Two-Photon Fluorescence in N-Doped Graphene Quantum Dots
Nitrogen-doped graphene quantum dots (N-GQDs)
were fabricated by microwave-assisted hydrothermal technique. The
optical properties of the N-GQDs were studied. The luminescence of
the N-GQDs can be tuned by varying the excitation wavelength.
Furthermore, two-photon luminescence of the N-GQDs excited by
near-infrared laser can be obtained. It is shown that N-doping play a
key role on two-photon luminescence. The N-GQDs are expected to
find application in biological applications including bioimaging and
sensing.
[1] X. Yan, X. Cui, B. S. Li, L. S. Li, “Large, Solution-Processable Graphene
Quantum Dots as Light Absorbers for Photovoltaics”, Nano. Letter, 2010,
10, 1869-1873.
[2] L. A. Ponomarenko, F.Schedin, M. I. Katsnelson, R.Yang, E. W. Hill, K.
S. Novoselov, A. K. Geim, “Chaotic Dirac Billiard in Graphene Quantum
Dots. Science 2008, 320, 356–358.
[3] C. O. Girit, J. C. Meyer, R. Erni, M. D. Rossell, C. Kisielowski, L.Yang,
C. H. Park,; M. F. Crommie,; M. L. Cohen, S. G. Louie,et al. “Graphene
at the Edge: Stability and Dynamics”, Science 2009, 323, 1705–1708.
[4] X. Yan, X. Cui, L. S. Li, “Stable Colloidal Graphene Quantum Dots with
Tunable Size” J. Am. Chem. Soc. 2010, 132, 5944–5945.
[5] C. X. Guo, H. B. Yang, Z. M. Sheng, Z. S. Lu, Q. L. Song, C. M. Li,
“Layered Graphene/Quantum Dots for Photovoltaic Devices”, Angew.
Chem., Int. Ed. 2010, 49, 3014–3017.
[6] C. M. Luk, L. B. Tang, W. F. Zhang, S. F. Yu, K. S. Teng and S. P. Lau,
“An Efficient and Stable Fluorescent Graphene Quantum Dot–Agar
Composite as a Converting Material in White Light Emitting Diodes”, J.
Mater. Chem., 2012, 22, 22378.
[7] V. Gupta, N. Chaudhary, R. Srivastava, G. Datt Sharma, R. Bhardwaj, S.
Chand, “Luminscent Graphene Quantum Dots for Organic Photovoltaic
Devices”, J. Am. Chem. Soc. 2011, 133, 9960–9963.
[8] X. M. Geng, L. Niu, Z. Y. Xing, R. S. Song, G. T. Liu, M. T. Sun, G. S.
Cheng, H. J. Zhong, Z. H. Liu, Z. J. Zhang, et al. “Aqueous-Processable
Noncovalent Chemically Converted GrapheneQuantum Dot Composites
for Flexible and Transparent Optoelectronic Films”, Adv. Mater. 2010,
22,638–642.
[9] S. J. Zhu, J. H. Zhang, C. Y. Qiao, S. J. Tang, Y. F. Li, W. J. Yuan, B.
Li, L. Tian, F. Liu, R. Hu, et al. “Strongly Green-Photoluminescent
Graphene Quantum Dots for Bioimaging Applications”, Chem.
Commun. 2011, 47, 6858– 6860.
[10] L. Ma, H. Hu, L. Y. Zhu, J. H. Wang, “Boron and Nitrogen Doping
Induced Half-Metallicity in Zigzag Triwing Graphene Nanoribbons”, J.
Phys. Chem. C, 2011, 115, 6195.
[11] K. P. Gong, F. Du, Z. H. Xia, M. Durstock, L. M. Dai, “Nitrogen-Doped
Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen
Reduction”, Science 2009, 323, 760.
[12] D. S. Yu, Q. Zhang, L. M. Dai, “Highly Efficient Metal-Free Growth of
Nitrogen-Doped Single-Walled Carbon Nanotubes on Plasma-Etched
Substrates for Oxygen Reduction”, J. Am. Chem. Soc. 2010, 132, 15127.
[13] M. Deifallah, P. F. McMillan, F. J. Cora, “Electronic and Structural
Properties of Two-Dimensional Carbon Nitride Graphenes”, Phys. Chem.
C 2008, 112, 5447.
[14] Y. Li, Y. Zhao, H. Cheng, Y. Hu, G. Shi,; L. Dai, L. Qu, “Nitrogen-Doped
Graphene Quantum Dots with Oxygen-Rich Functional Groups”, J. Am.
Chem. Soc. 2012, 134, 15–18.
