AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Nitrogen-doped graphene quantum dots: Optical properties modification and photovoltaic applications

Md Tanvir Hasan1,§, Roberto Gonzalez-Rodriguez1,§, Conor Ryan1, Kristof Pota2, Kayla Green2, Jeffery L. Coffer2, Anton V. Naumov1( )
Department of Physics and Astronomy,Texas Christian University, TCU Box 298840, Fort Worth,Texas,76129,USA;
Department of Chemistry and Biochemistry,Texas Christian University, TCU Box 298860, Fort Worth,Texas,76129,USA;

§ Md Tanvir Hasan and Roberto Gonzalez-Rodriguez contributed equally to this work.

Show Author Information

Graphical Abstract

Abstract

In this work, we utilize a bottom-up approach to synthesize nitrogen self-doped graphene quantum dots (NGQDs) from a single glucosamine precursor via an eco-friendly microwave-assisted hydrothermal method. Structural and optical properties of as-produced NGQDs are further modified using controlled ozone treatment. Ozone-treated NGQDs (Oz-NGQDs) are reduced in size to 5.5 nm with clear changes in the lattice structure and ID/IG Raman ratios due to the introduction/alteration of oxygen-containing functional groups detected by Fourier-transform infrared (FTIR) spectrometer and further verified by energy dispersive X-ray spectroscopy (EDX) showing increased atomic/weight percentage of oxygen atoms. Along with structural modifications, GQDs experience decrease in ultraviolet–visible (UV–vis) absorption coupled with progressive enhancement of visible (up to 16 min treatment) and near-infrared (NIR) (up to 45 min treatment) fluorescence. This allows fine-tuning optical properties of NGQDs for solar cell applications yielding controlled emission increase, while controlled emission quenching was achieved by either blue laser or thermal treatment. Optimized Oz-NGQDs were further used to form a photoactive layer of solar cells with a maximum efficiency of 2.64% providing a 6-fold enhancement over untreated NGQD devices and a 3-fold increase in fill factor/current density. This study suggests simple routes to alter and optimize optical properties of scalably produced NGQDs to boost the photovoltaic performance of solar cells.

Keywords

nitrogen-doped graphene quantum dotsozone treatmentoptical propertiesphotovoltaicssolar cells

Electronic Supplementary Material

Download File(s)
12274_2019_2337_MOESM1_ESM.pdf (3.1 MB)

References

1

Sun, J.; Yang, S. W.; Wang, Z. Y.; Shen, H.; Xu, T.; Sun, L. T.; Li, H.; Chen, W. W.; Jiang, X. Y.; Ding, G. Q. et al. Ultra-high quantum yield of graphene quantum dots: Aromatic-nitrogen doping and photoluminescence mechanism. Part. Part. Syst. Charact. 2015, 32, 434-440.
Crossref Google Scholar
2

Niu, F. S.; Xu, Y. H.; Liu, J. X.; Song, Z. Q.; Liu, M. L.; Liu, J. Q. Controllable electrochemical/electroanalytical approach to generate nitrogen-doped carbon quantum dots from varied amino acids: Pinpointing the utmost quantum yield and the versatile photoluminescent and electrochemiluminescent applications. Electrochim. Acta 2017, 236, 239-251.
Crossref Google Scholar
3

Qu, D.; Zheng, M.; Zhang, L. G.; Zhao, H. F.; Xie, Z. G.; Jing, X. B.; Haddad, R. E.; Fan, H. Y.; Sun, Z. C. Formation mechanism and optimization of highly luminescent N-doped graphene quantum dots. Sci. Rep. 2014, 4, 5294.
Crossref Google Scholar
4

Liu, Q.; Guo, B. D.; Rao, Z. Y.; Zhang, B. H.; Gong, J. R. Strong two-photon-induced fluorescence from photostable, biocompatible nitrogen-doped graphene quantum dots for cellular and deep-tissue imaging. Nano Lett. 2013, 13, 2436-2441.
Crossref Google Scholar
5

