTA. We take FM Mn-, Fe- and Co-BTA as examples. Bader charge analysis (Table 1) indicate that metal is divalent. As


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shown in Figure 4, metal ions are planar-quadrilateral coordinated with D2h symmetry, leading to nondegenerate d orbitals. Figure 4c displays the d-electron configuration, which is consistent with the local magnetic moment of 3.59, 2.39 and 1.08 µB on metal for Mn-, Fe-, and Co-BTA, respectively. In addition, benefitting from a spatially conjugated frontier orbitals on ligand (Figure 4b), long range magnetic order of TM-BTA can be stabilized through super-exchange interaction via π* antibonding orbital of ligand,44 as shown in Figure 4d, consistent with the spin charge distribution in Figure 2. Table 2. The summary of MAE in the unit µeV/Fe and the EA for TM-BTA. (001), (010), and (100) are the orientations along the periodic direction, parallel and perpendicular to benzene plane, respectively. Orientation MAE

001

010

100

0

1361

813

EA 001

Above discussion shows that TM-BTA could exhibit FM ground states, and can be turned into HM with controllable spin-polarization orientation via carrier doping. Further, the magnetic properties of TM-BTA at finite temperature are considered. Note that there is no long-range FM or AFM order in infinite strictly 1D isotropic system with a finite range exchange interaction at nonzero temperature.45,46 However, the occurrence of FM or AFM order in 1D system at finite temperature is possible due to the magnetic anisotropic energy (MAE) or interchain coupling. The large MAE could block the thermal fluctuation and stabilize the long-range magnetic order, for instance, 1D Co atomic chains on Pt substrate with MAE of 2.0 meV/Co atom exhibit longrange FM order at the temperature below 15 K.47 As summarized in Table 2, the easy axis of TM-BTA is along the chain direction, and the largest MAE of Fe-BTA is 1.361 meV/Fe atom. In addition, the interchain coupling could also stabilize long-rang magnetic order in quasi 1D


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materials at finite temperature.48,49 Herein, we study the interchain interaction of TM-BTA. As shown in Figure S8, two TM-BTA chains are arranged in AA-staking, AB-stacking, AA-parallel, or AB-parallel configurations. The calculated energies indicate that the most stable configuration is AA-stacking with interchain coupling energies of -278.5, -327.0, and -225.5 meV per stoichiometric formula for Mn-BTA, Fe-BTA, and Co-BTA, respectively, as summarized in Table S2. The negative energies denote that formation of TM-BTA bundle is more favorable in energy than isolated TM-BTA chain. The interchain coupling of both Mn-BTA and Co-BTA are AFM, which is more favorable than FM coupling with energy differences of 197.5 and 51.5 meV per TM atom, respectively. In contrast, the interchain coupling of Fe-BTA is FM with the interchain coupling J of -40.0 meV per TM atom, which is large enough to stabilize the FM coupling at finite temperature. Note that the interchain coupling J is 0.009 meV for p-nitrophenyl nitronyl nitroxide (p-NPNN) with a Curie temperature of 0.65 K.48 4. CONCLUSIONS To summarize, we report a family of 1D TM-BTA CPs with novel magnetic properties by coordinative assembly of metal and BTA and first-principles calculations. We establish that 1D TM-BTA are semiconductors, and Mn-, Fe-, and Co-BTA are FM. In particular, Mn- and FeBTA are BMS, which could be turned into HMs with controlled orientation of spin-polarization via carriers doping. 1D TM-BTA has high structural stability, which is confirmed with phonon calculations and BOMD simulation at the temperature up to 800 K. The strong super-exchange interaction through ligand’s π* orbitals result in the tunable magnetism. The experimental feasible synthesis, delocalized π-type states around the fermi energy level, and ambipolar half metallicity in 1D TM-BTA make them suitable for nanoscale spintronics applications. ASSOCIATED CONTENT


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Supporting Information. Lattice constants and energies of T-type TM-BTA; phonon dispersion spectra; BOMD simulation results; band structure and PDOS results; spin charge density; partial charge distribution; interchain coupling (PDF) AUTHOR INFORMATION Corresponding Author *Email: [email protected] Tel: (+86) 0551-63607915. Notes The authors declare no competing financial interests. ACKNOWLEDGMENT This work is supported by NSFC (21573204, 21421063), MOST (2016YFA0200602), Fundamental Research Funds for the Central Universities, National Program for Support of Topnotch Young Professional, CAS Interdisciplinary Innovation Team, and by Super Computer Center of USTCSCC and SCCAS,.

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Ambipolar Half-Metallicity in One-Dimensional Metalâ(1,2,4,5

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