[15] Q. Li, S. Zhang, L. Dai, L.-S. Li, “Nitrogen-Doped Colloidal Graphene
Quantum Dots and Their Size-Dependent Electrocatalytic Activity for the
Oxygen Reduction Reaction”, J. Am. Chem. Soc. 2012, 134,
18932–18935.
[16] C. Hu, Y. Liu, Y. Yang, J. Cui, Z. Huang, Y. Wang, L. Yang, H. Wang, Y.
Xiao, J. Rong, “One-Step Preparation of Nitrogen- Doped Graphene
Quantum Dots from Oxidized Debris of Graphene Oxide”, J. Mater.
Chem. B 2013, 1, 39–42.
[17] M. Li, W. Wu, W. Ren, H.-M. Cheng, N.Tang, W. Zhong, Y. Du,
“Synthesis and Upconversion Luminescence of N-Doped Graphene
Quantum Dots”, Appl. Phys. Lett. 2012, 101, 103107.
[18] L. B. Tang, R. B. Ji, X. M. Li, K. S. Teng, S. P. Lau, “ Energy-level
Structure of Nitrogen-doped Graphene Quantum Dots”, J. Mater. Chem.
C, 2013, 1, 4908.
[19] L. B. Tang, R. B. Ji, X. M. Li, G. X. Bai, C. P. Liu, J. H. Hao, J. Y. Lin, H.
X. Jiang, K. S. Teng, Z. B. Yang, S. P. Lau, “Deep Ultraviolet to
Near-infrared Emission and Photoresponse in Layered N-Doped
Graphene Quantum Dots” ACS Nano, 2014, 8(6), 6312-6320.
[20] L. B. Tang, R. B. Ji, X. K. Cao, J. Y. Lin, H. X. Jiang, K. S. Teng, C. M.
Luk, S. Zeng, J. H. Hao, S. P. Lau, Deep Ultraviolet Photoluminescence
of Water-Soluble Self-Passivated Graphene Quantum Dots”, ACS Nano,
2012, 6, 5102-5110.
[21] L. B. Tang, R. B. Ji, X. M. Li, K. S. Teng, S. P. Lau, “Size-dependent
Structural and Optical Characteristics of Glucose-Derived Graphene
Quantum Dots”, Part. Part. Syst. Charact., 2013, 30, 523-531.
[22] C. M. Luk, B. L. Chen, K. S. Teng, L. B. Tang, S. P. Lau, “Optically and
Electrically tunable Graphene Quantum Dots-Polyaniline Composite
Films”, J. Mater. Chem. C, 2014, 2, 4526.
[23] D. Pan, J. Zhang, Z. Li, M. Wu, “Hydrothermal Route for Cutting
Graphene Sheets into Blue-Luminescent Graphene Quantum Dots”, Adv.
Mater., 2010, 22, 734-738.
[24] S. Zhuo, M. Shao, S. T. Lee, “Upconversion and Downconversion
Fluorescent Graphene Quantum Dots: Ultrasonic Preparation and
Photocatalysis”, ACS Nano, 2012, 6 (2), 1059-1064
[25] S. Zhu, J. Zhang, S. Tang, C. Qiao, L. Wang, H. Wang, X. Liu, B. Li, Y.
Li, W. Yu, X. Wang, H. Sun, B. Yang, “Surface Chemistry Routes to
Modulate the Photoluminescence of Graphene Quantum Dots: From
Fluorescence Mechanism to Up-Conversion Bioimaging Applications”,
Adv. Funt. Mater. 2012, 22, 4732-4740.
[26] R. Hoffmann, “Trimethylene and the Addition of Methylene to Ethylene”,
J. Am. Chem. Soc., 90, 1968, 1475.
[27] L. Cao, X. Wang, M. J. Meziani, F. Lu, H. F. Wang, P. G. Luo, Y. Lin, B.
A. Harruff, L. M. Veca, D. Murray, S. Y. Xie, Y. P. Sun, “Carbon Dots
for Multiphoton Bioimaging”, J. Am. Chem. Soc., 2007, 129,
11318-11319.
[28] C. Xu, W. W. Webb, “Measurement of Two-Photon Excitation Cross
Sections of Molecular Fluorophores with Data from 690 to 1050 nm”, J.
Opt. Soc. Am. B 1996, 13, 481−491.
[29] S. H. Jin, D. H. Kim, G. H. Jun, S. H. Hong, S. K. Jeon, “Tuning the
Photoluminescence of Graphene Quantum Dots Through the Charge
Transfer Effect of Functional Groups”, ACS Nano, 2013, 7(2), 1239.
[1] X. Yan, X. Cui, B. S. Li, L. S. Li, “Large, Solution-Processable Graphene
Quantum Dots as Light Absorbers for Photovoltaics”, Nano. Letter, 2010,
10, 1869-1873.
