Fundamentals and applications of phosphorus nanomaterials

Fundamentals and Applications of Phosphorus Nanomaterials......Page 2
 Fundamentals and Applications of Phosphorus Nanomaterials......Page 4
  Library of Congress Cataloging-in-Publication Data......Page 5
Foreword......Page 6
Subject Index......Page 8
 Figure 1. The structures of phosphorus allotropes.......Page 10
Synthesis of Red and Black Phosphorus Nanomaterials......Page 12
 Mechanical Methods......Page 13
 Thermal Growth Strategies......Page 14
  Figure 3. (a) Schematic figure of one example of the vaporization-condensation synthesis method: red phosphorus nanodots on reduced graphene oxide 13. Reproduced with permission from reference 13. Copyright 2017 American Chemical Society. Nanomaterials synthesized by the vaporization-condensation method: (b) SEM image of the red phosphorus-carbon nanotube composite 15. Reproduced with permission from reference 15. Copyright 2014 American Chemical Society. (c) SEM image of the red phosphorus-porous carbon nanofiber composite 16. Reprinted from Li, W.; Yang, Z.; Jiang, Y.; Yu, Z.; Gu, L.; Yu, Y. Crystalline red phosphorus incorporated with porous carbon nanofibers as flexible electrode for high performance lithium-ion batteries. Carbon 2014, 78, 455-462, Copyright 2014, with permission from Elsevier. (d) TEM image of the phosphorus-metal organic framework 18. Reproduced with permission from reference 18. Copyright 2017 John Wiley and Sons.......Page 16
  Figure 4. (a) High-resolution TEM image and selected area diffraction pattern of the fibrous red phosphorus synthesized with iodine as a catalyst 19. Reproduced with permission from reference 19. Copyright 2005 John Wiley and Sons. (b) Crystalline red phosphorus synthesized by heating amorphous phosphorus under vacuum 21. Reprinted from Wang, F.; Ng, W. K. H.; Jimmy, C. Y.; Zhu, H.; Li, C.; Zhang, L.; Liu, Z.; Li, Q. Red phosphorus: an elemental photocatalyst for hydrogen formation from water. Appl. Catal., B 2012, 111, 409-414, Copyright 2012, with permission from Elsevier. (c) SEM image of the crystalline red phosphorus nanorods synthesized on the bismuth-doped silicon wafer 23. Reproduced with permission from reference 23. Copyright 2009 John Wiley and Sons. (d) SEM image of the Hittorf’s phosphorus microbelt synthesized with the assistance of bismuth nanodroplet 24. Reprinted from Liu, Y.; Hu, Z.; Jimmy, C. Y. Liquid bismuth initiated growth of phosphorus microbelts with efficient charge polarization for photocatalysis. Appl. Catal., B 2019, 247, 100-106, Copyright 2019, with permission from Elsevier.......Page 17
  Figure 5. (a) SEM image of the iodine doped red phosphorus nanosphere 25. Reproduced with permission from reference 25. Copyright 2017 American Chemical Society. (b) TEM image of the porous red phosphorus nanoparticles on graphene 26. Reproduced with permission from reference 26. Copyright 2018 American Chemical Society. (c) TEM image of the red phosphorus hollow sphere synthesized through the solution route 27. Reproduced with permission from reference 27. Reproduced with permission from reference 27. Copyright 2017 John Wiley and Sons.......Page 18
  Figure 6. Optical image of the low-pressure transport route synthesized large black phosphorus single crystals in a silica ampoule, where areas marked with 1, 2 and 3 represent the bulk precursor residue, violet phosphorus and the black phosphorus as the main product, respectively 38. Reprinted from Nilges, T.; Kersting, M.; Pfeifer, T. A fast low-pressure transport route to large black phosphorus single crystals. J. Solid State Chem. 2008, 181 (8), 1707-1711, Copyright 2008, with permission from Elsevier.......Page 19
