Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Graphical Abstract
Abstract
Keywords
Electronic Supplementary Material
References
Show full outline
Hide outline
Research Article

Correlation between types of defects/vacancies of Bi2S3 nanostructures and their transient photocurrent

Mingyang Liu1,§, Luqing Wang1,§, Pei Dong1, Liangliang Dong2, Xifan Wang1, Jarin Joyner1, Xiangjian Wan3, Boris I. Yakobson1(), Robert Vajtai1(), Pulickel Ajayan1, Pol Spanos1()
Department of Materials Science and Nanoengineering Rice University Houston TX 77005 USA
Department of Chemistry Rice University Houston TX 77005 USA
College of Chemistry Nankai University Tianjin 300071 China

§ These authors contributed equally to this work.

Show Author Information

Graphical Abstract

View original image Download original image

Abstract

Crystalline nanostructures possess defects/vacancies that affect their physical and chemical properties. In this regard, the electronic structure of materials can be effectively regulated through defect engineering; therefore, the correlation between defects/vacancies and the properties of a material has attracted extensive attention. Here, we report the synthesis of Bi2S3 microspheres by nanorod assemblies with exposed {211} facets, and the investigation of the types and concentrations of defects/vacancies by means of positron annihilation spectrometry. Our studies revealed that an increase in the calcined temperature, from 350 to 400 ℃, led the predominant defect/vacancy densities to change from isolated bismuth vacancies (VBi) to septuple Bi3+-sulfur vacancy associates (VBiBiBiSSSS). Furthermore, the concentration of septuple Bi3+-sulfur vacancy associates increased as the calcined temperature was increased from 400 to 450 ℃. The characterized transient photocurrent spectrum demonstrates that the photocurrent values closely correlate with the types and concentrations of the predominant defects/vacancies. Our theoretical computation, through first principles, showed that VBiBiBiSSSS strongly absorbs I2(sol), easily desorbs I−(sol), and enhances the electrocatalytic activity of the nanostructures.

Keywords

Bi2S3 microspheresnanorod assemblydefects/vacanciespositron annihilation spectrometrytransient photocurrent

Electronic Supplementary Material

Download File(s)
nr-10-7-2405_ESM.pdf (736.2 KB)

References

1

Scherrer, B.; Döbeli, M.; Felfer, P.; Spolenak, R.; Cairney, J.; Galinski, H. The hidden pathways in dense energy materials-oxygen at defects in nanocrystalline metals. Adv. Mater. 2015, 27, 6220-6224.

Crossref Google Scholar
2

Rong, H. P.; Mao, J. J.; Xin, P. Y.; He, D. S.; Chen, Y. J.; Wang, D. S.; Niu, Z. Q.; Wu, Y. E.; Li, Y. D. Kinetically controlling surface structure to construct defect-rich intermetallic nanocrystals: Effective and stable catalysts. Adv. Mater. 2016, 28, 2540-2546.

Crossref Google Scholar
3

Lahiri, J.; Lin, Y.; Bozkurt, P.; Oleynik, I. I.; Batzill, M. An extended defect in graphene as a metallic wire. Nat. Nanotechnol. 2010, 5, 326-329.

Crossref Google Scholar
4

Kwon, K. D.; Refson, K.; Sposito, G. Defect-induced photoconductivity in layered manganese oxides: A density functional theory study. Phys. Rev. Lett. 2008, 100, 146601.

Crossref Google Scholar
5

Wang, H.; Zhang, J. J.; Hang, X. D.; Zhang, X. D.; Xie, J. F.; Pan, B. C.; Xie, Y. Half-metallicity in single-layered manganese dioxide nanosheets by defect engineering. Angew. Chem., Int. Ed. 2015, 54, 1195-1199.

Crossref Google Scholar
6

Liu, X. W.; Zhou, K. B.; Wang, L.; Wang, B. Y.; Li, Y. D. Oxygen vacancy clusters promoting reducibility and activity of ceria nanorods. J. Am. Chem. Soc. 2009, 131, 3140-3141.

