Defects Generation and Surface Functionalization on Epitaxial Blue

Subscriber access provided by UNIV OF LOUISIANA

C: Surfaces, Interfaces, Porous Materials, and Catalysis

Defects Generation and Surface Functionalization on Epitaxial Blue Phosphorene by C Adsorption 60

Dechun Zhou, Nan Si, Qin Tang, Bohong Jiang, Xiufeng Song, Han Huang, Miao Zhou, Qingmin Ji, and Tianchao Niu J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.9b03344 • Publication Date (Web): 29 Apr 2019 Downloaded from http://pubs.acs.org on April 30, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

Defects Generation and Surface Functionalization on Epitaxial Blue Phosphorene by C60 Adsorption Dechun Zhou†,#, Nan Si†,#, Qin Tang†,#, Bohong Jiang†, Xiufeng Song‡, Han Huang§, Miao Zhou , Qingmin Ji*,†, Tianchao Niu*,† † Herbert Gleiter Institute of Nanoscience, School of Material Science and Engineering, Nanjing University of Science & Technology, No. 200, Xiaolingwei, Nanjing, 210094 China ‡ MIIT Key Laboratory of Advanced Display Materials and Devices, Institute of Optoelectronics & Nanomaterials, School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing, 210094 China § Hunan Key Laboratory of Super-microstructure and Ultrafast Process, College of Physics and Electronics, Central South University, Changsha 410083 China School of Physics, Beihang University, No. 37 XueYuan Road, Haidian District, Beijing, 100191 China

ACS Paragon Plus Environment

The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Abstract We present a molecular beam epitaxial growth of Blue phosphorene (BlueP), a new allotrope of black phosphorene, on Au(111) and its surface functionalization with fullerene (C60) molecules by using low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS). In contrast to the well-ordered aggregation on conventional surfaces, C60 molecules favor to adsorb at the domain boundaries of BlueP and create defects and disordered phase nearby. STS reveals a shift of the conduction band minimum of BlueP and a remarkable broadening of the lowest unoccupied molecular orbital of C60, indicating an interfacial charge transfer. In addition, co-deposition of C60 with phosphorous precursors on Au(111) followed by annealing generates a new reconstruction of BlueP comprising larger triangles and higher density of dislocation lines that are favorable for anchoring bulky C60 balls.


Page 2 of 20

Page 3 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Introduction Since the discovery of black phosphorus as a direct band gap semiconductor1-3 and the tremendous advancement of its unique properties4-8, great efforts have been devoted to the fabrication of high quality, wafer-scale phosphorene9-13. However, up to now, preparation of black phosphorene mainly relies on mechanical, liquid phase isolation, laser exfoliation and plasma etching with low yield14-16. Moreover, molecular beam epitaxy growth on Au(111) surface generates a new allotrope of phosphorene, Blue Phosphorene (BlueP) 17-22, which has also been theoretically predicted to exist in single layer form with high carrier mobility and wide fundamental band gap23, showing great promise in electronic devices24-26. However, the knowledge BlueP is currently unbalanced in particular for its surface functionalization: the amount of theoretical work largely exceeds its experimental counterpart26-33. Surface functionalization of two-dimensional nanomaterials with organic molecules is an effective approach to tune electronic properties and to broaden their applications in molecular and 2D material-based devices34-38. Buckminsterfullerene (Figure 1A), C60, has attracted intense research interest due to its exciting chemical, electronic and physical properties39-42. It and its derivates are building blocks that have been widely applied in solar cells as an electron acceptor43-45. Although behaving as an insulator at room temperature, its low-lying lowest unoccupied molecular orbital



(LUMO) can make charge transfer take place when contacted with electrodes46-48. Meanwhile, its electronic transport property may also differ according to the interactions and the contacting positions with the electrodes49-50. Therefore, studying the adsorption of C60s on BlueP may serve as a model system for a better understanding of molecular-surface interactions in phosphorene-based electronics51. In this work, we have used scanning tunneling microscopy and spectroscopy to explore the microscopic growth and electronic properties of C60 molecules adsorbed onto the monolayer BlueP that has been grown on Au(111). It is striking that C60 barely can assemble into ordered molecular arrays on BlueP but create defects and disordered phase near the adsorption sites. C60 resides at large holes surrounded by irregular triangles comprising densely packed phosphorus atoms. STS measurements on C60 and BlueP near the adsorbates indicate a remarkable charge transfer from BlueP to C60. Finally, by using the co-adsorption of C60 and phosphorous precursors on Au(111) followed by annealing, a new surface reconstruction of BlueP has been created with larger triangles and pores as well as higher density of dislocation lines. Experimental Methods The experiments were performed in an ultra-high vacuum (UHV) chamber combining a molecular beam epitaxy (MBE) system and a SPECS low-temperature scanning probe microscopy (77K) with a bare pressure of