  Figure 7. (a) AFM images of a piece of black phosphorus flake obtained immediately after cleaving (left) and after exposure to air for 3 days (right) 40. Reprinted by permission from Springer Nature Customer Service Centre GmbH: Springer Nature, Nature Nanotechnology, Li, L.; Yu, Y.; Ye, G. J.; Ge, Q.; Ou, X.; Wu, H.; Feng, D.; Chen, X. H.; Zhang, Y. Black phosphorus field-effect transistors. Nat. Nanotechnol. 2014, 9 (5), 372. Copyright 2014.. (b) Optical image of multilayered phosphorene after Ar+ plasma thinning. Scale bar is 5 μm 43. Reprinted by permission from Springer Nature Customer Service Centre GmbH: Springer Nature, Nano Research, Lu, W.; Nan, H.; Hong, J.; Chen, Y.; Zhu, C.; Liang, Z.; Ma, X.; Ni, Z.; Jin, C.; Zhang, Z. Plasma-assisted fabrication of monolayer phosphorene and its Raman characterization. Nano Res. 2014, 7 (6), 853-859. Copyright 2014.......Page 20
  Figure 8. (a) Schematic diagram of the solvent exfoliation of black phosphorus in various solvents via tip ultrasonication 47. Reproduced with permission from reference 47. Copyright 2015 American Chemical Society. (b) Optical photograph of solvent-exfoliated black phosphorus dispersions in NMP solvent with various centrifugation conditions (1: as-prepared, 2:500 rpm, 3:5000 rpm, 4:10000 rpm, and 5:15000 rpm) 47. Reproduced with permission from reference 47. Copyright 2015 American Chemical Society. (c) Concentration of black phosphorus dispersions from part (b) 47. Reproduced with permission from reference 47. Copyright 2015 American Chemical Society. (d) AFM height profile of black phosphorus nanosheets in (b). Black phosphorus solution was deposited onto a 300 Si substrate with 300nm SiO2 for measurement. The heights are 1:16, 2:40, 3:29, and 4:128 nm 47. Reproduced with permission from reference 47. Copyright 2015 American Chemical Society. (e) and (f) Preparation diagram and TEM characterization of liquid exfoliated black phosphorus quantum dots 50. Reproduced with permission from reference 50. Copyright 2015 John Wiley and Sons.......Page 22
  Figure 9. (a) Schematic diagram of the electrochemical exfoliation process of phosphorene using tetrabutylammonium hexafluorophosphate (TBAP) and DMF as the electrolyte 54. Reproduced with permission from reference 54. Copyright 2017 John Wiley and Sons (b) Schematic of the in-situ Raman measurement setup to monitor electrochemical intercalation process of black phosphorus, (left: before intercalation, right: after intercalation) where the cetyl-trimethylammonium bromide (CTAB) and NMP were used as the electrolyte 56. (c) Electrochemical gate current as a function of the applied electrochemical voltage potential, where the inset is the false-color scanning electron microscope (SEM) image of the intercalated black phosphorus transistors with the scale bar of 5 μm 56. Reprinted by permission from Springer Nature Customer Service Centre GmbH: Springer Nature, Nature,Wang, C.; He, Q.; Halim, U.; Liu, Y.; Zhu, E.; Lin, Z.; Xiao, H.; Duan, X.; Feng, Z.; Cheng, R.; Weiss, N.; Ye, G.; Huang, Y. C.; Wu, H.; Cheng, H. C.; Shakir, I.; Liao, L.; Chen, X.; Goddard, W.; Huang, Y.; Duan, X. Monolayer atomic crystal molecular superlattices. Nature 2018, 555, 231-236. Copyright 2018. (d) Optical images of a piece of MoS2 crystal before (left) and after (right) THAB intercalation. The scale bars of 5 mm 57. Reprinted by permission from Springer Nature Customer Service Centre GmbH: Springer Nature, Nature, Lin, Z.; Liu, Y.; Halim, U.; Ding, M.; Liu, Y.; Wang, Y.; Jia, C.; Chen, P.; Duan, X.; Wang, C. Solution-processable 2D semiconductors for high-performance large-area electronics. Nature 2018, 562 (7726), 254. Copyright 2018. (e) AFM image of the exfoliated black phosphorus with the quaternary ammonium intercalation 57. Reprinted by permission from Springer Nature Customer Service Centre GmbH: Springer Nature, Nature, Lin, Z.; Liu, Y.; Halim, U.; Ding, M.; Liu, Y.; Wang, Y.; Jia, C.; Chen, P.; Duan, X.; Wang, C. Solution-processable 2D semiconductors for high-performance large-area electronics. Nature 2018, 562 (7726), 254. Copyright 2018.......Page 23
 Bottom-Up Growth Strategies......Page 24