Crossref Google Scholar
7

Zheng, H. L.; Yang, B. S.; Wang, D. D.; Han, R. L.; Du, X. B.; Yan, Y. Tuning magnetism of monolayer MoS2 by doping vacancy and applying strain. Appl. Phys. Lett. 2014, 104, 132403.

Crossref Google Scholar
8

Nan, H. Y.; Wang, Z. L.; Wang, W. H.; Liang, Z.; Lu, Y.; Chen, Q.; He, D. W.; Tan, P. H.; Miao, F.; Wang, X. R. et al. Strong photoluminescence enhancement of MoS2 through defect engineering and oxygen bonding. ACS Nano 2014, 8, 5738-5745.

Crossref Google Scholar
9

Stone, A. J.; Wales, D. J. Theoretical studies of icosahedral C60 and some related species. Chem. Phys. Lett. 1986, 128, 501-503.

Crossref Google Scholar
10

Li, L.; Reich, S.; Robertson, J. Defect energies of graphite: Density-functional calculations. Phys. Rev. B 2005, 72, 184109.

Crossref Google Scholar
11

Peng, X. Y.; Ahuja, R. Symmetry breaking induced bandgap in epitaxial graphene layers on SiC. Nano Lett. 2008, 8, 4464-4468.

Crossref Google Scholar
12

Kim, P. Graphene: Across the border. Nat. Mater. 2010, 9, 792-793.

Crossref Google Scholar
13

Li, K.; Zeng, X. Q.; Gao, S. M.; Ma, L.; Wang, Q. Y.; Xu, H.; Wang, Z. Y.; Huang, B. B.; Dai, Y.; Lu, J. Ultrasonic-assisted pyrolyzation fabrication of reduced SnO2-x/g-C3N4 heterojunctions: Enhance photoelectrochemical and photocatalytic activity under visible LED light irradiation. Nano Res. 2016, 9, 1969-1982.

Crossref Google Scholar
14

Wang, F.; Lin, J.; Zhao, T. B.; Hu, D. D.; Wu, T.; Liu, Y. Intrinsic "vacancy point defect" induced electrochemiluminescence from coreless supertetrahedral chalcogenide nanocluster. J. Am. Chem. Soc. 2016, 138, 7718-7724.

Crossref Google Scholar
15

Clark, G.; Schaibley, J. R.; Ross, J.; Taniguchi, T.; Watanabe, K. J.; Hendrickson, J. R.; Mou, S.; Yao, W.; Xu, X. D. Single defect light-emitting diode in a van der Waals heterostructure. Nano Lett. 2016, 16, 3944-3948.

Crossref Google Scholar
16

Zhang, L.; Wang, W. Z.; Jiang, D.; Gao, E. P.; Sun, S. M. Photoreduction of CO2 on BiOCl nanoplates with the assistance of photoinduced oxygen vacancies. Nano Res. 2015, 8, 821-831.

Crossref Google Scholar
17

Wu, T.; Zhou, X. G.; Zhang, H.; Zhong, X. H. Bi2S3 nanostructures: A new photocatalyst. Nano Res. 2010, 3, 379-386.

Crossref Google Scholar
18

Mohan, R. Green bismuth. Nat. Chem. 2010, 2, 336.

Crossref Google Scholar
19

Ye, C. H.; Meng, G. W.; Jiang, Z.; Wang, Y. H.; Wang, G. Z.; Zhang, L. D. Rational growth of Bi2S3 nanotubes from quasi-two-dimensional precursors. J. Am. Chem. Soc. 2002, 124, 15180-15181.

Crossref Google Scholar
20

Peter, L. M.; Wijayantha, K. G. U.; Riley, D. J.; Waggett, J. P. Band-edge tuning in self-assembled layers of Bi2S3 nanoparticles used to photosensitize nanocrystalline TiO2. J. Phys. Chem. B 2003, 107, 8378-8381.

Crossref Google Scholar
21

Biswas, K.; Zhao, L. D.; Kanatzidis, M. G. Tellurium-free thermoelectric: The anisotropic n-type semiconductor Bi2S3. Adv. Energy Mater. 2012, 2, 634-638.