Page 4 of 20

Page 5 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


2×10-10 mbar. All the samples were prepared in the MBE chamber, and transferred directly to the STM chamber without breaking the vacuum. Single-crystal Au(111) (Mateck GmbH, https://mateck.com) were cleaned by repeated argon ion sputtering and annealing cycles. Phosphorous was deposited by evaporation from a crucible containing bulk black phosphorus crystals (Nanjing mknano tech.Co., Ltd. ; http://www.mukenano.com/) at 250ºC. Pure C60 (80 mg: 99.5% pure, MTR Ltd., USA) was evaporated at 318ºC from a Knudsen cell onto the clean substrates while keeping the substrates at room temperature. STM characterizations were performed at ~78K, and the bias voltages were defined as the sample bias. STM images were collected with a constant current mode. All the dI/dV measurements were carried out using a standard lock-in technique with an ac modulation of 15 mV at a frequency of 913 Hz. All STM images were processed using free WSxM52 and Gwyddion53 software, and involved plane flattening and calibrating to reflect the known unit cell of the clean BlueP surface. Results and Discussion BlueP has a buckled honeycomb lattice similar to silicene54-55 (Figure 1B). The unit cell size of free-standing BlueP is 3.33 Å with a buckling height of ~1.24 Å23. Epitaxial growth on the Au(111) surface results in a surface reconstruction19, 21 that is also similar to the (4×4) reconstruction of silicene on Ag(111)56-57. From the atomically resolved STM image in Figure 1C, it comprises trimers that aggregate into honeycomb structure with wellACS Paragon Plus Environment



Page 6 of 20

Page 7 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Examining the size of C60, these periodic pores in BlueP are too small to hold such bulky balls. Meanwhile, it is noted that direct deposition of C60 on BlueP at room temperature barely can provide stable image due to the high mobility of C60 on the atomic flat BlueP. Mild annealing at 400K effectively removes the physisorbed C60 and generates randomly dispersed individual C60 molecules, as shown in Figure 2A (Figure S1 A and B). This temperature is comparable with stacking C60 arrays on molecular templates58 (330K) and the formation of densely packed C60 islands on graphite(425K)59; but much lower than the typical annealing temperature on Au(111)60 (540K) and Ag(111)61 (685K). Scrutinizing the adsorption sites of C60, we find that the defect-free areas are free-from molecules, while the C60 molecules preferentially reside at the domain boundaries surrounded by disordered phase which are generated after the adsorption of C60. Figure 2B representatively demonstrates the adsorption structures of C60 and their atomic environment. Figure 2C is the corresponding differentiate image with enhanced visibility. It is clear that BlueP near C60 all transforms into either disordered phase or large triangles. Moreover, these C60 molecules still reside at the pores of the distorted honeycomb lattice. Furthermore, the configuration of C60 varies from each other that would depend on the atomic environment of BlueP. It is noted that the domain boundaries are the most favorable to anchor C60 that benefit from the lone-pair electron in the sp3 orbitals and the flexible edges for



A

B

C

disorder D. B.

21.0 Å

9.5 Å

III II

D. F. D

disorder

I

F

E

D

LUMO

III II

dI/dV (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 20

1.06 0.29

I

-0.8 VBM

-1

D. B.

21.0 Å 7 6

~1.16

0.36

5 4

CBM

0 1 Sample Bias (V)

3

L=21.2 Å

2 1

2 0

1

2

3

4

5

6

7

Profile (x)

Figure 2. C60 on BlueP. (A) STM topographic image of C60 on BlueP, the bright balls are individual C60 molecules. Defect free area is marked with ‘D.F.’; (B) Enlarged STM image showing the adsorption site and the atomic environment of C60 on BlueP; domain boundary is indicated by ‘D.B.’. (C) Differentiate image of (B) showing different atomic configurations of C60; (D) C60 molecules at the domain boundary aggregate into a hexagon; (E) dI/dV spectra of BlueP and single C60. Spectra I, II and III were taken at indicated spots in panel B; (F) STM image obtained on the area marked by the yellow square in (A). Scanning parameters: (A) 55nm, 900mV, 100pA (B) and (C) 20nm, 300mV, 200pA; (D) 15nm, 300mV, 500pA; (F) 10nm, 300mV, 100pA. reconstruction62-63. A C60 hexagon with an average intermolecular distance of ~21.2 ±1 Å forms near a domain boundary (Figure 2D). Such distance