  Figure 10. (a) Schematic for CVD growth of black phosphorus 59. Republished with permission of IOP Publishing, from Smith, J. B.; Hagaman, D.; Ji, H.-F. Growth of 2D black phosphorus film from chemical vapor deposition. Nanotechnology 2016, 27 (21), 215602. (b) Cross-sectional TEM images of amorphous black phosphorus thin films synthesized by PLD method 60. Reproduced with permission from reference 60. Copyright 2015 John Wiley and Sons. (c) AFM morphology of the black phosphorus quantum dots on silicon substrate synthesized by MBE method 61. Reproduced with permission from reference 61. Copyright 2018 John Wiley and Sons. (d) Height profiles along line 1 and 2, respectively 61. Reproduced with permission from reference 61. Copyright 2018 John Wiley and Sons.......Page 26
 High-Pressure Conversion......Page 27
  Figure 12. (a) TEM image of the ball-milling synthesized black phosphorus-carbon black nanocomposite as a lithium-ion battery electrode material 6. Reproduced with permission from reference 6. Copyright 2007 John Wiley and Sons. (b) Schematic apparatus for the pressurization synthesis of black phosphorus thin film 68. Republished with permission of IOP Publishing, from Li, X.; Deng, B.; Wang, X.; Chen, S.; Vaisman, M.; Karato, S.-i.; Pan, G.; Lee, M. L.; Cha, J.; Wang, H. Synthesis of thin-film black phosphorus on a flexible substrate. 2D Mater. 2015, 2 (3), 031002.. (c) Optical photo of the synthesized black phosphorus thin film on a PET substrate 68. Republished with permission of IOP Publishing, from Li, X.; Deng, B.; Wang, X.; Chen, S.; Vaisman, M.; Karato, S.-i.; Pan, G.; Lee, M. L.; Cha, J.; Wang, H. Synthesis of thin-film black phosphorus on a flexible substrate. 2D Mater. 2015, 2 (3), 031002. (d) Schematic diagram of the synthesis process of the crystalline black phosphorus thin film on a sapphire substrate 69. Reproduced with permission from reference 69. Copyright 2018 John Wiley and Sons.......Page 28
 Other Methods......Page 29
  Figure 13. (a) Schematic diagram of the wet-chemical synthesis of phosphorus nanosheets 71. (b) TEM image of the wet-chemically synthesized polycrystalline holey black phosphorus nanosheets 71. Reproduced with permission from reference 71. Copyright 2016 John Wiley and Sons. Copyright 2016 John Wiley and Sons.......Page 30
  Figure 14. (a) Schematic diagram of the production process of the black phosphorus nanoribbon 72. (b) TEM micrograph of black phosphorus nanoribbon drop-cast from the liquid dispersion shown in the inset, where the scale bar is 10 µm 72. Reprinted by permission from Springer Nature Customer Service Centre GmbH: Springer Nature, Nature, Watts, Mitchell C., Picco, L.; Russell-Pavier, F. S.; Cullen, P. L.; Miller, T. S.; Bartuś, S. P.; Payton, O. D.; Skipper, N. T.; Tileli, V.; Howard, C. A. Production of phosphorene nanoribbons. Nature 2019, 568, 216-220, Copyright 2019.......Page 31
 References......Page 32
 Introduction......Page 38
  Figure 1. Morphologies of different types of red phosphorus. a) and b) crystals believed to belong to red phosphorus type III and type II, respectively, synthesized through heating red phosphorus. Adapted with permission from reference 2. Copyright 1947, American Chemical Society. c) and d) type II phosphorus synthesized from white phosphorus vapor deposition on bismuth-doped silicon wafer, scale bars are 100 μm and 1 μm for b) and c), respectively. Reproduced with permission from reference 11. Copyright 2009, Wiley-VCH. e) wire structures of fibrous red phosphorus synthesized through deposition under vacuum of amorphous red phosphorus. Reproduced with permission from reference 12. Copyright 2014, Royal Society of Chemistry. f) platelets of violet phosphorus. Reproduced with permission from reference 13. Copyright 2014, Royal Society of Chemistry. g) mixture of fibrous phosphorus and violet phosphorus made through reaction between amorphous red phosphorus, tin, tin(IV) iodide, and red phosphorus thin film using an evacuated ampoule, scale bar is 500 μm. Reproduced with permission from reference 14. Copyright 2016, Wiley-VCH. h) fibrous phosphorus synthesized using amorphous red phosphorus and CuCl2 in an evacuated silica ampoule. Reproduced with permission from reference 15. Copyright 2013, Wiley-VCH.......Page 39