Hasan, M. T.; Gonzalez-Rodriguez, R.; Ryan, C.; Faerber, N.; Coffer, J. L.; Naumov, A. V. Photo-and electroluminescence from nitrogen-doped and nitrogen-sulfur codoped graphene quantum dots. Adv. Funct. Mater. 2018, 28, 1804337.
Crossref Google Scholar
6

Zhou, L.; Geng, J. L.; Liu, B. Graphene quantum dots from polycyclic aromatic hydrocarbon for bioimaging and sensing of Fe3+ and hydrogen peroxide. Part. Part. Syst. Charact. 2013, 30, 1086-1092.
Crossref Google Scholar
7

Nurunnabi, M.; Khatun, Z.; Huh, K. M.; Park, S. Y.; Lee, D. Y.; Cho, K. J.; Lee, Y. -K. In vivo biodistribution and toxicology of carboxylated graphene quantum dots. ACS Nano 2013, 7, 6858-6867.
Crossref Google Scholar
8

Shang, W. H.; Zhang, X. Y.; Zhang, M.; Fan, Z. T.; Sun, Y.; Han, M.; Fan, L. Z. The uptake mechanism and biocompatibility of graphene quantum dots with human neural stem cells. Nanoscale 2014, 6, 5799-5806.
Crossref Google Scholar
9

Coe, S.; Woo, W. -K.; Bawendi, M.; Bulović, V. Electroluminescence from single monolayers of nanocrystals in molecular organic devices. Nature 2002, 420, 800-803.
Crossref Google Scholar
10

Tessler, N.; Medvedev, V.; Kazes, M.; Kan, S. H.; Banin, U. Efficient near-infrared polymer nanocrystal light-emitting diodes. Science 2002, 295, 1506-1508.
Crossref Google Scholar
11

Son, D. I.; Kwon, B. W.; Park, D. H.; Seo, W. -S.; Yi, Y.; Angadi, B.; Lee, C. -L.; Choi, W. K. Emissive ZnO-graphene quantum dots for white-light-emitting diodes. Nat. Nanotechnol. 2012, 7, 465-471.
Crossref Google Scholar
12

Moon, B. J.; Jang, D.; Yi, Y.; Lee, H.; Kim, S. J.; Oh, Y.; Lee, S. H.; Park, M.; Lee, S.; Bae, S. Multi-functional nitrogen self-doped graphene quantum dots for boosting the photovoltaic performance of BHJ solar cells. Nano Energy 2017, 34, 36-46.
Crossref Google Scholar
13

Carolan, D.; Rocks, C.; Padmanaban, D. B.; Maguire, P.; Svrcek, V.; Mariotti, D. Environmentally friendly nitrogen-doped carbon quantum dots for next generation solar cells. Sustainable Energy Fuels 2017, 1, 1611-1619.
Crossref Google Scholar
14

Gupta, V.; Chaudhary, N.; Srivastava, R.; Sharma, G. D.; Bhardwaj, R.; Chand, S. Luminscent graphene quantum dots for organic photovoltaic devices. J. Am. Chem. Soc. 2011, 133, 9960-9963.
Crossref Google Scholar
15

Wang, H.; Sun, P. F.; Cong, S.; Wu, J.; Gao, L. J.; Wang, Y.; Dai, X.; Yi, Q. H.; Zou, G. F. Nitrogen-doped carbon dots for "green" quantum dot solar cells. Nanoscale Res. Lett. 2016, 11, 27.
Crossref Google Scholar
16

Alivisatos, A. P.; Gu, W. W.; Larabell, C. Quantum dots as cellular probes. Annu. Rev. Biomed. Eng. 2005, 7, 55-76.
Crossref Google Scholar
17

Zhu, S. J.; Zhang, J. H.; Qiao, C. Y.; Tang, S. J.; Li, Y. F.; Yuan, W. J.; Li, B.; Tian, L.; Liu, F.; Hu, R. et al. Strongly green-photoluminescent graphene quantum dots for bioimaging applications. Chem. Commun. 2011, 47, 6858-6860.
Crossref Google Scholar
18