Page 9 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


indicates the nearest intermolecular packing on the defective BlueP (Figure S1 C to F, supporting information). To gain further insight into the local electronic properties of C60 on BlueP, we measured the differential conductance (dI/dV) spectroscopy. We first measured a dI/dV for clean BlueP far away from adsorbate. As shown in Figure 2E, the spectra ‘I-III’ are corresponding to the spots marked in panel B. The valence band maximum (VBM) and conduction band minimum (CBM) is located at -0.8 V (red arrow) and 0.36 V (blue arrow), respectively. Therefore, the band gap value of BlueP is 1.16 eV, as displayed in Figure 2E, which is comparable with previous reported values obtained from STS17 and angle-resolved photoemission spectroscopy (ARPES) measurements19-21. It should be noted that this measured gap size is smaller than the theoretically predicated wide band gap of ~2 eV23. This deviation is mainly caused by the in-plane strain in the surface reconstruction on Au(111) and the interaction between pz orbitals of BlueP and Au(111)19. The differential conductance of BlueP adjacent to C60 exhibits a peak shift from 0.36 V to 0.29 V, implying electron pumping out from BlueP to C60. The local electronic structure of C60 on Au(111) has been extensively explored via dI/dV in the past decades64-67. The typical highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), and LUMO+1 of C60 on Au(111) are centered at -1.7±0.2V,



Page 10 of 20

1.0±0.2V and 2.2±0.2V. It is obvious that the HOMO of C60 locates much lower than the VBM of BlueP. Furthermore, the HOMO and LUMO+1 strongly depend on the positions detected on individual molecule while the molecular orientation has minimal effect64. Comparing the LUMO of C

6

0

A

o

n

B

B

l C

u

e

1.01 0.96

P

1.24

iii i ii

ii

iii

i 0

D

E

1

2

3

4

Length (nm)

5

6

F

disorder

Bare Au(111)

Figure 3. (A) Defective BlueP on Au(111) after the co-deposition of C60 followed by annealing; (B) Enlarged STM image showing the different triangles, large pores and irregular aggregates; (C) Line-scan profile taken along the yellow arrow in (B) depicting the pore sizes; (D) C60 on this BlueP; (E) Zoom-in scan STM image of individual C60 molecule residing at the pore site; (F) Clean Au(111) surface with the herringbone reconstruction after high temperature annealing. Scanning parameters: (A) 35nm, 2.2V, 100pA; (B) 9nm, 1.2V, 200pA; (D) 26nm, 2.8V, 80pA; (E) 500mV, 200pA; (F) 125nm, 2.2V, 95pA. ACS Paragon Plus Environment

Page 11 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


with C60 on other metal substrates or graphene68-69, it is significantly broadened with a fwhm (full-width-at-half-maximum) of ~0.6 eV, indicating a remarkable hybridization of molecular orbitals of C60 with electronic states of BlueP. Although the freshly prepared BlueP on Au(111) has domain boundaries and dislocation lines, there is barely visible defects or different reconstructed domains comprising triangles larger than trimer with a high density (Figure S2, Supporting information). The adsorption of C60 creates versatile defects and a variety of new superstructures on BlueP as shown above. Therefore, we intentionally deposit 0.2 monolayer C60 on Au(111) followed by deposition of 1.5 monolayer phosphorous, and then annealing at 450K that is the temperature for the formation of BlueP and the desorption of C60 (Figure S3 A, Supporting information). Figure 3A shows the as-prepared BlueP which exhibits short-range ordered honeycomb structure with an average pore-to-pore distance of ~16 Å. Furthermore, the honeycomb lattice is composed of triangles with different sizes. A zoomin scan presented in Figure 3B reveals three types of triangles which comprise three, six and ten dots, as highlighted by yellow, orange and green colors. Besides these, the pore size of the honeycomb lattice with large triangles is above ~1.0 nm, as depicted in the line profile of Figure 3C. To evaluate the incorporating capability of C60 on this defective BlueP with large pores, we further deposit C60 and anneal at 410K to monitor the



distribution and structure of C60. As shown in Figure 3D (and Figure S3B, supporting information), the coverage of C60 is much higher than that on the defect-free BlueP (Figure 2A). The large pores and high density of defects are beneficial for incorporating C60 into the lattice of BlueP. Enlarged STM image of Figure 3E presents that the C60 still resides at a hole surrounded by triangles. Finally, we would like to address the instability of BlueP. First of all, high temperature annealing results in the disappearance of the BlueP17. Figure 3F is the STM image taken on the Au(111) after annealing C60/BlueP at 510K for 10min. Except for few clusters on the step edges and atoms at the elbow sites, annealing gives rise to a clean substrate with the typical herringbone reconstructions. Meanwhile, different from C60 on graphene, that both can assemble into well-ordered molecular arrays at room temperature70 and intercalate at the graphene/metal interface at high temperature (above 700K)71, C60 creates defects and disordered phases that destroys the original lattice of BlueP. We also intentionally deposit bismuth from a Knudsen-cell (source temperature 678K) onto BlueP held at room temperature, followed by annealing at 400K. Figure 4A is an STM image taken on 0.6 ML bismuth on BlueP. The bright dotted areas are bismuth atoms while the BlueP preserves its original honeycomb lattice, as shown in the enlarged STM image of Figure 4B. Figure 4C shows a domain boundary between BlueP and bismuth. The irregular area covered by bright