  Figure 2. Structural differences between fibrous phosphorus and violet phosphorus. a) crystal structure of fibrous phosphorus with enhanced image depicting the P9, P2 and P8 groups; b) crystal structure of violet phosphorus with enhanced images showing the P9, P2 and P8 groups and how the bonds between groups of cages are made through the P9 group forming and angle of almost 90°. The crystal structure for fibrous phosphorus was obtained from reference 6. and the crystal structure for violet phosphorus was obtained from reference 7. Structures were plotted using VESTA 16.......Page 40
 Characterization of Red Phosphorus Type II......Page 41
 Characterization of Red Phosphorus Type III......Page 42
 Characterization of Fibrous Phosphorus and Violet Phosphorus......Page 43
 Introduction of Black Phosphorus and Phosphorene......Page 44
  Figure 6. Structure of phosphorene showing a) the armchair direction on a sideview; b) zigzag direction on a sideview; c) top view of a single layer with preferred thermal and electrical conductance; d) P-P atomic configuration, with bond angles and bond lengths. Adapted with permission from reference 47. Copyright 2015, American Chemical Society.......Page 46
 Characterization of BP and Phosphorene......Page 47
  Figure 7. Raman, AFM, photoluminescence, and powder XRD characterization of black phosphorus and phosphorene. a) Raman spectra of bulk black phosphorus (green), one-layer phosphorene (blue), and two-layers phosphorene (red). Reproduced with permission from reference 28. Copyright 2014, American Chemical Society. b) Visual representation of the Raman vibrational modes of orthorhombic black phosphorus. Reproduced with permission from reference 60. Copyright 2015, Wiley-VCH. c) Polarization resolved Raman spectra for one-layer phosphorene by laser excitation for different polarization angles. Reproduced with permission from reference 61. Copyright 2015, Springer Nature. d) AFM image of a one-layer phosphorene sheet showing a height of 0.85 nm. Reproduced with permission from reference 28. Copyright 2014, American Chemical Society. e) Photoluminescence spectra for bulk black phosphorus (red) and one-layer phosphorene (blue), the high intensity peak for phosphorene corresponds to its electronic band gap. Reproduced with permission from reference 28. Copyright 2014, American Chemical Society. f) Powder XRD diffractogram of bulk black phosphorus showing the (020), (040), and (060) planes. Reproduced with permission from reference 29. Copyright 2014, Springer Nature. The inset shows the morphology of bulk black phosphorus crystals synthesized through a mineralizer agent process in a sealed ampoule. Reproduced with permission from reference 64 under a Creative Commons License (http://creativecommons.org/licenses/by/4.0).......Page 48
 Phosphorus Vapor......Page 49
 Phosphorus Clusters......Page 50
 References......Page 51
 Introduction......Page 58
  Figure 1. a)-c) Selected AFM scans of three BP flakes in air taken at different times after exfoliation. a) Adapted with permission from 22. Copyright 2015 IOP Publishing Ltd. b) Adapted with permission from 26 under a Creative Commons License (http://creativecommons.org/licenses/by/4.0/). c) Gamage, S.; Li, Z.; Yakovlev, V. S.; Lewis, C.; Wang, H.; Cronin, S. B.; Abate, Y. Nanoscopy of Black Phosphorus Degradation. Adv. Mater. Interfaces 2016, 3 (12), 1600121. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.......Page 59
