Abstract

Black phosphorous (BP), the most thermodynamically stable allotrope of phosphorus, is a high-mobility layered semiconductor with direct band-gap determined by the number of layers from 0.3 eV (bulk) to 2.0 eV (single layer). Therefore, BP is considered as a natural candidate for broadband optical applications, particularly in the infrared (IR) and mid-IR part of the spectrum. The strong light-matter interaction, narrow direct band-gap, and wide range of tunable optical response make BP as a promising nonlinear optical material, particularly with great potentials for infrared and mid-infrared opto-electronics. Herein, we experimentally verified its broadband and enhanced saturable absorption of multi-layer BP (with a thickness of ~10 nm) by wide-band Z-scan measurement technique, and anticipated that multi-layer BPs could be developed as another new type of two-dimensional saturable absorber with operation bandwidth ranging from the visible (400 nm) towards mid-IR (at least 1930 nm). Our results might suggest that ultra-thin multi-layer BP films could be potentially developed as broadband ultra-fast photonics devices, such as passive Q-switcher, mode-locker, optical switcher etc.

© 2015 Optical Society of America

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References

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2014 (26)

H. O. H. Churchill and P. Jarillo-Herrero, “Two-dimensional crystals: Phosphorus joins the family,” Nat. Nanotechnol. 9(5), 330–331 (2014).
[Crossref] [PubMed]

K. Wang, Y. Feng, C. Chang, J. Zhan, C. Wang, Q. Zhao, J. N. Coleman, L. Zhang, W. J. Blau, and J. Wang, “Broadband ultrafast nonlinear absorption and nonlinear refraction of layered molybdenum dichalcogenide semiconductors,” Nanoscale 6(18), 10530–10535 (2014).
[Crossref] [PubMed]

S. Wang, H. Yu, H. Zhang, A. Wang, M. Zhao, Y. Chen, L. Mei, and J. Wang, “Broadband few-layer MoS2 saturable absorbers,” Adv. Mater. 26(21), 3538–3544 (2014).
[Crossref] [PubMed]

L. Tao, H. Long, B. Zhou, S. F. Yu, S. P. Lau, Y. Chai, K. H. Fung, Y. H. Tsang, J. Yao, and D. Xu, “Preparation and characterization of few-layer MoS2 nanosheets and their good nonlinear optical responses in the PMMA matrix,” Nanoscale 6(16), 9713–9719 (2014).
[Crossref] [PubMed]

D. J. Clark, V. Senthilkumar, C. T. Le, D. L. Weerawarne, B. Shim, J. I. Jang, J. H. Shim, J. Cho, Y. Sim, M. J. Seong, S. H. Rhim, A. J. Freeman, K. H. Chung, and Y. S. Kim, “Strong optical nonlinearity of CVD-grown MoS2 monolayer as probed by wavelength-dependent second-harmonic generation,” Phys. Rev. B 90(12), 121409 (2014).
[Crossref]

J. Du, Q. Wang, G. Jiang, C. Xu, C. Zhao, Y. Xiang, Y. Chen, S. Wen, and H. Zhang, “Ytterbium-doped fiber laser passively mode locked by few-layer Molybdenum Disulfide (MoS2) saturable absorber functioned with evanescent field interaction,” Sci. Rep. 4, 6346 (2014).
[Crossref] [PubMed]

L. Li, Y. Yu, G. J. Ye, Q. Ge, X. Ou, H. Wu, D. Feng, X. H. Chen, and Y. Zhang, “Black phosphorus field-effect transistors,” Nat. Nanotechnol. 9(5), 372–377 (2014).
[Crossref] [PubMed]

H. Liu, A. T. Neal, Z. Zhu, Z. Luo, X. Xu, D. Tománek, and P. D. Ye, “Phosphorene: an unexplored 2D semiconductor with a high hole mobility,” ACS Nano 8(4), 4033–4041 (2014).
[Crossref] [PubMed]