Page 12 of 20

Page 13 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


A

B

C

Bi

BlueP

Bi BlueP

Bi

D

E Bi

F Bi

60º 60º 0.5 nm

Figure 4. Instability of BlueP after deposition of bismuth. (A) Large-scale STM image of 0.6 ML Bi on BlueP; (B) zoom-in scan showing the boundary of Bi and BlueP; (C) High-resolution STM image of the honeycomb structure of BlueP and the disordered phase of Bi; (D) after increasing the coverage of Bi above 0.9 ML, all the surface was covered by Bi stripes; (E) zoom-in scan of different domains of Bi stripes; (F) the typical (p× 3) superstructure of Bi on Au(111). Scanning parameters: (A) 50nm, and (B) 20nm, 1.2V, 85pA; (C) 10nm, -800Mv, 120pA; (D)110nm, -1.7V, 400pA; (E) 30nm, -400mV, 1nA; (F) 5nm, -100mV, 1nA. dots is corresponding to a poor ordering superstructure of bismuth at low coverage72. It is noted that differing from the C60 adsorption generated defects and large triangles, bismuth atoms replace the surface phosphorene to show a coverage dependent growth behavior. Increasing the coverage



above 0.9 ML, the whole surface is covered by bismuth with periodic stripes (Figure 4D). Different domains of Bi stripes exhibit a well-defined orientation of 60º due to the three-fold symmetry of Au(111) substrate (Figure 4E). High-resolution STM image in Figure 4F demonstrates a square unit cell of 0.5nm while the periodicity of the stripes is 1.4nm. Such stripes are the typical 5 × 3 superstructure of Bi on Au(111).72-73 This feature further proves the fragile BlueP on Au(111) that is ascribed to its high strain and surface reconstruction. In conclusion, we have explored the adsorption and electronic properties of C60 on a monolayer of epitaxial BlueP on Au(111) using lowtemperature STM/STS. We find that C60 creates defects and disordering phases after the adsorption on BlueP. The defect free area barely can capture C60 while the C60 prefers the domain boundaries which are rich of lone pair electrons and have flexible edges with large pores. Co-adsorption of C60 with phosphorous precursors followed by annealing leads to a new superstructure of BlueP comprising large triangles and pores along with the high density of defects and dislocation lines. ASSOCIATED CONTENT Supporting Information STM images showing the adsorption of C60 molecules at the domain boundaries and the average intermolecular distance (Figure S1); Dislocation lines and defects of BlueP (Figure S2); Defective BlueP with


Page 14 of 20

Page 15 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


large triangles (Figure S3). Author Information Corresponding Authors * E-mail: Q. J. ([email protected]); T. N. ([email protected]) Author contributions # D.

Z., N. S. and Q. T. contributed equally to this work.

Notes The authors declare no competing financial interest. Acknowledgments This work is financially supported by the Natural Science Foundation of Jiangsu Province under BK20181297, the National Natural Science Foundation of China under contract Nos. 11674042, 21875108, 21403282 and 11874427, the Science Challenge Project (TZ2018004), the Fundamental Research Funds for Central Universities (30917015106), and the 111 project (B12015). The authors acknowledge Dr. Evangelos Golias (Freie Universität Berlin) for sharing the theoretical model of BlueP on Au(111) with us. The authors thank Dr. Jialin Zhang for helpful discussions. References 1.

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. Nanotech. 2014, 9, 372. 2.

Ling, X.; Wang, H.; Huang, S.; Xia, F.; Dresselhaus, M. S., The Renaissance of Black Phosphorus.

Proc. Natl. Acad. Sci. U.S.A. 2015, 112, 4523. 3.

Gusmão, R.; Sofer, Z.; Pumera, M., Black Phosphorus Rediscovered: From Bulk Material to

Monolayers. Angew. Chem. Int. Ed. 2017, 56, 8052-8072.



4.

Hu, Z.; Niu, T.; Guo, R.; Zhang, J.; Lai, M.; He, J.; Wang, L.; Chen, W., Two-Dimensional Black

Phosphorus: Its Fabrication, Functionalization and Applications. Nanoscale 2018, 10, 21575-21603. 5.