  Figure 2. a) Integrated intensity of the Ag2 Raman mode as a function of time under different exposure conditions: air, vacuum, O2/H2O mixture and 300 nm thick parylene layer-capped flake in air. The faster decay rate observed in air (5.5 min-1) compared to under the O2/H2O mixture exposure (36 min-1) is due to the photon flux (1.7 × 104 W cm-2 and 1.8 × 103 W cm-2, respectively). Reproduced with permission from 28. Copyright 2015 Springer Nature. b) Transfer characteristics (IVg) of a BP FET device at selected times over the first hour of exposure (curves are offset by 100 nA for clarity). Adapted with permission from 22. Copyright 2015 IOP Publishing Ltd. c) Local sheet resistance maps of a 24 nm thick flake capped by ~3 nm Al2O3 layer. Adapted with permission from 26 under a Creative Commons License (http://creativecommons.org/licenses/by/4.0/). d) F(δ) curves for a 5.3 nm thick BP drumhead in high vacuum and after 3, 7, 11 and 26 h of exposure to ambient conditions. Adapted with permission from 30 under a Creative Commons License (http://creativecommons.org/licenses/by/3.0/).......Page 60
 Passivation Methods: Encapsulation and Functionalization......Page 61
  Figure 3. a) Hole mobility for encapsulated and unencapsulated BP FETs versus ambient exposure time. Reproduced with permission from 25. Copyright 2014 American Chemical Society. b) Sheet resistance maps of a 16 nm-thick flake capped by 25 nm Al2O3. Adapted with permission from 26 under a Creative Commons License (http://creativecommons.org/licenses/by/4.0/). c) (Left) Schematic of the BN–BP–BN heterostructure device fabrication process. (Right) Optical image of the BN–BP–BN heterostructure after O2-plasma etching (the etched area is enclosed within the white line) and of the BN–BP–BN Hall-bar device. Adapted with permission from 47 under a Creative Commons License (http://creativecommons.org/licenses/by/4.0/).......Page 62
  Figure 4. a) Time dependence of the normalized PL intensity of the monolayer phosphorene samples treated by different methods: exfoliated 1L phosphorene (red), 1L phosphorene with PxOy (~11 nm) capping layer produced by O2 plasma etching (green) and 1L phosphorene with dual passivation layers of PxOy and 5 nm of ALD Al2O3 (black). All PL was measured in ambient condition under the same laser excitation. Inset: zoom in plot for the exfoliated 1L phosphorene sample. Adapted with permission from 53 under a Creative Commons License (http://creativecommons.org/licenses/by/4.0/). b) Optical images of flakes covered by a thin PxOy layer and a Al2O3 + PxOy double layer after fabrication and respectively, after 3 days and 30 days. The images show the higher passivation effect of the double capping layer. Adapted with permission from 53 under a Creative Commons License (http://creativecommons.org/licenses/by/4.0/). c) HRTEM image of the hybrid structure, where the C60 molecules can be seen passivating the edges of the BP layer. Inset: low magnification TEM image (top). STEM image (middle) and EDX elemental mapping (bottom) of the C60-BP hybrid structure to show the successful presence of the fullerenes along the borders. Adapted with permission from 60 under a Creative Commons License (http://creativecommons.org/licenses/by/4.0/).......Page 63
  Figure 5. a) Preparation process to obtain few-layer phosphorene enriched aqueous dispersions. The workflow is represented by the test tubes, going the order of the different steps from left to right. Deoxygenated water with 2% (wt/vol) SDS was prepared by ultrahigh-purity Ar purging. The exfoliation of the BP crystal was performed in a sealed container using tip ultrasonication. Then, this solution was centrifuged to remove unexfoliated BP crystals. The remaining FL-BP dispersion was ultracentrifuged to precipitate large flakes. The supernatant was finally redispersed in deoxygenated water. Reproduced with permission from 67. Copyright 2016 National Academy of Sciences. b) Relative absorbance as a function of time, measured at 465 nm for: the standard few-layer BP dispersion exfoliated in CHP, in NMP, in IPA and the BP exfoliated in CHP in a glovebox (CHP GB). Adapted with permission from 66 under a Creative Commons License (http://creativecommons.org/licenses/by/4.0/).......Page 64
 References......Page 65
 Introduction......Page 72
 Structure and Properties of White Phosphorus......Page 73
  Figure 1. Comparison between the violet and fibrous red phosphorus. a) Building units of the violet and fibrous phosphorus 22. b) Interconnecting tubes of fibrous phosphorus (left) versus violet phosphorus (right). Reproduced with permission from 22. Copyright 2005 Wiley.......Page 74