Ge, J. C.; Lan, M. H.; Zhou, B. J.; Liu, W. M.; Guo, L.; Wang, H.; Jia, Q. Y.; Niu, G. L.; Huang, X.; Zhou, H. Y. et al. A graphene quantum dot photodynamic therapy agent with high singlet oxygen generation. Nat. Commun. 2014, 5, 4596.
Crossref Google Scholar
19

Tabish, T. A.; Scotton, C. J.; Ferguson, D. C. J.; Lin, L. X.; van der Veen, A.; Lowry, S.; Ali, M.; Jabeen, F.; Ali, M.; Winyard, P. G. et al. Biocompatibility and toxicity of graphene quantum dots for potential application in photodynamic therapy. Nanomedicine 2018, 13, 1923-1937.
Crossref Google Scholar
20

Zeng, Z. P.; Chen, S. F.; Tan, T. T. Y.; Xiao, F. -X. Graphene quantum dots (GQDs) and its derivatives for multifarious photocatalysis and photoelectrocatalysis. Catal. Today 2018, 315, 171-183.
Crossref Google Scholar
21

Lu, Q.; Zhang, Y. J.; Liu, S. Q. Graphene quantum dots enhanced photocatalytic activity of zinc porphyrin toward the degradation of methylene blue under visible-light irradiation. J. Mater. Chem. A 2015, 3, 8552-8558.
Crossref Google Scholar
22

Tao, H. Q.; Yang, K.; Ma, Z.; Wan, J. M.; Zhang, Y. J.; Kang, Z. H.; Liu, Z. In vivo NIR fluorescence imaging, biodistribution, and toxicology of photoluminescent carbon dots produced from carbon nanotubes and graphite. Small 2012, 8, 281-290.
Crossref Google Scholar
23

Dong, Y. Q.; Chen, C. Q.; Zheng, X. T.; Gao, L. L.; Gui, Z. M.; Yang, H. B.; Guo, C. X.; Chi, Y. W.; Li, C. M. One-step and high yield simultaneous preparation of single- and multi-layer graphene quantum dots from CX-72 carbon black. J. Mater. Chem. 2012, 22, 8764-8766.
Crossref Google Scholar
24

Li, H. T.; He, X. D.; Kang, Z. H.; Huang, H.; Liu, Y.; Liu, J. L.; Lian, S. Y.; Tsang, C. H. A.; Yang, X. B.; Lee, S. -T. Water-soluble fluorescent carbon quantum dots and photocatalyst design. Angew. Chem., Int. Ed. 2010, 49, 4430-4434.
Crossref Google Scholar
25

Li, Y.; Hu, Y.; Zhao, Y.; Shi, G. Q.; Deng, L. E.; Hou, Y. B.; Qu, L. T. An electrochemical avenue to green-luminescent graphene quantum dots as potential electron-acceptors for photovoltaics. Adv. Mater. 2011, 23, 776-780.
Crossref Google Scholar
26

Liu, R. L.; Wu, D. Q.; Feng, X. L.; Müllen, K. Bottom-up fabrication of photoluminescent graphene quantum dots with uniform morphology. J. Am. Chem. Soc. 2011, 133, 15221-15223.
Crossref Google Scholar
27

Liu, C. J.; Zhang, P.; Tian, F.; Li, W. C.; Li, F.; Liu, W. G. One-step synthesis of surface passivated carbon nanodots by microwave assisted pyrolysis for enhanced multicolor photoluminescence and bioimaging. J. Mater. Chem. 2011, 21, 13163-13167.
Crossref Google Scholar
28

Zhai, X. Y.; Zhang, P.; Liu, C. J.; Bai, T.; Li, L. M.; Dai, L. M.; Liu, W. G. Highly luminescent carbon nanodots by microwave-assisted pyrolysis. Chem. Commun. 2012, 48, 7955-7957.
Crossref Google Scholar
29

