† Corresponding author. E-mail:
Project supported by the Research Foundation of Key Laboratory of Neutron Physics (Grant No. 2015BB03), the National Natural Science Foundation of China (Grant Nos. 11774247), the Science Foundation for Excellent Youth Scholars of Sichuan University (Grant No. 2015SCU04A04), and the Joint Usage/Research Center PRIUS (Ehime University, Japan) and Chinese Academy of Sciences (Grant No. 2017-BEPC-PT-000568).
Tantalum nitride (TaN) compact with a Vickers hardness of 26 GPa is prepared by a high-pressure and hightemperature (HPHT) method. The crystal structure and atom occupations of WC-type TaN have been investigated by neutron powder diffraction, and the compressibility of WC-type TaN has been investigated by using in-situ high-pressure synchrotron x-ray diffraction. The third-order Birch–Murnaghan equation of state fitted to the x-ray diffraction pressure–volume (P – V) sets of data, collected up to 41 GPa, yields ambient pressure isothermal bulk moduli of B0 = 369(2) GPa with pressure derivatives of
Tantalum nitrides are attractive materials for making wear-resistant coatings and as diffusion barriers for copper in semiconductor devices.[1,2] Their outstanding heat resistance, chemical stability, and hardness also make them potentially useful as industrial materials.[3–5] In particular, tantalum mononitride (TaN), at least has three structures, an ambient CoSn-type (P-62m) phase,[6] a high-pressure WC-type phase (space group P-6m2),[7,8] and a high-pressure NaCl-type phase (space group Fm-3m).[9,10] When starting from CoSn-type TaN, Boiko and Popova reported that the WC-type TaN could be obtained at the pressure (3 GPa–10 GPa) and the temperature (673 K–2073 K), and the NaCl-type TaN could be obtained at above 2073 K in the same pressure conditions,[11] which were also consistent with experiment results by Brauer et al.[12] Sequentially, a density functional theory (DFT) calculation predicted that the WC-type TaN should be a potential hard alloy as hard as WC with the hardness up to 37.1 GPa.[13] A recent theoretical work indicated that the bulk modulus of the WC-type TaN could be up to 378 GPa.[14] However, a recent experimental study on this material showed that the Vickers hardness of the obtained WC-type TaN bulk only reached 11 GPa with B0 = 351(1) GPa.[15] Whether or not the WC-type TaN is a potential hard material as hard as WC (Hv ˃ 20 GPa) is not known. In addition, TaN is an interstitial compound with variable amounts of nitrogen atoms. It is the high valence electron density and covalent bond that enhance the hardness of Ta significantly, because the hardness of pure Ta is only 0.9 GPa.[16] Previous theoretical works predicted that the powerful covalent bonding between the Ta atom and its neighboring N atoms may play an important role in strengthening the crystal structure to increase the hardness of the compound,[13] and Ta atoms would contribute high valence electron density to enhance incompressibility of WC-type TaN.[17–19] However, there is still no experimental investigation on the origin of the incompressibility of WC-type TaN as far as we are aware and no evidence indicates that it is a hard material. It stimulates us to further explore crystal structure and compressibility of WC-type TaN under high pressure.
Neutron powder diffraction is a unique and powerful probe for precisely determining the atomic occupancy and crystal structure for 5d transition metal nitrides, because of the similar neutron scattering lengths for Ta atom (0.6910 × 10−12 cm) and N atom (0.936 × 10−12 cm). The occupation of N atom also can be determined by neutron powder diffraction, so NPD is an effective way to confirm the crystal structure for the compounds consisting of heavy transition metals and light elements like N and H, compared to the x-ray powder diffraction. In this work, we employ neutron powder diffraction (NPD) to determine crystal structure and atomic occupation and in-situ high-pressure synchrotron x-ray diffraction to investigate the structural response of tantalum nitrides to pressure.