  Figure 2. High-resolution electron micrograph for a) Violet phosphorus b) fibrous phosphorus. Reproduced with permission from 22. Copyright 2005 Wiley.......Page 75
  Figure 3. Atomic structure of (a) multi-layer and (b) monolayer black-P 34. Reproduced with permission from 34. Copyright 2015 Royal Society of Chemistry.......Page 76
  Figure 5. Band Structure of Phosphorene 42. Reprinted by permission from Springer Nature: Springer Nature, Nature Reviews Materials (ref 42), Copyright 2016.......Page 77
  Figure 6. Functionalization of monolayer black-P using a nitrene moiety 47. Reproduced with permission from 47. Copyright 2018 American Chemical Society.......Page 79
  Figure 7. (a) Top and side view of Black-P and (b) Blue-P structures (c) dislocations that part of converting from Black-P to Blue-P (d) A-B stacks of Blue-P structure at equilibrium 33. Reproduced with permission from 33. Copyright 2014 American Physical Society.......Page 80
 References......Page 82
 Introduction......Page 90
 Phosphorus Cluster Cations......Page 91
  Figure 2. CID mass spectra of selected ions obtained at relatively low collisional energies: (a) , (b) , (c) , (d) , (e) (f) (g) and (h) . Reproduced with permission from 19. Copyright 2015 John Wiley & Sons.......Page 92
  Figure 3. Lowest-energy configurations of odd-numbered cluster cations of (m= 1-12). Reproduced with permission from 28. Copyright 2010 Elsevier.......Page 93
  Figure 4. CID mass spectra of selected ions obtained at relatively high collisional energies: (a) , (b) , (c) , (d) , (e) and (f) . Reproduced with permission from 19. Copyright 2015 John Wiley & Sons.......Page 95
  Figure 6. Mass spectrum of phosphorus cluster anions obtained by laser ablation of RP in the m/z range of 3000–16000, A portion of the spectrum is shown in the inset. The experiment was performed on the FT ICR MS. Reproduced with permission from 18. Copyright 2019 Acta Physico-Chimica Sinica.......Page 96
  Figure 7. Photoelectron spectra of -clusters (n=2-9) recorded at photo energy = 3.49 eV (left) and = 4.66 eV (right). Reproduced with permission from 34. Copyright 1931 American Institute of Physics.......Page 98
  Figure 9. CID mass spectra of selected ions obtained at relatively high collisional energies: (a) , (b) , (c) , (d) , (e) , (f) (g) , (h) and (i) . Reproduced with permission from 33. Copyright 2016 Elsevier.......Page 99
  Figure 10. Lowest-energy configurations of odd-numbered cluster anions of (m= 1-9). Reproduced with permission from 33. Copyright 2016 Elsevier.......Page 100
  Figure 11. CID mass spectra of some selected anions, which were obtained at different values of ’s: (a) = 0.15 V; (b) = 0.4 V; (c) = 0.3 V; (d) = 0.5 V; (e) = 0.225 V; and (f) = 0.5 V; The frequency offset is set to be 100 Hz relative to cyclotron frequencies of corresponding precursor ions. Reproduced with permission from 33. Copyright 2016 Elsevier.......Page 101
  Figure 12. Lowest energy structures and their corresponding isomers for (n = 1–14) clusters. For each size, the lowest-energy isomers are reported in bold character. Reproduced with permission from 41. Copyright 2017 Elsevier.......Page 102
 Metal Phosphide Clusters......Page 103
 Other Relative Clusters......Page 104
 A Brief Overview......Page 105
  Figure 13. Morphology characterization of BPQDs. a) TEM image of BPQDs. b) Enlarged TEM image of BPQDs. c,d) HRTEM images of BPQDs with different lattice fringes. Scale bar=5 nm. e) Statistical analysis of the sizes of 200 BPQDs measured from TEM images. f) AFM image of BPQDs. g,h) Height profiles along the white lines in (f). i) Statistical analysis of the heights of 200 BPQDs measured by AFM. A morphology sketch of BPQD is shown as an inset in (a). Reproduced with permission from 11. Copyright 2015 John Wiley & Sons.......Page 106
 Applications of Laser Ablation in PQDs......Page 107
 Summary and Outlook......Page 108
 References......Page 109