S. P. Koenig, R. A. Doganov, H. Schmidt, A. H. C. Neto, and B. Özyilmaz, “Electric field effect in ultrathin black phosphorus,” Appl. Phys. Lett. 104(10), 103106 (2014).
[Crossref]

M. Buscema, D. J. Groenendijk, S. I. Blanter, G. A. Steele, H. S. van der Zant, and A. Castellanos-Gomez, “Fast and broadband photoresponse of few-layer black phosphorus field-effect transistors,” Nano Lett. 14(6), 3347–3352 (2014).
[Crossref] [PubMed]

F. Xia, H. Wang, and Y. Jia, “Rediscovering black phosphorus as an anisotropic layered material for optoelectronics and electronics,” Nat. Commun. 5, 4458 (2014).
[Crossref] [PubMed]

T. Hong, B. Chamlagain, W. Lin, H. J. Chuang, M. Pan, Z. Zhou, and Y. Q. Xu, “Polarized photocurrent response in black phosphorus field-effect transistors,” Nanoscale 6(15), 8978–8983 (2014).
[Crossref] [PubMed]

J. Dai and X. C. Zeng, “Bilayer phosphorene: effect of stacking order on bandgap and its potential applications in thin-film solar cells,” J. Phys. Chem. Lett. 5(7), 1289–1293 (2014).
[Crossref]

Y. Deng, Z. Luo, N. J. Conrad, H. Liu, Y. Gong, S. Najmaei, P. M. Ajayan, J. Lou, X. Xu, and P. D. Ye, “Black phosphorus-monolayer MoS2 van der Waals heterojunction p-n diode,” ACS Nano 8(8), 8292–8299 (2014).
[Crossref] [PubMed]

X. Peng, Q. Wei, and A. Copple, “Strain-engineered direct-indirect band gap transition and its mechanism in two-dimensional phosphorene,” Phys. Rev. B 90(8), 085402 (2014).
[Crossref]

A. S. Rodin, A. Carvalho, and A. H. Castro Neto, “Strain-induced gap modification in black phosphorus,” Phys. Rev. Lett. 112(17), 176801 (2014).
[Crossref] [PubMed]

Q. Wei and X. Peng, “Superior mechanical flexibility of phosphorene and few-layer black phosphorus,” Appl. Phys. Lett. 104(25), 251915 (2014).
[Crossref]

F. Bonaccorso and Z. Sun, “Solution processing of graphene, topological insulators and other 2d crystals for ultrafast photonics,” Opt. Mater. Express 4(1), 63–78 (2014).
[Crossref]

S. Chen, C. Zhao, Y. Li, H. Huang, S. Lu, H. Zhang, and S. Wen, “Broadband optical and microwave nonlinear response in topological insulator,” Opt. Mater. Express 4(4), 587–596 (2014).
[Crossref]

H. Zhang, S. B. Lu, J. Zheng, J. Du, S. C. Wen, D. Y. Tang, and K. P. Loh, “Molybdenum disulfide (MoS₂) as a broadband saturable absorber for ultra-fast photonics,” Opt. Express 22(6), 7249–7260 (2014).
[PubMed]

H. Xia, H. Li, C. Lan, C. Li, X. Zhang, S. Zhang, and Y. Liu, “Ultrafast erbium-doped fiber laser mode-locked by a CVD-grown molybdenum disulfide (MoS2) saturable absorber,” Opt. Express 22(14), 17341–17348 (2014).
[Crossref] [PubMed]

H. Liu, A. P. Luo, F. Z. Wang, R. Tang, M. Liu, Z. C. Luo, W. C. Xu, C. J. Zhao, and H. Zhang, “Femtosecond pulse erbium-doped fiber laser by a few-layer MoS2 saturable absorber,” Opt. Lett. 39(15), 4591–4594 (2014).
[Crossref] [PubMed]

M. Liu, X.-W. Zheng, Y.-L. Qi, H. Liu, A.-P. Luo, Z.-C. Luo, W.-C. Xu, C.-J. Zhao, and H. Zhang, “Microfiber-based few-layer MoS2 saturable absorber for 2.5 GHz passively harmonic mode-locked fiber laser,” Opt. Express 22(19), 22841–22846 (2014).
[Crossref] [PubMed]