Castellanos-Gomez, A., Black Phosphorus: Narrow Gap, Wide Applications. J. Phys. Chem. Lett.

2015, 6, 4280-4291. 6.

Carvalho, A.; Wang, M.; Zhu, X.; Rodin, A. S.; Su, H.; Castro Neto, A. H., Phosphorene: From

Theory to Applications. Nat. Rev. Mater. 2016, 1, 16061. 7.

Kou, L.; Ma, Y.; Smith, S. C.; Chen, C., Anisotropic Ripple Deformation in Phosphorene. J. Phys.

Chem. Lett. 2015, 6, 1509-1513. 8.

Zhang, Z.; Li, L.; Horng, J.; Wang, N. Z.; Yang, F.; Yu, Y.; Zhang, Y.; Chen, G.; Watanabe, K.;

Taniguchi, T., et al., Strain-Modulated Bandgap and Piezo-Resistive Effect in Black Phosphorus FieldEffect Transistors. Nano. Lett. 2017, 17, 6097-6103. 9.

Shriber, P.; Samanta, A.; Nessim, G. D.; Grinberg, I., First-Principles Investigation of Black

Phosphorus Synthesis. J. Phys. Chem. Lett. 2018, 9, 1759-1764. 10. Cho, K.; Yang, J.; Lu, Y., Phosphorene: An Emerging 2d Material. Journal of Materials Research 2017, 32, 2839-2847. 11. Akhtar, M.; Anderson, G.; Zhao, R.; Alruqi, A.; Mroczkowska, J. E.; Sumanasekera, G.; Jasinski, J. B., Recent Advances in Synthesis, Properties, and Applications of Phosphorene. npj 2D Mater. Appl. 2017, 1, 5. 12. Kou, L.; Chen, C.; Smith, S. C., Phosphorene: Fabrication, Properties, and Applications. J. Phys. Chem. Lett. 2015, 6, 2794-2805. 13. Mannix, A. J.; Kiraly, B.; Hersam, M. C.; Guisinger, N. P., Synthesis and Chemistry of Elemental 2d Materials. Nat. Rev. Chem. 2017, 1, 0014. 14. Zhang, J.; Shin, H.; Lu, W., Highly Ambient-Stable Few-Layer Black Phosphorene by Pulsed Laser Exfoliation and Hemm. Chem. Comm. 2019. 15. Pei, J.; Gai, X.; Yang, J.; Wang, X.; Yu, Z.; Choi, D.-Y.; Luther-Davies, B.; Lu, Y., Producing AirStable Monolayers of Phosphorene and Their Defect Engineering. Nat. Comm. 2016, 7, 10450. 16. Li, B.; Lai, C.; Zeng, G.; Huang, D.; Qin, L.; Zhang, M.; Cheng, M.; Liu, X.; Yi, H.; Zhou, C., et al., Black Phosphorus, a Rising Star 2d Nanomaterial in the Post-Graphene Era: Synthesis, Properties, Modifications, and Photocatalysis Applications. Small 2019, 0, 1804565. 17. Zhang, J. L.; Zhao, S.; Han, C.; Wang, Z.; Zhong, S.; Sun, S.; Guo, R.; Zhou, X.; Gu, C. D.; Yuan, K. D., et al., Epitaxial Growth of Single Layer Blue Phosphorus: A New Phase of Two-Dimensional Phosphorus. Nano. Lett. 2016, 16, 4903-4908. 18. Xu, J.-P.; Zhang, J.-Q.; Tian, H.; Xu, H.; Ho, W.; Xie, M., One-Dimensional Phosphorus Chain and Two-Dimensional Blue Phosphorene Grown on Au(111) by Molecular-Beam Epitaxy. Phys. Rev. Lett. 2017, 1, 061002. 19. Golias, E.; Krivenkov, M.; Varykhalov, A.; Sánchez-Barriga, J.; Rader, O., Band Renormalization of Blue Phosphorus on Au(111). Nano. Lett. 2018, 18, 6672-6678. 20. Zhuang, J.; Liu, C.; Gao, Q.; Liu, Y.; Feng, H.; Xu, X.; Wang, J.; Zhao, J.; Dou, S. X.; Hu, Z., et al., Band Gap Modulated by Electronic Superlattice in Blue Phosphorene. ACS Nano 2018, 12, 50595065. 21. Zhang, W.; Enriquez, H.; Tong, Y.; Bendounan, A.; Kara, A.; Seitsonen, A. P.; Mayne, A. J.; Dujardin, G.; Oughaddou, H., Epitaxial Synthesis of Blue Phosphorene. Small 2018, 14, 1804066. 22. Gu, C.; Zhao, S.; Zhang, J. L.; Sun, S.; Yuan, K.; Hu, Z.; Han, C.; Ma, Z.; Wang, L.; Huo, F., et al., Growth of Quasi-Free-Standing Single-Layer Blue Phosphorus on Tellurium Monolayer Functionalized