Wang, L.; Zhu, S. -J.; Wang, H. -Y.; Qu, S. -N.; Zhang, Y. -L.; Zhang, J. -H.; Chen, Q. -D.; Xu, H. -L.; Han, W.; Yang, B. et al. Common origin of green luminescence in carbon nanodots and graphene quantum dots. ACS Nano 2014, 8, 2541-2547.
Crossref Google Scholar
30

Wang, L.; Wang, H. Y.; Wang, Y.; Zhu, S. J.; Zhang, Y. L.; Zhang, J. H.; Chen, Q. D.; Han, W.; Xu, H. L.; Yang, B. et al. Direct observation of quantum-confined graphene-like states and novel hybrid states in graphene oxide by transient spectroscopy. Adv. Mater. 2013, 25, 6539-6545.
Crossref Google Scholar
31

Yang, Z. -C.; Li, X.; Wang, J. Intrinsically fluorescent nitrogen-containing carbon nanoparticles synthesized by a hydrothermal process. Carbon 2011, 49, 5207-5212.
Crossref Google Scholar
32

Bao, L.; Zhang, Z. -L.; Tian, Z. -Q.; Zhang, L.; Liu, C.; Lin, Y.; Qi, B. P.; Pang, D. -W. Electrochemical tuning of luminescent carbon nanodots: From preparation to luminescence mechanism. Adv. Mater. 2011, 23, 5801-5806.
Crossref Google Scholar
33

Shang, J. Z.; Ma, L.; Li, J. W.; Ai, W.; Yu, T.; Gurzadyan, G. G. The origin of fluorescence from graphene oxide. Sci. Rep. 2012, 2, 792.
Crossref Google Scholar
34

Mirtchev, P.; Henderson, E. J.; Soheilnia, N.; Yip, C. M.; Ozin, G. A. Solution phase synthesis of carbon quantum dots as sensitizers for nanocrystalline TiO2 solar cells. J. Mater. Chem. 2012, 22, 1265-1269.
Crossref Google Scholar
35

Zhang, Y. -Q.; Ma, D. -K.; Zhang, Y. -G.; Chen, W.; Huang, S. -M. N-doped carbon quantum dots for TiO2-based photocatalysts and dye-sensitized solar cells. Nano Energy 2013, 2, 545-552.
Crossref Google Scholar
36

Briscoe, J.; Marinovic, A.; Sevilla, M.; Dunn, S.; Titirici, M. Biomass-derived carbon quantum dot sensitizers for solid-state nanostructured solar cells. Angew. Chem., Int. Ed. 2015, 54, 4463-4468.
Crossref Google Scholar
37

Kwon, W.; Lee, G.; Do, S.; Joo, T.; Rhee, S. W. Size-controlled soft-template synthesis of carbon nanodots toward versatile photoactive materials. Small 2014, 10, 506-513.
Crossref Google Scholar
38

Narayanan, R.; Deepa, M.; Srivastava, A. K. Förster resonance energy transfer and carbon dots enhance light harvesting in a solid-state quantum dot solar cell. J. Mater. Chem. A 2013, 1, 3907-3918.
Crossref Google Scholar
39

Qian, F. L.; Li, X. M.; Tang, L. B.; Lai, S. K.; Lu, C. Y.; Lau, S. P. Potassium doping: Tuning the optical properties of graphene quantum dots. AIP Adv. 2016, 6, 075116.
Crossref Google Scholar
40

Dong, Y.; Zhang, S.; Shi, L. L.; Chen, Y. X.; Ma, J.; Guo, S. S.; Chen, X. H.; Song, H. H. The photoluminescence of step-wise reduced graphene oxide quantum dots. Mater. Chem. Phys. 2018, 203, 125-132.
Crossref Google Scholar
41

Jin, S. H.; Kim, D. H.; Jun, G. H.; Hong, S. H.; Jeon, S. Tuning the photoluminescence of graphene quantum dots through the charge transfer effect of functional groups. ACS Nano 2013, 7, 1239-1245.
Crossref Google Scholar
42

Basak, T.; Basak, T. Effect of carrier doping and external electric field on the optical properties of graphene quantum dots. IOP Conf. Ser. : Mater. Sci. Eng. 2018, 310, 012014.
Crossref Google Scholar
43

