Abstract：SnO2, as an important conductive oxide, can be used in solar cells, electrodes, oxidation catalysts, etc. The electronic structures and ionic radii of Sn4+ and Pb4+ are similar, and doping Pb into the crystal structure of SnO2 can change its optoelectronic properties without destroying the structure. Pressure to change the lattice structure and electronic band gap of materials can effectively enhance the material properties. To investigate the effects of elemental doping and pressure on the structural properties of SnO2, the structural phase transitions and electronic band gap changes of 10% Pb-doped and 25% Pb-doped SnO2 under high pressure were investigated. Pure SnO2, 10% Pb-doped and 25% Pb-doped SnO2 samples were prepared hydrothermal. Scanning electron microscopy showed that the samples were composed of multiple nanorods arranged in the center of the dispersion, and the whole was in the shape of a flower; X-ray diffraction showed that the samples were of a tetragonal rutile structure (space group P42); and the EDS spectra showed that the Pb was completely doped in the SnO2 lattice. The effects of different ratios of Pb doping on the high-voltage structure and electrical properties of SnO2 were investigated using a diamond pressure cavity combined with in situ Raman spectroscopy. Raman spectroscopy results show that there are four Raman vibrational modes of SnO2 at ambient pressure, which are B1g (88 cm-1), Eg (480 cm-1), A1g (639 cm-1) and B2g (775 cm-1). When the system pressure increases to 14 GPa, the Eg peak splits, a new peak appears at 563 cm-1 and SnO2 changes from a tetragonal rutile structure to a high-pressure CaCl2-type structure; the two Raman peaks at A1g and 576 cm-1 of 10% Pb-doped SnO2 gradually broaden with the increase of the pressure, and then merge to form a packet-like peak at 13 GPa, the degree of atomic disorder on the surface of the crystal increases, the symmetry decreases, the B1g mode changes to the A1g mode, the structural phase transition begins to appear, and the system changes to amorphous when the pressure increases to 25 GPa; the Raman peaks of 25% Pb-doped SnO2 appear at 190 and 775 cm-1, respectively, with the Pb4+ and B2g peaks, and the intensity of the Eg peak becomes weaker when the pressure reaches 10 GPa, the two Raman peaks at 576 cm-1 and A1g merge, the structural phase transition occurs, and amorphization occurs at 25.4 GPa. Using first-principles calculations to study the electrical properties of pure SnO2 and 10% Pb-doped SnO2 under pressure results show that: increased system pressure will make the forbidden band width of pure SnO2 from 0.645 to 1.759 eV, the electrons are more difficult to jump to the conduction band, the electrical conductivity is reduced; at the same time, doping will make the Pb into the crystal lattice to form defects, resulting in an increase in the density of defects in the vicinity of the valence band, valence band energy level decreases, the conductivity is enhanced, but the increase in system pressure does not change the conductivity of doped SnO2. This study provides new ideas in the field of SnO2 elemental doping. It enriches the study of the properties of SnO2 under extreme conditions by combining it with in situ high-pressure technology.
黄宇轩，王亚林，高金金，王晓雨，王世霞. 不同比例Pb掺杂对二氧化锡高压结构和电学性能影响研究[J]. 光谱学与光谱分析, 2025, 45(02): 364-370.
HUANG Yu-xuan, WANG Ya-lin, GAO Jin-jin, WANG Xiao-yu, WANG Shi-xia. Study on the Effect of Different Ratios of Pb Doping on the High-Pressure Structure and Electrical Properties of Tin Dioxide. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(02): 364-370.
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