R. Khazaeizhad, S. H. Kassani, H. Jeong, D. I. Yeom, and K. Oh, “Mode-locking of Er-doped fiber laser using a multilayer MoS2 thin film as a saturable absorber in both anomalous and normal dispersion regimes,” Opt. Express 22(19), 23732–23742 (2014).
[Crossref] [PubMed]

Z. Luo, Y. Huang, M. Zhong, Y. Li, J. Wu, B. Xu, H. Xu, Z. Cai, J. Peng, and J. Weng, “1-, 1.5-, and 2-μm fiber lasers Q-switched by a broadband few-Layer MoS2 saturable absorber,” J. Lightwave Technol. 32(24), 4077–4084 (2014).
[Crossref]

A. C. Gomez, L. Vicarelli, E. Prada, J. O. Island, K. L. N. Acharya, S. I. Blanter, D. J. Groenendijk, M. Buscema, G. A. Steele, J. V. Alvarez, H. W. Zandbergen, J. J. Palacios, and H. S. J. Zant, “Isolation and characterization of few-layer black phosphorus,” 2D Materials 1(2), 025001 (2014).

2013 (2)

K. Wang, J. Wang, J. Fan, M. Lotya, A. O’Neill, D. Fox, Y. Feng, X. Zhang, B. Jiang, Q. Zhao, H. Zhang, J. N. Coleman, L. Zhang, and W. J. Blau, “Ultrafast saturable absorption of two-dimensional MoS2 nanosheets,” ACS Nano 7(10), 9260–9267 (2013).
[Crossref] [PubMed]

M. Xu, T. Liang, M. Shi, and H. Chen, “Graphene-like two-dimensional materials,” Chem. Rev. 113(5), 3766–3798 (2013).
[Crossref] [PubMed]

2012 (4)

C. Ataca, H. Sahin, and S. Ciraci, “Stable, single-layer MX2 transition-netal oxides and dichalcogenides in a honeycomb-like structure,” J. Phys. Chem. C 116(16), 8983–8999 (2012).
[Crossref]

S. Thongrattanasiri, F. H. L. Koppens, and F. J. García de Abajo, “Complete optical absorption in periodically patterned graphene,” Phys. Rev. Lett. 108(4), 047401 (2012).
[Crossref] [PubMed]

M. Furchi, A. Urich, A. Pospischil, G. Lilley, K. Unterrainer, H. Detz, P. Klang, A. M. Andrews, W. Schrenk, G. Strasser, and T. Mueller, “Microcavity-integrated graphene photodetector,” Nano Lett. 12(6), 2773–2777 (2012).
[Crossref] [PubMed]

M. Engel, M. Steiner, A. Lombardo, A. C. Ferrari, H. V. Löhneysen, P. Avouris, and R. Krupke, “Light-matter interaction in a microcavity-controlled graphene transistor,” Nat. Commun. 3, 906 (2012).
[Crossref] [PubMed]

2011 (4)

F. H. L. Koppens, D. E. Chang, and F. J. García de Abajo, “Graphene plasmonics: a platform for strong light-matter interactions,” Nano Lett. 11(8), 3370–3377 (2011).
[Crossref] [PubMed]

A. H. C. Neto and K. Novoselov, “Two-dimensional crystals: beyond graphene,” Mater. Express 1(1), 10–17 (2011).
[Crossref]

R. Mas-Ballesté, C. Gómez-Navarro, J. Gómez-Herrero, and F. Zamora, “2D materials: to graphene and beyond,” Nanoscale 3(1), 20–30 (2011).
[Crossref] [PubMed]