[2] L. A. Ponomarenko, F.Schedin, M. I. Katsnelson, R.Yang, E. W. Hill, K.
S. Novoselov, A. K. Geim, “Chaotic Dirac Billiard in Graphene Quantum
Dots. Science 2008, 320, 356–358.
[3] C. O. Girit, J. C. Meyer, R. Erni, M. D. Rossell, C. Kisielowski, L.Yang,
C. H. Park,; M. F. Crommie,; M. L. Cohen, S. G. Louie,et al. “Graphene
at the Edge: Stability and Dynamics”, Science 2009, 323, 1705–1708.
[4] X. Yan, X. Cui, L. S. Li, “Stable Colloidal Graphene Quantum Dots with
Tunable Size” J. Am. Chem. Soc. 2010, 132, 5944–5945.
[5] C. X. Guo, H. B. Yang, Z. M. Sheng, Z. S. Lu, Q. L. Song, C. M. Li,
“Layered Graphene/Quantum Dots for Photovoltaic Devices”, Angew.
Chem., Int. Ed. 2010, 49, 3014–3017.
[6] C. M. Luk, L. B. Tang, W. F. Zhang, S. F. Yu, K. S. Teng and S. P. Lau,
“An Efficient and Stable Fluorescent Graphene Quantum Dot–Agar
Composite as a Converting Material in White Light Emitting Diodes”, J.
Mater. Chem., 2012, 22, 22378.
[7] V. Gupta, N. Chaudhary, R. Srivastava, G. Datt Sharma, R. Bhardwaj, S.
Chand, “Luminscent Graphene Quantum Dots for Organic Photovoltaic
Devices”, J. Am. Chem. Soc. 2011, 133, 9960–9963.
[8] X. M. Geng, L. Niu, Z. Y. Xing, R. S. Song, G. T. Liu, M. T. Sun, G. S.
Cheng, H. J. Zhong, Z. H. Liu, Z. J. Zhang, et al. “Aqueous-Processable
Noncovalent Chemically Converted GrapheneQuantum Dot Composites
for Flexible and Transparent Optoelectronic Films”, Adv. Mater. 2010,
22,638–642.
[9] S. J. Zhu, J. H. Zhang, C. Y. Qiao, S. J. Tang, Y. F. Li, W. J. Yuan, B.
Li, L. Tian, F. Liu, R. Hu, et al. “Strongly Green-Photoluminescent
Graphene Quantum Dots for Bioimaging Applications”, Chem.
Commun. 2011, 47, 6858– 6860.
[10] L. Ma, H. Hu, L. Y. Zhu, J. H. Wang, “Boron and Nitrogen Doping
Induced Half-Metallicity in Zigzag Triwing Graphene Nanoribbons”, J.
Phys. Chem. C, 2011, 115, 6195.
[11] K. P. Gong, F. Du, Z. H. Xia, M. Durstock, L. M. Dai, “Nitrogen-Doped
Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen
Reduction”, Science 2009, 323, 760.
[12] D. S. Yu, Q. Zhang, L. M. Dai, “Highly Efficient Metal-Free Growth of
Nitrogen-Doped Single-Walled Carbon Nanotubes on Plasma-Etched
Substrates for Oxygen Reduction”, J. Am. Chem. Soc. 2010, 132, 15127.
[13] M. Deifallah, P. F. McMillan, F. J. Cora, “Electronic and Structural
Properties of Two-Dimensional Carbon Nitride Graphenes”, Phys. Chem.
C 2008, 112, 5447.
[14] Y. Li, Y. Zhao, H. Cheng, Y. Hu, G. Shi,; L. Dai, L. Qu, “Nitrogen-Doped
Graphene Quantum Dots with Oxygen-Rich Functional Groups”, J. Am.
Chem. Soc. 2012, 134, 15–18.
[15] Q. Li, S. Zhang, L. Dai, L.-S. Li, “Nitrogen-Doped Colloidal Graphene
Quantum Dots and Their Size-Dependent Electrocatalytic Activity for the
Oxygen Reduction Reaction”, J. Am. Chem. Soc. 2012, 134,
18932–18935.
[16] C. Hu, Y. Liu, Y. Yang, J. Cui, Z. Huang, Y. Wang, L. Yang, H. Wang, Y.
Xiao, J. Rong, “One-Step Preparation of Nitrogen- Doped Graphene
Quantum Dots from Oxidized Debris of Graphene Oxide”, J. Mater.
Chem. B 2013, 1, 39–42.