Page 16 of 20

Page 17 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Au(111). ACS Nano 2017, 11, 4943-4949. 23. Zhu, Z.; Tománek, D., Semiconducting Layered Blue Phosphorus: A Computational Study. Phys. Rev. Lett. 2014, 112, 176802. 24. Zhang, J. L.; Han, C.; Hu, Z.; Wang, L.; Liu, L.; Wee, A. T. S.; Chen, W., 2d Phosphorene: Epitaxial Growth and Interface Engineering for Electronic Devices. Adv. Mater. 2018, 30, 1802207. 25. Li, J.; Sun, X.; Xu, C.; Zhang, X.; Pan, Y.; Ye, M.; Song, Z.; Quhe, R.; Wang, Y.; Zhang, H., et al., Electrical Contacts in Monolayer Blue Phosphorene Devices. Nano Res. 2018, 11, 1834-1849. 26. Montes, E.; Schwingenschlögl, U., High-Performance Field-Effect Transistors Based on ^8 and _8. Adv. Mater. 2019, 0, 1807810. 27. Tian, X.; Duan, J.; Wei, Y.; Feng, N.; Wang, X.; Gong, Z.; Du, Y.; Yakobson, B. I., Modulating Blue Phosphorene by Synergetic Codoping: Indirect to Direct Gap Transition and Strong Bandgap Bowing. Adv. Funct. Mater. 2019, 0, 1808721. 28. Fernández-Escamilla, H. N.; Guerrero-Sánchez, J.; Garcia-Diaz, R.; Martínez-Guerra, E.; Takeuchi, N., Adsorption of Dimethyl Sulfoxide on Blue Phosphorene. Surf. Sci. 2019, 680, 88-94. 29. Pontes, R. B.; Miwa, R. H.; da Silva, A. J. R.; Fazzio, A.; Padilha, J. E., Layer-Dependent Band Alignment of Few Layers of Blue Phosphorus and Their Van Der Waals Heterostructures with Graphene. Phys. Rev. B 2018, 97, 235419. 30. Du, L.; Zheng, K.; Cui, H.; Wang, Y.; Tao, L.; Chen, X., Novel Electronic Structures and Enhanced Optical

Properties

of

Boron

Phosphide/Blue

Phosphorene

and

F4tcnq/Blue

Phosphorene

Heterostructures: A Dft + Negf Study. Phys. Chem. Chem. Phys. 2018, 20, 28777-28785. 31. Xu, W.; Zhao, J.; Xu, H., Adsorption Induced Indirect-to-Direct Band Gap Transition in Monolayer Blue Phosphorus. J. Phys. Chem. C 2018, 122, 15792-15798. 32. Su, B.; Li, N., Lanthanide Atom Substitutionally Doped Blue Phosphorene: Electronic and Magnetic Behaviors. Phys. Chem. Chem. Phys. 2018, 20, 11003-11012. 33. Sun, M.; Wang, S.; Yu, J.; Tang, W., Hydrogenated and Halogenated Blue Phosphorene as Dirac Materials: A First Principles Study. Appl. Surf. Sci. 2017, 392, 46-50. 34. Krawiec, M., Functionalization of Group-14 Two-Dimensional Materials. J. Phys.: Condens. Matter 2018, 30, 233003. 35. Niu, T.; Zhang, J.; Chen, W., Surface Engineering of Two-Dimensional Materials. ChemNanoMat 2019, 5, 6-23. 36. Liu, Z.; Lau, S. P.; Yan, F., Functionalized Graphene and Other Two-Dimensional Materials for Photovoltaic Devices: Device Design and Processing. Chem. Soc. Rev. 2015, 44, 5638-5679. 37. Chen, W.; Chen, S.; Qi, D. C.; Gao, X. Y.; Wee, A. T. S., Surface Transfer P-Type Doping of Epitaxial Graphene. J. Am. Chem. Soc. 2007, 129, 10418-10422. 38. Ryder, C. R.; Wood, J. D.; Wells, S. A.; Hersam, M. C., Chemically Tailoring Semiconducting Two-Dimensional Transition Metal Dichalcogenides and Black Phosphorus. ACS Nano 2016, 10, 39003917. 39. Shrestha, L. K.; Ji, Q.; Mori, T.; Miyazawa, K. i.; Yamauchi, Y.; Hill, J. P.; Ariga, K., Fullerene Nanoarchitectonics: From Zero to Higher Dimensions. Chem. Asian J. 2013, 8, 1662-1679. 40. Cai, Z.-F.; Dong, W.-L.; Chen, T.; Yan, H.-J.; Wang, D.; Xu, W.; Wan, L.-J., Directed Assembly of Fullerene on Modified Au(111) Electrodes. Chem. Comm. 2018, 54, 8052-8055. 41. Tang, Q.; Zhang, S.; Liu, X.; Sumita, M.; Ishihara, S.; Fuchs, H.; Ji, Q.; Shrestha, L. K.; Ariga, K., Manipulation of Fullerene Superstructures by Complexing with Polycyclic Aromatic Compounds. Phys. Chem. Chem. Phys. 2017, 19, 29099-29105.



