1Xi’an Modern Chemistry Research Institute, Xi’an 710065, China 2Key Laboratory of Materials Physics, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei 230031, China 3University of Science and Technology of China, Hefei 230026, China 4Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Since the discoveries of polymeric nitrogen, named cg-N (2004), LP-N (2014), HLP-N (2019), another polymorph named black phosphorus nitrogen (BP-N) was synthesized at high-pressure-high-temperature conditions. The narrow existing pressure region and similar synthesized pressure of BP-N compared with cg-N indicate that the stable energy and enthalpy of formation of these two structures are close to each other, which was confirmed by our theoretical calculation. In order to obtain the pressure region of BP-N phase, pure N2 and TiN/Pb + N2 precursors were used for laser-heating high pressure experiments in diamond anvil cell (DAC), and the phase identity was examined by Raman and XRD mapping. BP-N can be synthesized in the pressure range of 130 GPa to 140 GPa with the assistance of heating absorber. With the decrease of the pressure, BP-N can be quenched to ∼ 40 GPa. The synthesizing pressure–temperature and the stable pressure region of BP-N are important for further exploration of BP-N and its kinetic and thermal dynamic relationship with other polymeric nitrogen, especially cg-N.
* Project supported by the National Natural Science Foundation of China (Grant No. 11904281).
Cite this article:
Ying Liu(刘影)†, Haipeng Su(苏海鹏), Caoping Niu(牛草萍), Xianlong Wang(王贤龙), Junran Zhang(张俊然), Zhongxue Ge(葛忠学), and Yanchun Li(李延春) Synthesis of black phosphorus structured polymeric nitrogen 2020 Chin. Phys. B 29 106201
Fig. 1.
(a) Raman spectra of nitrogen heated at 143 GPa from run I (black) compared with the experimental spectra for BP-structured polymeric nitrogen (red bars) at 138 GPa, 2200 K.[16] Inset shows the microscopic images of the sample under illumination with both reflected and transmitted light before and after laser heating. (b) Crystal structure of BP-N under 140 GPa.
Fig. 2.
Raman spectra of nitrogen before and after heating at 130 GPa using TiN and Pb as laser absorber, respectively.
#
Pressure/GPa
Temperature/K
Absorber
Results
I
∼ 143
∼ 2500
–
BP-N
II
∼ 130
∼ 1800
–
cg-N
III
∼ 130
∼ 2500
TiN
BP-N
IV
∼ 130
∼ 2500
Pb
BP-N
V
∼ 120
∼ 2500
TiN
–
Table 1.
Experimental details of the five experimental runs, including the experimental conditions and major results.
Fig. 3.
(a) Raman spectra of BP-N during the decompression. (b) Measured pressure dependence of Raman shift (run III) of BP-N and (run II) of CG-N compared with calculations and previously reported values[10,13,15,16] of polymeric nitrogen. All measurements were performed during decompression.
Fig. 4.
(a) The equation of state, (b) formation enthalpy, and (c) energy density of CH-N, BP-N, and cg-N. The values of CH-N, BP-N, and cg-N phases are shown in red triangle, red circle, and blue square, respectively. The red vertical dotted line indicates the pressure (20 GPa), where CH-N becomes stable.
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