[17] M. Li, W. Wu, W. Ren, H.-M. Cheng, N.Tang, W. Zhong, Y. Du,
“Synthesis and Upconversion Luminescence of N-Doped Graphene
Quantum Dots”, Appl. Phys. Lett. 2012, 101, 103107.
[18] L. B. Tang, R. B. Ji, X. M. Li, K. S. Teng, S. P. Lau, “ Energy-level
Structure of Nitrogen-doped Graphene Quantum Dots”, J. Mater. Chem.
C, 2013, 1, 4908.
[19] L. B. Tang, R. B. Ji, X. M. Li, G. X. Bai, C. P. Liu, J. H. Hao, J. Y. Lin, H.
X. Jiang, K. S. Teng, Z. B. Yang, S. P. Lau, “Deep Ultraviolet to
Near-infrared Emission and Photoresponse in Layered N-Doped
Graphene Quantum Dots” ACS Nano, 2014, 8(6), 6312-6320.
[20] L. B. Tang, R. B. Ji, X. K. Cao, J. Y. Lin, H. X. Jiang, K. S. Teng, C. M.
Luk, S. Zeng, J. H. Hao, S. P. Lau, Deep Ultraviolet Photoluminescence
of Water-Soluble Self-Passivated Graphene Quantum Dots”, ACS Nano,
2012, 6, 5102-5110.
[21] L. B. Tang, R. B. Ji, X. M. Li, K. S. Teng, S. P. Lau, “Size-dependent
Structural and Optical Characteristics of Glucose-Derived Graphene
Quantum Dots”, Part. Part. Syst. Charact., 2013, 30, 523-531.
[22] C. M. Luk, B. L. Chen, K. S. Teng, L. B. Tang, S. P. Lau, “Optically and
Electrically tunable Graphene Quantum Dots-Polyaniline Composite
Films”, J. Mater. Chem. C, 2014, 2, 4526.
[23] D. Pan, J. Zhang, Z. Li, M. Wu, “Hydrothermal Route for Cutting
Graphene Sheets into Blue-Luminescent Graphene Quantum Dots”, Adv.
Mater., 2010, 22, 734-738.
[24] S. Zhuo, M. Shao, S. T. Lee, “Upconversion and Downconversion
Fluorescent Graphene Quantum Dots: Ultrasonic Preparation and
Photocatalysis”, ACS Nano, 2012, 6 (2), 1059-1064
[25] S. Zhu, J. Zhang, S. Tang, C. Qiao, L. Wang, H. Wang, X. Liu, B. Li, Y.
Li, W. Yu, X. Wang, H. Sun, B. Yang, “Surface Chemistry Routes to
Modulate the Photoluminescence of Graphene Quantum Dots: From
Fluorescence Mechanism to Up-Conversion Bioimaging Applications”,
Adv. Funt. Mater. 2012, 22, 4732-4740.
[26] R. Hoffmann, “Trimethylene and the Addition of Methylene to Ethylene”,
J. Am. Chem. Soc., 90, 1968, 1475.
[27] L. Cao, X. Wang, M. J. Meziani, F. Lu, H. F. Wang, P. G. Luo, Y. Lin, B.
A. Harruff, L. M. Veca, D. Murray, S. Y. Xie, Y. P. Sun, “Carbon Dots
for Multiphoton Bioimaging”, J. Am. Chem. Soc., 2007, 129,
11318-11319.
[28] C. Xu, W. W. Webb, “Measurement of Two-Photon Excitation Cross
Sections of Molecular Fluorophores with Data from 690 to 1050 nm”, J.
Opt. Soc. Am. B 1996, 13, 481−491.
[29] S. H. Jin, D. H. Kim, G. H. Jun, S. H. Hong, S. K. Jeon, “Tuning the
Photoluminescence of Graphene Quantum Dots Through the Charge
Transfer Effect of Functional Groups”, ACS Nano, 2013, 7(2), 1239.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:68554", author = "Chi Man Luk and Ming Kiu Tsang and Chi Fan Chan and Shu Ping Lau", title = "Two-Photon Fluorescence in N-Doped Graphene Quantum Dots", abstract = "Nitrogen-doped graphene quantum dots (N-GQDs)
were fabricated by microwave-assisted hydrothermal technique. The
optical properties of the N-GQDs were studied. The luminescence of
the N-GQDs can be tuned by varying the excitation wavelength.
Furthermore, two-photon luminescence of the N-GQDs excited by
near-infrared laser can be obtained. It is shown that N-doping play a
key role on two-photon luminescence. The N-GQDs are expected to
find application in biological applications including bioimaging and
sensing.
", keywords = "Graphene quantum dots, nitrogen doping,
photoluminescence, two-photon fluorescence.", volume = "8", number = "12", pages = "1387-4", }