42. Tang, Q.; Bairi, P.; Shrestha, R. G.; Hill, J. P.; Ariga, K.; Zeng, H.; Ji, Q.; Shrestha, L. K., Quasi 2d Mesoporous Carbon Microbelts Derived from Fullerene Crystals as an Electrode Material for Electrochemical Supercapacitors. ACS Applied Materials & Interfaces 2017, 9, 44458-44465. 43. Schwarze, M.; Gaul, C.; Scholz, R.; Bussolotti, F.; Hofacker, A.; Schellhammer, K. S.; Nell, B.; Naab, B. D.; Bao, Z.; Spoltore, D., et al., Molecular Parameters Responsible for Thermally Activated Transport in Doped Organic Semiconductors. Nat. Mater. 2019, 18, 242-248. 44. Hou, J.; Inganäs, O.; Friend, R. H.; Gao, F., Organic Solar Cells Based on Non-Fullerene Acceptors. Nat. Mater. 2018, 17, 119. 45. Yan, C.; Barlow, S.; Wang, Z.; Yan, H.; Jen, A. K. Y.; Marder, S. R.; Zhan, X., Non-Fullerene Acceptors for Organic Solar Cells. Nat. Rev. Mater. 2018, 3, 18003. 46. Isshiki, Y.; Fujii, S.; Nishino, T.; Kiguchi, M., Fluctuation in Interface and Electronic Structure of Single-Molecule Junctions Investigated by Current Versus Bias Voltage Characteristics. J. Am. Chem. Soc. 2018, 140, 3760-3767. 47. Kiguchi, M.; Murakoshi, K., Conductance of Single C60 Molecule Bridging Metal Electrodes. J. Phys. Chem. C 2008, 112, 8140-8143. 48. Kim, Y.; Jeong, W.; Kim, K.; Lee, W.; Reddy, P., Electrostatic Control of Thermoelectricity in Molecular Junctions. Nat. Nanotech. 2014, 9, 881. 49. Néel, N.; Kröger, J.; Limot, L.; Frederiksen, T.; Brandbyge, M.; Berndt, R., Controlled Contact to a C60 Molecule. Phys. Rev. Lett. 2007, 98, 065502. 50. Saffarzadeh, A., Electronic Transport through a C60 Molecular Bridge: The Role of Single and Multiple Contacts. J. Appl. Phys. 2008, 103, 083705. 51. Wang, C.; Niu, D.; Wang, S.; Zhao, Y.; Tan, W.; Li, L.; Huang, H.; Xie, H.; Deng, Y.; Gao, Y., Energy Level Evolution and Oxygen Exposure of Fullerene/Black Phosphorus Interface. J. Phys. Chem. Lett. 2018, 9, 5254-5261. 52. Horcas, I.; Fernández, R.; Gómez-Rodríguez, J. M.; Colchero, J.; Gómez-Herrero, J.; Baro, A. M., Wsxm: A Software for Scanning Probe Microscopy and a Tool for Nanotechnology. Rev. Sci. Instrum. 2007, 78, 013705. 53.

c & D.; Klapetek, P., Gwyddion: An Open-Source Software for Spm Data Analysis. In Open

Physics, 2012; Vol. 10, p 181. 54. Vogt, P.; De Padova, P.; Quaresima, C.; Avila, J.; Frantzeskakis, E.; Asensio, M. C.; Resta, A.; Ealet, B.; Le Lay, G., Silicene: Compelling Experimental Evidence for Graphenelike Two-Dimensional Silicon. Phys. Rev. Lett. 2012, 108, 155501. 55. Feng, B.; Ding, Z.; Meng, S.; Yao, Y.; He, X.; Cheng, P.; Chen, L.; Wu, K., Evidence of Silicene in Honeycomb Structures of Silicon on Ag(111). Nano. Lett. 2012, 12, 3507-3511. 56. Zhao, J.; Liu, H.; Yu, Z.; Quhe, R.; Zhou, S.; Wang, Y.; Liu, C. C.; Zhong, H.; Han, N.; Lu, J., et al., Rise of Silicene: A Competitive 2d Material. Prog. Mater Sci. 2016, 83, 24-151. 57. Takagi, N.; Lin, C.-L.; Kawahara, K.; Minamitani, E.; Tsukahara, N.; Kawai, M.; Arafune, R., Silicene on Ag(111): Geometric and Electronic Structures of a New Honeycomb Material of Si. Prog. Surf. Sci. 2015, 90, 1-20. 58. Chen, W.; Zhang, H.; Huang, H.; Chen, L.; Wee, A. T. S., Orientationally Ordered C60 on PSexiphenyl Nanostripes on Ag(111). ACS Nano 2008, 2, 693-698. 59. Guo, L. a.; Wang, Y.; Kaya, D.; Palmer, R. E.; Chen, G.; Guo, Q., Orientational Epitaxy of Van Der Waals Molecular Heterostructures. Nano. Lett. 2018, 18, 5257-5261. 60. Gardener, J. A.; Briggs, G. A. D.; Castell, M. R., Scanning Tunneling Microscopy Studies of C60