J. N. Coleman, M. Lotya, A. O’Neill, S. D. Bergin, P. J. King, U. Khan, K. Young, A. Gaucher, S. De, R. J. Smith, I. V. Shvets, S. K. Arora, G. Stanton, H.-Y. Kim, K. Lee, G. T. Kim, G. S. Duesberg, T. Hallam, J. J. Boland, J. J. Wang, J. F. Donegan, J. C. Grunlan, G. Moriarty, A. Shmeliov, R. J. Nicholls, J. M. Perkins, E. M. Grieveson, K. Theuwissen, D. W. McComb, P. D. Nellist, and V. Nicolosi, “Two-dimensional nanosheets produced by liquid exfoliation of layered materials,” Science 331(6017), 568–571 (2011).
[Crossref] [PubMed]

2010 (2)

C. Lee, H. Yan, L. E. Brus, T. F. Heinz, J. Hone, and S. Ryu, “Anomalous lattice vibrations of single- and few-layer MoS2,” ACS Nano 4(5), 2695–2700 (2010).
[Crossref] [PubMed]

F. Bonaccorso, Z. Sun, T. Hasan, and A. C. Ferrari, “Graphene photonics and optoelectronics,” Nat. Photonics 4(9), 611–622 (2010).
[Crossref]

2009 (1)

Q. Bao, H. Zhang, Y. Wang, Z. Ni, Y. Yan, Z. X. Shen, K. P. Loh, and D. Y. Tang, “Atomic-layer graphene as a saturable absorber for ultrafast pulsed lasers,” Adv. Funct. Mater. 19(19), 3077–3083 (2009).
[Crossref]

2007 (1)

A. K. Geim and K. S. Novoselov, “The rise of graphene,” Nat. Mater. 6(3), 183–191 (2007).
[Crossref] [PubMed]

2000 (1)

E. Garmire, “Resonant optical nonlinearities in semiconductors,” IEEE J. Sel. Top. Quantum Electron. 6(6), 1094–1110 (2000).
[Crossref]