 Introduction......Page 114
 General Methods......Page 115
 Alkali and Alkaline-Earth Metal Phosphides......Page 117
 Transition Metal Phosphides......Page 119
 Lanthanide and Actinide Phosphides......Page 120
 Main-Group (Post-Transition) Metal Phosphides......Page 122
 Conclusion......Page 123
 References......Page 137
Black Phosphorus Based Photodetectors......Page 146
 Overview of Surface Illuminated BP Based Photodetectors......Page 147
  Figure 1. (a) Typical surface-illuminated BP based photodetector with bottom gate. (b) Fast response to visible light, and (c) Slow response to ultraviolet in a BP based photodetector. (d) Schematics of a MIR BP based photodetector with interdigitated electrodes and its power-dependent response. ((a) Reproduced with permission from reference 5. Copyright 2014 American Chemical Society; (b)&(c) Reproduced with permission from reference 7. Copyright 2015 American Chemical Society; (d) Reproduced with permission from reference 10. Copyright 2016 American Chemical Society.)......Page 148
 Photodetectors Based on BP Homojunctions......Page 149
 Photodetectors Based on BP-TMDCs Heterojunctions......Page 150
  Figure 4. (a) Cross section schematics of a BP based dual-gate field-effect transistor for bandgap tuning to enable longer wavelength detection. (b) Photocurrent tuned by top and bottom gate at 7.7 µm wavelength at a cryogenic temperature of 77K. (c) Absorption spectra of black arsenic-phosphorus, indicating smaller bandgap and wider spectral detection range up to 10 µm. ((a)&(b) Reprinted by permission from Springer Nature: Springer Nature, Nature Communication 12, Widely tunable black phosphorus mid-infrared photodetector, X. Chen et al., Copyright (2017); (c) Reprinted with permission of AAAS from Science Advances 30 Jun 2017: Vol. 3, no. 6, e1700589. © The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC) http://creativecommons.org/licenses/by-nc/4.0/).......Page 151
  Figure 5. Illustration of BP based photodetector with plasmonics from of bowtie antenna and bowtie apertures. Bowtie antennas were utilized to enahance responsivity while bowtie apertures were designed to increase polarization sensistivity. (Reproduced with permission from reference 25. Copyright 2018 American Chemical Society.)......Page 152
  Figure 6. (a) Structure of a BP/MoS2/BP/Au photodetector for polarization resolving. (b) Polarization-resolved spectral photoresponse of the two diodes. (Reprinted by permission from Springer Nature: Springer Nature, Nature Photonics 26, Polarization-resolved black phosphorus/molybdenum disulfide mid-wave infrared photodiodes with high detectivity at room temperature, J. Bullock et al., Copyright (2018).)......Page 153
 Waveguide-Integrated Photodetectors in the Near-Infrared......Page 154
  Figure 7. Common types of waveguide-integrated photodetectors. (a) Schematic of the waveguide- integrated Ge based photodetector. (b) Schematic of the waveguide-integrated III-V based photodetector/laser. (c) Schematic of the waveguide-integrated graphene based photodetector working at 1.55 µm. (d) Schematic of the waveguide-integrated TMDC based photodetector working at 1.16 µm. ((a) Reprinted by permission from Springer Nature: Springer Nature, Optical and Quantum Electronics 30, Heterostructure modeling consideration for Ge-on-Si waveguide photodetectors, A. Palmieri et al., Copyright (2018); (b) Reproduced with permission from reference 36. Copyright 2015 MDPI; (c) Reprinted by permission from Springer Nature: Springer Nature, Nature Photonics 40, Chip-integrated ultrafast graphene photodetector with high responsivity, X. Gan et al., Copyright (2013); (d) Reprinted by permission from Springer Nature: Springer Nature, Nature Nanotechnology 42, A MoTe2-based light-emitting diode and photodetector for silicon integrated circuits, Y. Bie et al., Copyright (2017).)......Page 155
