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A New Cubic Phase of Li3n: Stability of the N3− Ion to 200

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A New Cubic Phase of Li3n: Stability of the N3− Ion to 200 3¡ A New Cubic Phase of Li3N: Stability of the N Ion to 200 GPa A. Lazicki1;2, B. Maddox1;2, W. J. Evans, C. -S. Yoo and A. K. McMahan 1Lawrence Livermore National Laboratory, Livermore, California 94550 W. E. Pickett and R. T. Scalettar 2Physics Department, University of California, Davis, California 95616 M. Y. Hu and P. Chow HPCAT/APS, Argonne National Laboratory, Argonne, Illinois 60439 Diamond anvil cell experiments augmented by ¯rst principles calculations have found a remarkable 3¡ stability of the N ion in Li3N to a six-fold volume reduction. A new (γ) phase is discovered above 40(§5) GPa, with an 8% volume collapse and a bandgap quadrupling at the transition determined by synchrotron x-ray di®raction and inelastic x-ray scattering. γ-Li3N (Fm3m, Li3Bi-like structure) remains stable up to 200 GPa, and calculations do not predict metallization until »8 TPa. The high structural stability, wide bandgap and simple electronic structure make this N3¡ based system analogous to lower valency compounds (MgO, NaCl, Ne), meriting its use as an internal pressure standard. PACS numbers: 62.50.+p, 61.10.-i, 64.70.Kb, 71.20.Nr Nitrogen can form compounds with elements from al- particular interest. most every column in the periodic table, with chemi- In this paper, we present the ¯rst concrete experimen- cal bonding ranging from covalent to ionic to metallic. tal evidence that ¯-Li3N indeed transforms to a cubic Lithium nitride is the only known thermodynamically structure (γ-Li3N) in the pressure range of 36-45 GPa. stable alkali metal nitride and is one of the most ionic This transformation represents an increase in structural of all known nitrides. At ambient pressure, the nitrogen and bonding strength and isotropy, and is accompanied 3¡ exists in an anomalous multiply charged (N ) state [1, 2] by a relatively large volume collapse and a fourfold widen- which is stable only because of its crystal environment - ing of the electronic band gap. γ-Li3N is uncommonly + a hexagonal bipyramid of Li ions. This layered struc- stable and quite compressible in this pressure regime and ture (®-Li3N, P6/mmm) consists of Li2N layers, widely up to at least 200 GPa, making it a good candidate for separated and connected by one lithium atom per unit an internal pressure standard. cell occupying a site between the nitrogen atoms in adja- Polycrystalline lithium nitride powder (99.5 % purity, cent layers [3, 4]. This material is a superionic conductor CERAC, Inc) was loaded into a membrane diamond-anvil via vacancy-induced Li+ di®usion within the Li N lay- 2 cell of LLNL design. Several diamond sizes were used to ers. [5{7] Its potential for use as an electrolyte in lithium obtain an extended range of pressure up to 200 GPa. batteries [4], a hydrogen storage medium [8{11] and a In the lower pressure experiments, argon was used as a component in the synthesis of GaN [12] has prompted several studies including an investigation into its behav- ior at high pressure [13]. Cu (111) (220) (200) At »0.5 GPa, ®-Li3N transforms into a second layered Cu Cu (311) hexagonal structure (¯, P63/mmc) with BN-like honey- GPa 201 P= comb LiN layers [14]. In this structure, each nitrogen binds an additional lithium atom above and below the plane and, unlike the Li2N layers in ®-Li3N, adjacent (220) (111) LiN layers are shifted relative to one another. ¯-Li3N (422) is metastable at ambient pressure and is typically found (200) (400) (311) P = 43 GPa 43 P= mixed with the ®-phase. It remains stable up to 35 GPa units) (arbitrary Intensity { the high-pressure limit of experiments on Li3N to date. ¹ A second phase transition to a cubic structure - P43m at 2.5 2.0 1.5 1.0 37.9 GPa [13] or Fm3m at 27.6 GPa [15] - has been pre- d-spacing (A) dicted. If it exists, the similarity of this phase to those of other simple ionic cubic solids such as NaCl makes it an FIG. 1: ADXD diagrams of γ-Li3N at 43 and 201 GPa, with interesting study, particularly in light of its higher ion- re¯ned and di®erence patterns. Miller indices are based on the icity. Understanding the behavior of the unstable and cubic (Fm3m) structure shown, with large atoms representing highly charged N3¡ ions under large compression is of the highly negative nitrogen ions, small representing lithium. 