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M. Buscema, D. J. Groenendijk, S. I. Blanter, G. A. Steele, H. S. van der Zant, and A. Castellanos-Gomez, “Fast and broadband photoresponse of few-layer black phosphorus field-effect transistors,” Nano Lett. 14(6), 3347–3352 (2014).
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F. H. L. Koppens, D. E. Chang, and F. J. García de Abajo, “Graphene plasmonics: a platform for strong light-matter interactions,” Nano Lett. 11(8), 3370–3377 (2011).
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T. Hong, B. Chamlagain, W. Lin, H. J. Chuang, M. Pan, Z. Zhou, and Y. Q. Xu, “Polarized photocurrent response in black phosphorus field-effect transistors,” Nanoscale 6(15), 8978–8983 (2014).
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K. Wang, Y. Feng, C. Chang, J. Zhan, C. Wang, Q. Zhao, J. N. Coleman, L. Zhang, W. J. Blau, and J. Wang, “Broadband ultrafast nonlinear absorption and nonlinear refraction of layered molybdenum dichalcogenide semiconductors,” Nanoscale 6(18), 10530–10535 (2014).
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J. N. Coleman, M. Lotya, A. O’Neill, S. D. Bergin, P. J. King, U. Khan, K. Young, A. Gaucher, S. De, R. J. Smith, I. V. Shvets, S. K. Arora, G. Stanton, H.-Y. Kim, K. Lee, G. T. Kim, G. S. Duesberg, T. Hallam, J. J. Boland, J. J. Wang, J. F. Donegan, J. C. Grunlan, G. Moriarty, A. Shmeliov, R. J. Nicholls, J. M. Perkins, E. M. Grieveson, K. Theuwissen, D. W. McComb, P. D. Nellist, and V. Nicolosi, “Two-dimensional nanosheets produced by liquid exfoliation of layered materials,” Science 331(6017), 568–571 (2011).
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Y. Deng, Z. Luo, N. J. Conrad, H. Liu, Y. Gong, S. Najmaei, P. M. Ajayan, J. Lou, X. Xu, and P. D. Ye, “Black phosphorus-monolayer MoS2 van der Waals heterojunction p-n diode,” ACS Nano 8(8), 8292–8299 (2014).
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J. N. Coleman, M. Lotya, A. O’Neill, S. D. Bergin, P. J. King, U. Khan, K. Young, A. Gaucher, S. De, R. J. Smith, I. V. Shvets, S. K. Arora, G. Stanton, H.-Y. Kim, K. Lee, G. T. Kim, G. S. Duesberg, T. Hallam, J. J. Boland, J. J. Wang, J. F. Donegan, J. C. Grunlan, G. Moriarty, A. Shmeliov, R. J. Nicholls, J. M. Perkins, E. M. Grieveson, K. Theuwissen, D. W. McComb, P. D. Nellist, and V. Nicolosi, “Two-dimensional nanosheets produced by liquid exfoliation of layered materials,” Science 331(6017), 568–571 (2011).
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J. N. Coleman, M. Lotya, A. O’Neill, S. D. Bergin, P. J. King, U. Khan, K. Young, A. Gaucher, S. De, R. J. Smith, I. V. Shvets, S. K. Arora, G. Stanton, H.-Y. Kim, K. Lee, G. T. Kim, G. S. Duesberg, T. Hallam, J. J. Boland, J. J. Wang, J. F. Donegan, J. C. Grunlan, G. Moriarty, A. Shmeliov, R. J. Nicholls, J. M. Perkins, E. M. Grieveson, K. Theuwissen, D. W. McComb, P. D. Nellist, and V. Nicolosi, “Two-dimensional nanosheets produced by liquid exfoliation of layered materials,” Science 331(6017), 568–571 (2011).
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M. Engel, M. Steiner, A. Lombardo, A. C. Ferrari, H. V. Löhneysen, P. Avouris, and R. Krupke, “Light-matter interaction in a microcavity-controlled graphene transistor,” Nat. Commun. 3, 906 (2012).
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K. Wang, J. Wang, J. Fan, M. Lotya, A. O’Neill, D. Fox, Y. Feng, X. Zhang, B. Jiang, Q. Zhao, H. Zhang, J. N. Coleman, L. Zhang, and W. J. Blau, “Ultrafast saturable absorption of two-dimensional MoS2 nanosheets,” ACS Nano 7(10), 9260–9267 (2013).
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L. Li, Y. Yu, G. J. Ye, Q. Ge, X. Ou, H. Wu, D. Feng, X. H. Chen, and Y. Zhang, “Black phosphorus field-effect transistors,” Nat. Nanotechnol. 9(5), 372–377 (2014).
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K. Wang, Y. Feng, C. Chang, J. Zhan, C. Wang, Q. Zhao, J. N. Coleman, L. Zhang, W. J. Blau, and J. Wang, “Broadband ultrafast nonlinear absorption and nonlinear refraction of layered molybdenum dichalcogenide semiconductors,” Nanoscale 6(18), 10530–10535 (2014).
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F. Bonaccorso, Z. Sun, T. Hasan, and A. C. Ferrari, “Graphene photonics and optoelectronics,” Nat. Photonics 4(9), 611–622 (2010).
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K. Wang, J. Wang, J. Fan, M. Lotya, A. O’Neill, D. Fox, Y. Feng, X. Zhang, B. Jiang, Q. Zhao, H. Zhang, J. N. Coleman, L. Zhang, and W. J. Blau, “Ultrafast saturable absorption of two-dimensional MoS2 nanosheets,” ACS Nano 7(10), 9260–9267 (2013).
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D. J. Clark, V. Senthilkumar, C. T. Le, D. L. Weerawarne, B. Shim, J. I. Jang, J. H. Shim, J. Cho, Y. Sim, M. J. Seong, S. H. Rhim, A. J. Freeman, K. H. Chung, and Y. S. Kim, “Strong optical nonlinearity of CVD-grown MoS2 monolayer as probed by wavelength-dependent second-harmonic generation,” Phys. Rev. B 90(12), 121409 (2014).
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L. Tao, H. Long, B. Zhou, S. F. Yu, S. P. Lau, Y. Chai, K. H. Fung, Y. H. Tsang, J. Yao, and D. Xu, “Preparation and characterization of few-layer MoS2 nanosheets and their good nonlinear optical responses in the PMMA matrix,” Nanoscale 6(16), 9713–9719 (2014).
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M. Furchi, A. Urich, A. Pospischil, G. Lilley, K. Unterrainer, H. Detz, P. Klang, A. M. Andrews, W. Schrenk, G. Strasser, and T. Mueller, “Microcavity-integrated graphene photodetector,” Nano Lett. 12(6), 2773–2777 (2012).
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E. Garmire, “Resonant optical nonlinearities in semiconductors,” IEEE J. Sel. Top. Quantum Electron. 6(6), 1094–1110 (2000).
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J. N. Coleman, M. Lotya, A. O’Neill, S. D. Bergin, P. J. King, U. Khan, K. Young, A. Gaucher, S. De, R. J. Smith, I. V. Shvets, S. K. Arora, G. Stanton, H.-Y. Kim, K. Lee, G. T. Kim, G. S. Duesberg, T. Hallam, J. J. Boland, J. J. Wang, J. F. Donegan, J. C. Grunlan, G. Moriarty, A. Shmeliov, R. J. Nicholls, J. M. Perkins, E. M. Grieveson, K. Theuwissen, D. W. McComb, P. D. Nellist, and V. Nicolosi, “Two-dimensional nanosheets produced by liquid exfoliation of layered materials,” Science 331(6017), 568–571 (2011).
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L. Li, Y. Yu, G. J. Ye, Q. Ge, X. Ou, H. Wu, D. Feng, X. H. Chen, and Y. Zhang, “Black phosphorus field-effect transistors,” Nat. Nanotechnol. 9(5), 372–377 (2014).
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M. Sheik-Bahae, A. A. Said, T.-H. Wei, D. J. Hagan, and E. W. Van Stryland, “Sensitive measurement of optical nonlinearities using a single beam,” IEEE J. Quantum Electron. 26(4), 760–769 (1990).
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Figures (8)