Crossref Google Scholar
22

Konstantatos, G.; Levina, L.; Tang, J.; Sargent, E. H. Sensitive solution-processed Bi2S3 nanocrystalline photodetectors. Nano Lett. 2008, 8, 4002-4006.

Crossref Google Scholar
23

Bernechea, M.; Cao, Y. M.; Konstantatos, G. Size and bandgap tunability in Bi2S3 colloidal nanocrystals and its effect in solution processed solar cells. J. Mater. Chem. A 2015, 3, 20642-20648.

Crossref Google Scholar
24

Yang, Q.; Hu, C. G.; Wang, S. X.; Xi, Y.; Zhang, K. Y. Tunable synthesis and thermoelectric property of Bi2S3 nanowires. J. Phys. Chem. C 2013, 117, 5515-5520.

Crossref Google Scholar
25

Li, R. X.; Yue, Q.; Wei, Z. M. Abnormal low-temperature behavior of a continuous photocurrent in Bi2S3 nanowires. J. Mater. Chem. C 2013, 1, 5866-5871.

Crossref Google Scholar
26

Liu, Z. P.; Peng, S.; Xie, Q.; Hu, Z. K.; Yang, Y.; Zhang, S. Y.; Qian, Y. T. Large-scale synthesis of ultralong Bi2S3 nanoribbons via a solvothermal process. Adv. Mater. 2003, 15, 936-940.

Crossref Google Scholar
27

Lin, Y. M.; Dresselhaus, M. S. Thermoelectric properties of superlattice nanowires. Phys. Rev. B 2003, 68, 075304.

Crossref Google Scholar
28

Harman, T. C.; Taylor, P. J.; Walsh, M. P.; LaForge, B. E. Quantum dot superlattice thermoelectric materials and devices. Science 2002, 297, 2229-2232.

Crossref Google Scholar
29

Hsu, K. F.; Loo, S.; Guo, F.; Chen, W.; Dyck, J. S.; Uher, C.; Hogan, T.; Polychroniadis, E. K.; Kanatzidis, M. G. Cubic AgPbmSbTe2+m: Bulk thermoelectric materials with high figure of merit. Science 2004, 303, 818-821.

Crossref Google Scholar
30

Wang, Y.; Chen, J.; Wang, P.; Chen, L.; Chen, Y. B.; Wu, L. M. Syntheses, growth mechanism, and optical properties of [001] growing Bi2S3 nanorods. J. Phys. Chem. C 2009, 113, 16009-16014.

Crossref Google Scholar
31

Han, Q. F.; Chen, J.; Yang, X. J.; Lu, L. D.; Wang, X. Preparation of uniform Bi2S3 nanorods using xanthate complexes of bismuth (Ⅲ). J. Phys. Chem. C 2007, 111, 14072- 14077.

Crossref Google Scholar
32

Thomson, J. W.; Cademartiri, L.; MacDonald, M.; Petrov, S.; Calestani, G.; Zhang, P.; Ozin, G. A. Ultrathin Bi2S3 nanowires: Surface and core structure at the cluster-nanocrystal transition. J. Am. Chem. Soc. 2010, 132, 9058-9068.

Crossref Google Scholar
33

Cademartiri, L.; Scotognella, F.; O'Brien, P. G.; Lotsch, B. V.; Thomson, J.; Petrov, S.; Kherani, N. P.; Ozin, G. A. Cross-linking Bi2S3 ultrathin nanowires: A platform for nanostructure formation and biomolecule detection. Nano Lett. 2009, 9, 1482-1486.

Crossref Google Scholar
34

Wang, D. S.; Hao, C. H.; Zheng, W.; Ma, X. L.; Chu, D. R.; Peng, Q.; Li, Y. D. Bi2S3 nanotubes: Facile synthesis and growth mechanism. Nano Res. 2009, 2, 130-134.

Crossref Google Scholar
35

Tahir, A. A.; Ehsan, M. A.; Mazhar, M.; Wijayantha, K. G. U.; Zeller, M.; Hunter, A. D. Photoelectrochemical and photoresponsive properties of Bi2S3 nanotube and nanoparticle thin films. Chem. Mater. 2010, 22, 5084-5092.