Hai, X.; Feng, J.; Chen, X. W.; Wang, J. H. Tuning the optical properties of graphene quantum dots for biosensing and bioimaging. J. Mater. Chem. B 2018, 6, 3219-3234.
Crossref Google Scholar
44

Zhao, M. L. Direct synthesis of graphene quantum dots with different fluorescence properties by oxidation of graphene oxide using nitric acid. Appl. Sci. 2018, 8, 1303.
Crossref Google Scholar
45

Yu, P.; Wen, X. M.; Toh, Y. -R.; Tang, J. Temperature-dependent fluorescence in carbon dots. J. Phys. Chem. C 2012, 116, 25552-25557.
Crossref Google Scholar
46

Tian, Y.; Li, L.; Guo, X.; Wójtowicz, A.; Estevez, L.; Krysmann, M. J.; Kelarakis, A. Dramatic photoluminescence quenching in carbon dots induced by cyclic voltammetry. Chem. Commun. 2018, 54, 9067-9070.
Crossref Google Scholar
47

Gao, F. H.; Liu, F. C.; Bai, X. H.; Xu, X. F.; Kong, W. J.; Liu, J.; Lv, F. Z.; Long, L. Z.; Yang, Y.; Li, M. Tuning the photoluminescence of graphene oxide quantum dots by photochemical fluorination. Carbon 2019, 141, 331-338.
Crossref Google Scholar
48

Hasan, M. T.; Senger, B. J.; Mulford, P.; Ryan, C.; Doan, H.; Gryczynski, Z.; Naumov, A. V. Modifying optical properties of reduced/graphene oxide with controlled ozone and thermal treatment in aqueous suspensions. Nanotechnology 2017, 28, 065705.
Crossref Google Scholar
49

Hasan, M. T.; Senger, B. J.; Ryan, C.; Culp, M.; Gonzalez-Rodriguez, R.; Coffer, J. L.; Naumov, A. V. Optical band gap alteration of graphene oxide via ozone treatment. Sci. Rep. 2017, 7, 6411.
Crossref Google Scholar
50

Wang, L.; Wang, Y. L.; Xu, T.; Liao, H. B.; Yao, C. J.; Liu, Y.; Li, Z.; Chen, Z. W.; Pan, D. Y.; Sun, L. T. et al. Gram-scale synthesis of single-crystalline graphene quantum dots with superior optical properties. Nat. Commun. 2014, 5, 5357.
Crossref Google Scholar
51

Yang, Q. M.; Duan, J. L.; Yang, W.; Li, X. M.; Mo, J. H.; Yang, P. Z.; Tang, Q. W. Nitrogen-doped carbon quantum dots from biomass via simple one-pot method and exploration of their application. Appl. Surf. Sci. 2018, 434, 1079-1085.
Crossref Google Scholar
52

Fan, X. B.; Peng, W. C.; Li, Y.; Li, X. Y.; Wang, S. L.; Zhang, G. L.; Zhang, F. B. Deoxygenation of exfoliated graphite oxide under alkaline conditions: A green route to graphene preparation. Adv. Mater. 2008, 20, 4490-4493.
Crossref Google Scholar
53

Cai, W. W.; Piner, R. D.; Stadermann, F. J.; Park, S.; Shaibat, M. A.; Ishii, Y.; Yang, D. X.; Velamakanni, A.; An, S. J.; Stoller, M. et al. Synthesis and solid-state NMR structural characterization of 13C-labeled graphite oxide. Science 2008, 321, 1815-1817.
Crossref Google Scholar
54

He, H. Y.; Riedl, T.; Lerf, A.; Klinowski, J. Solid-state NMR studies of the structure of graphite oxide. J. Phys. Chem. 1996, 100, 19954-19958.
Crossref Google Scholar
55

Gu, J.; Zhang, Z. P.; Peng, A. M.; Yang, J. Facile synthesis and photoluminescence characteristics of blue-emitting nitrogen-doped graphene quantum dots. Nanotechnology 2016, 27, 165704.
Crossref Google Scholar
56