  Figure 8. Reported works of waveguide-integrated BP based photodetectors working in the NIR. (a) Schematic of the waveguide-integrated BP based photodetector with high responsivity and low dark current. (b) Mode profile showing light-BP interaction. (c) Eye diagram of the BP based photodetector working at 3 GHz. (d) Schematic of the 3D integration of BP based Photodetector with Si photonics and nanoplasmonics. (e) Mode profile showing Si photonics-BP-plasmonic interaction. ((a-c) Reproduced with permission from reference 45. Copyright 2015 Springer Nature; (d&e) Reproduced with permission from reference 46. Copyright 2017 American Chemical Society.)......Page 156
 Waveguide-Integrated BP Based Photodetectors in the MIR......Page 157
  Figure 9. Waveguide-integrated BP based photodetector working in the MIR. (a) Schematic of the device. (b) Zoom-in view of the BP based photodetector. (c) Optical image of the device. (d) Simulation of light propagation and distribution in the whole integrated system at 3.78 µm. (e) Light distribution in a cross section of the grating structure. (f) Contour plot of gate and drain dependent photocurrent under 237 µW illumination at 3.78 µm. (g) Energy band diagrams for the four quadrants labeled I, II, III, and IV in (f). (h) Power dependent photocurrent and responsivity of the phototransistor. (i) Spectral responsivity of three photoconductors with distinct BP thickness and orientation. (j) Percentage of light propagating upward and downward at the output grating coupler with and without metal gate. (Reproduced with permission from reference 11. Copyright 2019 Americal Chemical Society.)......Page 158
 Conclusion......Page 159
 References......Page 161
 Introduction......Page 166
  Figure 1. The molecular structures of (a) Hittorf phosphorus and (b) fibrous phosphorus. Reproduced with permission from reference 16. Copyright 2019, Elsevier.......Page 167
 Crystal Structure and Morphology Control......Page 168
  Figure 3. (a–c) Representative SEM images, (d) XRD patterns, the blue curve was the simulated pattern based on the crystallographic data, (e) atomic structure and (f–h) TEM, HRTEM and SAED analysis of fibrous phosphorus submicron fibers obtained at -0.06 MPa, 100 mg RP and 550 °C. Reproduced with permission from reference 13. Copyright 2014, The Royal Society of Chemistry.......Page 170
  Figure 4. SEM images of (a) micro-fibrous P/SiO2, (b) smashed-fibrous P, and XRD patterns of (c) micro-fibrous P/SiO2 and (d) smashed-fibrous P, bulk-fibrous P. The standard XRD patterns of fibrous P are placed in (c) and (d) as the references. (e) Time course of the hydrogen evolution on micro-fibrous P/SiO2 and smashed-fibrous P. (f) Comparison of the activity of photocatalytic hydrogen evolution on different elemental photocatalysts. The light source used or referred here are all visible light, except the mesoporous crystalline Si (full spectrum). Reproduced with permission from reference 18. Copyright 2016, Wiley-VCH.......Page 171
 Cocatalyst Loading......Page 172
  Figure 6. (a, b) SEM and (c, d) TEM images of resulted hierarchical YPO4/P hollow microspheres with different magnifications. Inset is the HRTEM image of the marked frame region in (d). (e) The possible formation process of hierarchical P/YPO4 hollow spheres. Reproduced with permission from reference 29. Copyright 2012, Elsevier.......Page 173
  Figure 8. (a) Schematic representation of the proposed charge trapping model in g-C3N4 (left) and RP/g-C3N4 (right). Normalized fs-TA decay kinetics (dotted lines) with exponential fitting curves (solid lines) of the sample dispersions (0.1 mg mL-1) in H2O probed at 560 nm under 400 nm excitation: (b) short time scale, (c) long time scale; (d) ns-TA decay kinetics of the sample dispersions (0.1 mg mL-1) in H2O probed at 460 nm under irradiation of 400 nm laser. Reproduced with permission from reference 34. Copyright 2017, Wiley-VCH.......Page 174
 Photocatalytic Mechanism......Page 175
  Figure 9. (a) Photocatalytic inactivation efficiencies, (b) Level of 1O2, (c) Level of •O2–, (d) Level of •OH, (e) Level of H2O2, were measured with red phosphorus in the presence of various scavengers (l-histid