Crossref Google Scholar
36

Mizoguchi, H.; Hosono, H.; Ueda, N.; Kawazoe, H. Preparation and electrical properties of Bi2S3 whiskers. J. Appl. Phys. 1995, 78, 1376-1378.

Crossref Google Scholar
37

Liu, M. Y.; Wang, L. Q.; Zhou, L. N.; Lei, S. D.; Joyner, J.; Yang, Y. C.; Vajtai, R.; , Ajayan, P.; Yakobson, B. I.; Spanos, P. Characterization of tin(Ⅱ) sulfide defects/vacancies and correlation with their photocurrent. Nano Res. 2017, 10, 218-228.

Crossref Google Scholar
38

Robles, J. M. C.; Ogando, E.; Plazaola, F. Positron lifetime calculation for the elements of the periodic table. J. Phys. : Condens. Matter 2007, 19, 176222.

Crossref Google Scholar
39

Barbiellini, B.; Puska, M. J.; Korhonen, T.; Harju, A.; Torsti, T.; Nieminen, R. M. Calculation of positron states and annihilation in solids: A density-gradient-correction scheme. Phys. Rev. B 1996, 53, 16201.

Crossref Google Scholar
40

Hasobe, T.; Fukuzumi, S.; Kamat, P. V. Stacked-cup carbon nanotubes for photoelectrochemical solar cells. Angew. Chem., Int. Ed. 2006, 45, 755-759.

Crossref Google Scholar
41

Liu, M. Y.; Wang, L. Q.; Zhou, L. N.; Lei, S. D.; Joyner, J.; Yang, Y. C.; Vajtai, R.; Ajayan, P.; Yakobson, B. I.; Spanos, P. Characterization of tin(Ⅱ) sulfide defects/vacancies and correlation with their photocurrent. Nano Res. 2017, 10, 218-228.

Crossref Google Scholar
42

Guo, S. Q.; Jing, T. Z.; Zhang, X.; Yang, X. B.; Yuan, Z. H.; Hu, F. Z. Mesoporous Bi2S3 nanorods with graphene-assistance as low-cost counter-electrode materials in dye-sensitized solar cells. Nanoscale 2014, 6, 14433-14440.

Crossref Google Scholar
43

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15-50.

Crossref Google Scholar
44

Kresse, G.; Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. J. Phys. Rev. B 1994, 49, 14251-14269.

Crossref Google Scholar
45

Hou, Y.; Wang, D.; Yang, X. H.; Fang, W. Q.; Zhang, B.; Wang, H. F.; Lu, G. Z.; Hu, P.; Zhao, H. J.; Yang, H. G. Rational screening low-cost counter electrodes for dye- sensitized solar cells. Nat. Commun. 2013, 4, 1583.

Crossref Google Scholar
46

Hou, Y.; Chen, Z. P.; Wang, D.; Zhang, B.; Yang, S.; Wang, H. F.; Hu, P.; Zhao, H. J.; Yang, H. G. Highly electrocatalytic activity of RuO2 nanocrystals for triiodide reduction in dye-sensitized solar cells. Small 2014, 10, 484-492.

Crossref Google Scholar
47

Hauch, A.; Georg, A. Diffusion in the electrolyte and charge-transfer reaction at the platinum electrode in dye- sensitized solar cells. Electrochim. Acta 2001, 46, 3457-3466.

Crossref Google Scholar
48

Calogero, G.; Calandra, P.; Irrera, A.; Sinopoli, A.; Citro, I.; Di Marco, G. A new type of transparent and low cost counter-electrode based on platinum nanoparticles for dye-sensitized solar cells. Energy Environ. Sci. 2011, 4, 1838-1844.

Crossref Google Scholar
Nano Research
Volume 10 Issue 7,
July 2017
Pages 2405-2414
DOI: 10.1007/s12274-017-1440-7
Cite this article:
Liu M, Wang L, Dong P, et al. Correlation between types of defects/vacancies of Bi2S3 nanostructures and their transient photocurrent. Nano Research, 2017, 10(7): 2405-2414. https://doi.org/10.1007/s12274-017-1440-7
Metrics & Citations  
Article History
Copyright
Return