Fig. 1
Fig. 1 The preparation process of BP nanoplatelets.
Fig. 2
Fig. 2 (a) SEM image of BP crystal; (b) XRD pattern of BP powder; (c) TEM and (d) High-resolution TEM images of as-prepared BP nanoplatelets, the inset image is the FFT of the image d.
Fig. 3
Fig. 3 (a) 2D topographical AFM image of BP NPs; (b) Height Profiles of the sections marked in (a); (c) and (d) are the histograms of thickness and width of the BP NPs, respectively.
Fig. 4
Fig. 4 (a) Raman spectrum of the multi-layer BP NPs; (b) The linear absorption spectrum of the multi-layer BP NPs.
Fig. 5
Fig. 5 (a) and (b) are the open aperture Z-scan measurements of BP NPs dispersions under different intensities at 400 nm and 800 nm, respectively; (c) Relation between normalized transmittance and input intensity for BP NPs dispersions at 800 nm; (d) The open aperture Z-scan measurements of BP NPs dispersions in IPA, NMP and EA at intensities of 515 GW/cm2.
Fig. 6
Fig. 6 (a) The open aperture Z-scan measurements of BP-PMMA on quartz at peak intensity of 4.1 MW/cm2 and (b) relation between normalized transmittance and intensity at 1563 nm band.
Fig. 7
Fig. 7 (a) The open aperture Z-scan measurement of BP-PMMA on quartz at peak intensity of 0.66 MW/cm2 and (b) relation between normalized transmittance and intensity at 1930 nm band.
Fig. 8
Fig. 8 The schematic diagram of the saturable absorption in multi-layer BP NPs.

Tables (1)

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Table 1 Linear and Nonlinear Optical Parameters of the BP dispersions

Equations (2)

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T(z)= m=0 ( α NL I 0 L eff ) m (1+ z 2 / z 0 2 ) m (m+1) 3/2 1 α NL I 0 L eff 2 2 1 (1+ z 2 / z 0 2 )
T=1 α s 1+I/ I s α ns

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