2 which remains stable up to 201 GPa, the maximum pres- TABLE I: Volume per formula unit V , bulk modulus B , its o o sure achieved in the present study. A possible beginning pressure derivative Bo', volume change at the ¯!γ transition and transition pressure as obtained in experimental(*) and of this transition was reported in [13] and [14]. An addi- theoretical work in present and other studies. Experimental tional transition to an orthorhombic structure predicted errors are primarily a result of non-hydrostaticity in the DAC. at 168 GPa [15] is not seen. Figure 1 shows the measured ¹ The γ-phase predicted in reference [13] is space group P43m. and re¯ned di®raction patterns of γ-Li3N at 43 GPa and Aº3 ¢V 201 GPa. The re¯nement was performed based on the V0 ( f:u: )B0(GPa) B0' V P(GPa) 0 Li Bi structure (Fm3m) with one formula unit per prim- Exp.* ¯ 34.4(.8) 71(19) 3.9(.9) 8(2)% 40(5) 3 itive fcc cell consisting of one lithium and one nitrogen γ 30.8(.8) 78(13) 4.2(.2) ion occupying m3m¹ sites, and the two additional lithium Th. ¯ 34.44(.08) 68(3) 3.6(.1) 6.7% 40.4 ions in the 43m¹ sites, each tetrahedrally coordinated with γ 31.16(.08) 73.1(.8) 3.85(.01) 4 nitrogen ions. Slight changes in relative intensities of [13]* ¯ 35.04 74(6) 3.7(.7) >35 the di®raction peaks appear to be due to increasing oc- [13] ¯ 30.88 78.2 3.77 8% 37.9 cupancy of the Li 43m¹ sites with pressure (92.2% at 43 γ 28.08 82.8 3.84 GPa and 99.9% at 201 GPa). [15] ¯ 33.36 28(5) The pressure-volume data for the ¯ and γ phases and γ 30.44 their 3rd order Birch-Murnaghan equation of state (BM- [14]* ¯ 34.48 >10 EOS) ¯ts are shown in Figure 2, with ¯tting parameters summarized in Table I. The ¯ ! γ transition is accom- panied by an 8% volume collapse and an increase in the pressure medium and internal pressure standard. For coordination number for every atom. In the ¯ phase the high-pressure experiments, no pressure medium was (a»3.20 A,º c»5.71 A,º at the transition), each N3¡ ion is 3+ used, and copper or ruby (Al2O3:Cr ) were included surrounded by 11 Li+ ions (three in the hexagonal planes in the sample chamber as pressure indicators. Under at 1.85 A,º two above and below the plane at 1.90 Aº and non-hydrostatic conditions, the equation of state ¯tting six in trigonal prismatic coordination at 2.1 A).º In the γ parameters di®ered from those obtained under quasi- phase (a»4.5 A),º 14 Li+ ions surround N3¡, eight tetra- hydrostatic conditions by 8.7%, 0.8% and 13% for Bo,Vo hedrally coordinated with N at 1.95 Aº and six octahe- and Bo', respectively. Samples were loaded in an argon drally at 2.25 A.º Across the phase transition there is no environment as Li3N is hygroscopic. High-pressure be- discontinuity in the nearest-neighbor N distance (»3.23 havior was investigated by angle-dispersive powder x-ray A),º and the nearest N-Li distance even increases slightly. di®raction (ADXD) at 16IDB and inelastic x-ray Raman The signi¯cant increase in packing without a decrease scattering (XRS) at 16IDD of the High-Pressure Collabo- in distance between highly charged N ions makes the γ rative Access Team (HPCAT) beamlines at the Advanced phase highly preferred at high pressures. The more pop- Photon Source (APS). For the ADXD experiments, we ulated and symmetric distribution of Li ions serves to used intense monochromatic x-rays (¸ = 0.3683 or 0.4126 e®ectively shield the highly charged N ions from one an- ºA) microfocused to »10 ¹m at the sample using a pair of other and even potentially to compress their ionic radii piezo-crystal controlled bimorphic mirrors. X-ray di®rac- 750 tion patterns were recorded on a high-resolution image ) 3 plate detector (MAR 350) and analyzed with the FIT2D, MgO 500 B B (GPa) XRDA and GSAS programs. For the XRS experiments, -Li N 28 3 Ne -Li N we used monochromatic x-rays (9.687 keV) focused to 3 »20 x 50 ¹m at the sample through an x-ray translucent 250 NaCl (B2) Be gasket by a pair of 1 m-long Kirkpatrick-Baez focusing 24 V/V ~ 8 % 0 mirrors. Six spherically bent Si(660) single crystal ana- 0 50 100 150 200 lyzers (50 mm in diameter) were vertically mounted on a P (GPa) 20 -Li N 870 mm Rowland circle to refocus inelastically scattered 3 x-ray photons onto a Si detector (Amp Tek) at a scat- Experimental data tering angle of 25± in a nearly back scattering geometry Volume per formula unit (A 16 (Bragg angle of 88.6±). This con¯guration corresponds to Birch-Murnaghan fit a momentum transfer of q »2.2 Aº¡1. The overall system 0 50 100 150 200 provides an energy resolution of »1 eV.
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