The high P–T synthesized experiments were performed using a DS 6 × 14 MN cubic press installed at Sichuan University, China. Tantalum nitride (Alfa Aesar No. 13093 Purity 99.5%) was used as the starting material. WC-type TaN bulk alloy was synthesized from hexagonal CoSn-type TaN by phase transformation sintering method under high pressure and high temperature (HPHT). After polishing the surface, the Vickers hardness was measured using a diamond indenter (FV-700B, Future-Tech, Japan). We conducted in situ high-pressure synchrotron x-ray diffraction on WC-type TaN in order to determine the well-constrained pressure dependence of its elastic modulus. The XRD measurements were made on the power of bulk sample in a diamond anvil cell up to 41 GPa. The in situ high-pressure synchrotron x-ray diffraction measurements were performed at the 4W2 beam line of the Beijing Synchrotron Radiation Facility (BSRF, China). High pressure was generated using a symmetric-type diamond anvil cell (DAC) with 300-μm culets.[20] A Si (111) monochromator was used to tune the synchrotron source with a wavelength of 0.6199 Å. The incident x-ray beam was focused to approximately 26 μm × 8 μm full width at half maximum (FWHM) spot by a pair of Kirkpatrick–Baez mirrors. The two-dimensional diffraction patterns were recorded by a Mar345 image plate detector and analyzed with the program Fit2D.[21] The NPD experiments were carried out at room temperature using a neutron powder diffractometer at the Institute of Nuclear Physics and Chemistry, China. NPD data were collected at a wavelength of λ = 1.59 Å over the range of 2θ = 20° – 140° with a step of 0.1°/s. The counting time was 10 h with a neutron flux of 3 × 105 n⋅cm−2⋅s −1 at the sample position. The obtained NPD patterns were refined by using FULLPROF SUITE ver.1.10 rietveld refinement software. The atomic ratios were roughly determined by an improved energy dispersive x-ray spectroscopy (EDX) method (Oxford Instruments, INCA E250), and then used for further NPD refinements. Before EDX quantitative analyses, the well-polished samples and the EDX standard samples were uniformly coated with an osmium layer (5 nm in thick) in an osmium coater (Neoc-STB, Meiwafosis Co., Ltd). The EDX method used in this work can effectively improve the accuracy of the quantification of light and heavy elements (such as Ta and N), and the accuracy of the quantification was evaluated to be less than 0.5%.[22,23] EDX analyses are consistent with the NPD results about the ratio of Ta atom and N atom.
The well-synthesized samples are cylinder-shaped chunks with a diameter of about 8 mm and thickness of about 8 mm (the inset of Fig.
Figure
The compressible behaviors of the WC-type TaN and Ta5N6 under high pressure were investigated by in situ high-pressure synchrotron x-ray diffraction. The diffraction spectra of WC-type TaN and Ta5N6 are displayed in Fig.
The pressure-dependent volume measurements are shown in Fig.
From in-situ high-pressure synchrotron x-ray diffraction Rietveld refinement data and the structure determined by NPD of WC-type TaN, the pressure dependence of distance of different atoms in WC-type TaN crystal is shown in Fig.
In summary, crystal structure and atomic occupation of WC-type TaN have been re-determined by neutron power diffraction. Phase stability and compressibility of WC-type TaN and Ta5N6 have been studied at pressures up to 41 GPa using in situ high-pressure synchrotron x-ray diffraction in a diamond anvil cell. WC-type TaN and Ta5N6 are found to be stable with the pressure below 41 GPa. The bulk modulus of WC-type TaN and Ta5N6 derived from the P–V measurement data are 369(2) GPa and 287(3) GPa, experimental observations demonstrate that the a axis is more compressible than the c axis in the WC-type TaN crystal. This anisotropy can be attributed to the Ta–N covalent bond strengthening between the layered stacking of Ta and N atoms along the c axis. In addition, experimental observations also demonstrate the covalent bond Ta–N and high valence electron density of Ta atoms play an important role in the incompressibility of WC-type TaN.
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