形貌可控及光学吸收性能可调的钙钛矿型SrTiO3纳米结构的原位生长

doi:10.15541/jim20180255

摘要/Abstract

摘要：

钙钛矿相SrTiO₃在太阳能电池、光催化、燃料电池, 超导等领域均有广泛应用, 这些应用均与其晶体质量、形貌、暴露晶面和光学吸收等特性息息相关。本文通过微弧氧化-水热两步法原位制备了两种典型形貌的SrTiO₃纳米晶。结果表明, 随着微弧氧化电解液锶源浓度的降低, SrTiO₃形貌从立方块状转变为超薄片状。进一步分析表明, 所得的SrTiO₃立方块和Sr_1-_δTiO₃纳米片均为结晶质量良好的单晶体, 通过分析两种形貌样品的紫外-可见漫反射光谱, 发现Sr_1-_δTiO₃纳米片相对于SrTiO₃立方块, 具有明显的尺寸效应诱导的光学吸收蓝移特性。最后, 本研究提出了SrTiO₃的原位生长及形貌演变机制。

关键词: 钛酸锶, 原位生长, 微弧氧化法, 形貌调控, 光学性能

Abstract:

As a perovskite family member, SrTiO₃ shows significant applications in the fields of solar cells, photocatalysis, fuel cells and superconducting as a dependence of its crystallinity, morphology, crystal facet and optical properties. In this work, we reported an in-situ synthetic approach of SrTiO₃ nanostructures with modified morphology and tunable optical absorption properties based on conventional plasma electrolytic oxidation (PEO) associated with hydrothermal method. The morphology of SrTiO₃ nanostructures can be selectively modified from microcubes with smooth facets to ultrathin nanosheets by controlling the concentration of Sr source during PEO process. It is found that both SrTiO₃ microcubes and Sr_1-_δTiO₃ nanosheets are well-crystallized single crystals. UV-Vis diffuse reactance spectrum (DRS) measurement reveals that Sr_1-_δTiO₃ nanosheets with thin thickness show obvious blue-shift of absorption edge in comparison with SrTiO₃ microcubes due to the size effect. Finally, the morphology evolution and nucleation mechanism of SrTiO₃ nanostructures in-situ grown on PEO film is discussed.

Key words: SrTiO₃, in-situ growth, plasma electrolytic oxidation, morphology tuning, optical property

中图分类号:

TQ174

刘小元, 刘宝丹, 姜亚南, 王柯, 周洋, 杨兵, 张兴来, 姜辛. 形貌可控及光学吸收性能可调的钙钛矿型SrTiO₃纳米结构的原位生长[J]. 无机材料学报, 2019, 34(1): 65-71.

LIU Xiao-Yuan, LIU Bao-Dan, JIANG Ya-Nan, WANG Ke, ZHOU Yang, YANG Bing, ZHANG Xing-Lai, JIANG Xin. In-situ Synthesis of Perovskite SrTiO₃ Nanostructures with Modified Morphology and Tunable Optical Absorption Property[J]. Journal of Inorganic Materials, 2019, 34(1): 65-71.

图/表 19

Fig. 1 XRD patterns of SrTiO3 samples prepared under different hydrothermal conditions

Fig. 2 (a,c) SEM image and TEM bright field image of SrTiO3 microcubes; (b) Crystallographic model of cube-like SrTiO3 nanostructure; (d,e) HRTEM image and FFT pattern of SrTiO3 microcubes

Fig. 3 (a,c) SEM image and TEM bright field image of Sr1-δTiO3 nanosheets; (b) Crystallographic model of sheet-like Sr1-δTiO3; (d,e) HRTEM image and FFT pattern of Sr1-δTiO3 nanosheets

Fig. 4 XPS spectra of (a) Sr3d, (b) Ti2p and (c) O1s of Sr1-δTiO3 nanosheets prepared under 1.0 mol/L NaOH solution for 8 h

Fig. 5 Schematic diagram describing the formation process of SrTiO3 microcubes and Sr1-δTiO3 nanosheets

Fig. 6 UV-Vis spectra of PEO film, SrTiO3 microcubes and Sr1-δTiO3 nanosheets under different hydrothermal conditions

Fig. s1 SEM images of PEO film

Fig. s2 (a, c) X-ray diffraction topography (XRT) images of PEO film surface morphology and (b, d) cross section images Table S1 EDS results of PEO film prepared in high Sr concentration electrolyte (HSCE) and low Sr concentration electrolyte (LSCE)

Table s1 EDS results of PEO film prepared in high Sr concentration electrolyte (HSCE) and low Sr concentration electrolyte (LSCE)

Sample	O/at%	Ti/at%	Sr/at%	n(Sr) : n(Ti)
HSCE	79.35	11.51	9.14	0.79
LSCE	53.93	37.32	8.75	0.23

Table s2 EDS results of SrTiO3 microcubes and Sr1-δTiO3 nanosheets

Sample	O/at%	Ti/at%	Sr/at%	n(Sr) : n(Ti)
Microcube	55.06	24.16	20.77	0.86
Nanosheet	61.65	31.65	6.7	0.21

Fig. s3 XRD patterns of PEO films prepared under different conditions LSCE, 7 min PEO treating time; LSCE, 12 min PEO treating time, HSCE, 7 min PEO treating time and HSCE, 12 min PEO treating time

Fig. s4 SEM images of SrTiO3 microcubes obtained on PEO film under HSCE and in 0.5 mol/L NaOH with different durations (a) 180℃, 1 h; (b) 180℃, 4 h; (c) 180℃, 6 h; (d) 180℃, 8 h

Fig. s5 Surface morphology of PEO film after hydrothermal treating (without NaOH, 180℃, 8 h)

Table s3 XPS element analysis of Sr1-δTiO3 nanosheets

Sample	O/at%	B/at%	Ti/at%	Sr/at%	n(Sr) : n(Ti)
Nanosheet	69.95	0.70	22.39	6.96	0.31

Fig. S6 SEM images of SrTiO3 microcubes obtained on PEO film under HSCE and in 1.0 mol/L NaOH with different durations (a) 180℃, 0.5 h; (b) 180℃, 1 h; (c) 180℃, 2 h; (d) 180℃, 8 h

Fig. S7 SEM images of SrTiO3 microcubes obtained on PEO film under HSCE and in 1.5 mol/L NaOH with different durations (a) 180℃, 4 h; (b) 180℃, 6 h; (c) 180℃, 8 h

Fig. S8 SEM images of Sr1-δTiO3 nanosheets obtained on PEO film under LSCE and in 1.0 mol/L NaOH with different durations (a) 180℃, 0.5 h; (b) 180℃, 1 h; (c) 180℃, 2 h; (d) 180℃, 4 h; (e) 180℃, 8 h

Fig. S9 SEM images of Sr1-δTiO3 nanosheets obtained on PEO film under LSCE and in 0.5 mol/L NaOH with different durations (a) 180℃, 2 h; (b) 180℃, 4 h; (c) 180℃, 8 h

Fig. S10 SEM images of Sr1-δTiO3 nanosheets obtained on PEO film under LSCE and in 1.5 mol/L NaOH with different durations (a) 180℃, 2 h; (b) 180℃, 4 h; (c) 180℃, 8 h

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形貌可控及光学吸收性能可调的钙钛矿型SrTiO₃纳米结构的原位生长

In-situ Synthesis of Perovskite SrTiO₃ Nanostructures with Modified Morphology and Tunable Optical Absorption Property

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