Ben Aoun, S. Nanostructured carbon electrode modified with N-doped graphene quantum dots-chitosan nanocomposite: A sensitive electrochemical dopamine sensor. R. Soc. Open Sci. 2017, 4, 171199.
Crossref Google Scholar
57

Kwon, W.; Kim, Y. -H.; Lee, C. -L.; Lee, M.; Choi, H. C.; Lee, T. -W.; Rhee, S. -W. Electroluminescence from graphene quantum dots prepared by amidative cutting of tattered graphite. Nano Lett. 2014, 14, 1306-1311.
Crossref Google Scholar
58

Guo, X. C.; Zhang, H. Y.; Sun, H. Q.; Tade, M. O.; Wang, S. B. Green synthesis of carbon quantum dots for sensitized solar cells. ChemPhotoChem 2017, 1, 116-119.
Crossref Google Scholar
59

Vougioukalakis, G. C.; Philippopoulos, A. I.; Stergiopoulos, T.; Falaras, P. Contributions to the development of ruthenium-based sensitizers for dye-sensitized solar cells. Coord. Chem. Rev. 2011, 255, 2602-2621.
Crossref Google Scholar
60

Lu, K. Y.; Wang, Y. J.; Liu, Z. K.; Han, L.; Shi, G. Z.; Fang, H. H.; Chen, J.; Ye, X. C.; Chen, S.; Yang, F. et al. High-efficiency PbS quantum-dot solar cells with greatly simplified fabrication processing via "Solvent-Curing". Adv. Mater. 2018, 30, 1707572.
Crossref Google Scholar
61

Huang, F.; Zhang, L. S.; Zhang, Q. F.; Hou, J.; Wang, H. G.; Wang, H. L.; Peng, S. L.; Liu, J. S.; Cao, G. Z. High efficiency CdS/CdSe quantum dot sensitized solar cells with two ZnSe layers. ACS Appl. Mater. Interfaces 2016, 8, 34482-34489.
Crossref Google Scholar
62

Derfus, A. M.; Chan, W. C. W.; Bhatia, S. N. Probing the cytotoxicity of semiconductor quantum dots. Nano Lett. 2004, 4, 11-18.
Crossref Google Scholar
63

Bottrill, M.; Green, M. Some aspects of quantum dot toxicity. Chem. Commun. 2011, 47, 7039-7050.
Crossref Google Scholar
64

Ba, L. X.; Liu, H.; Shen, W. Z. Perovskite/c-Si tandem solar cells with realistic inverted architecture: Achieving high efficiency by optical optimization. Prog. Photovolt. : Res. Appl. 2018, 26, 924-933.
Crossref Google Scholar
65

Shahrjerdi, D.; Bedell, S. W.; Bayram, C.; Lubguban, C. C.; Fogel, K.; Lauro, P.; Ott, J. A.; Hopstaken, M.; Gayness, M.; Sadana, D. Ultralight high-efficiency flexible InGaP/(In)GaAs tandem solar cells on plastic. Adv. Energy Mater. 2013, 3, 566-571.
Crossref Google Scholar
Nano Research
Volume 12 Issue 5,
May 2019
Pages 1041-1047
DOI: 10.1007/s12274-019-2337-4
Cite this article:
Hasan MT, Gonzalez-Rodriguez R, Ryan C, et al. Nitrogen-doped graphene quantum dots: Optical properties modification and photovoltaic applications. Nano Research, 2019, 12(5): 1041-1047. https://doi.org/10.1007/s12274-019-2337-4
Topics:
Doping (additives)Energy dispersive spectroscopyFourier transform infrared spectroscopyGrapheneInfrared devices NanocrystalsNitrogenSemiconductor quantum dotsSol-cellsSolar power generationSpectrometers

955

Views

90

Crossref

N/A

Web of Science

91

Scopus

0

CSCD

Altmetrics
Received: 19 November 2018
Revised: 11 February 2019
Accepted: 13 February 2019
Published: 11 March 2019
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019
Return