Page 18 of 20

Page 19 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Monolayers on Au(111). Phys. Rev. B 2009, 80, 235434. 61. Li, H. I.; Pussi, K.; Hanna, K. J.; Wang, L. L.; Johnson, D. D.; Cheng, H. P.; Shin, H.; Curtarolo, S.; Moritz, W.; Smerdon, J. A., et al., Surface Geometry of C60 on Ag(111). Phys. Rev. Lett. 2009, 103, 056101. 62. Wang, H.; Si, C.; Zhou, J.; Sun, Z., Vanishing Schottky Barriers in Blue Phosphorene/Mxene Heterojunctions. J. Phys. Chem. C 2017, 121, 25164-25171. 63. Wang, X.; Yang, X.; Wang, B.; Wang, G.; Wan, J., Significant Band Gap Induced by Uniaxial Strain in Graphene/Blue Phosphorene Bilayer. Carbon 2018, 130, 120-126. 64. Lu, X.; Grobis, M.; Khoo, K. H.; Louie, S. G.; Crommie, M. F., Charge Transfer and Screening in Individual C60 Molecules on Metal Substrates: A Scanning Tunneling Spectroscopy and Theoretical Study. Phys. Rev. B 2004, 70, 115418. 65. Nakaya, M.; Kuwahara, Y.; Aono, M.; Nakayama, T., Reversibility-Controlled Single Molecular Level Chemical Reaction in a C60 Monolayer Via Ionization Induced by Scanning Transmission Microscopy. Small 2008, 4, 538-541. 66. Picone, A.; Giannotti, D.; Riva, M.; Calloni, A.; Bussetti, G.; Berti, G.; Duò, L.; Ciccacci, F.; Finazzi, M.; Brambilla, A., Controlling the Electronic and Structural Coupling of C60 Nano Films on Fe(001) through Oxygen Adsorption at the Interface. ACS Appl. Mater. Interfaces 2016, 8, 26418-26424. 67. Fei, X.; Zhang, X.; Lopez, V.; Lu, G.; Gao, H.-J.; Gao, L., Strongly Interacting C60/Ir(111) Interface: Transformation of C60 into Graphene and Influence of Graphene Interlayer. J. Phys. Chem. C 2015, 119, 27550-27555. 68. Yamada, Y.; Yamada, S.; Nakayama, T.; Sasaki, M.; Tsuru, T., Electronic Modification of C60 Monolayers Via Metal Substrates. Jpn. J. Appl. Phys. 2011, 50, 08LB06. 69. Lu, J.; Yeo, P. S. E.; Zheng, Y.; Yang, Z.; Bao, Q.; Gan, C. K.; Loh, K. P., Using the Graphene Moiré Pattern for the Trapping of C60 and Homoepitaxy of Graphene. ACS Nano 2012, 6, 944-950. 70. Kim, K.; Lee, T. H.; Santos, E. J. G.; Jo, P. S.; Salleo, A.; Nishi, Y.; Bao, Z., Structural and Electrical Investigation of C60–Graphene Vertical Heterostructures. ACS Nano 2015, 9, 5922-5928. 71. Monazami, E.; Bignardi, L.; Rudolf, P.; Reinke, P., Strain Lattice Imprinting in Graphene by C60 Intercalation at the Graphene/Cu Interface. Nano. Lett. 2015, 15, 7421-7430. 72. He, B.; Tian, G.; Gou, J.; Liu, B.; Shen, K.; Tian, Q.; Yu, Z.; Song, F.; Xie, H.; Gao, Y., et al., Structural and Electronic Properties of Atomically Thin Bismuth on Au(111). Surf. Sci. 2019, 679, 147153. 73. Kawakami, N.; Lin, C.-L.; Kawahara, K.; Kawai, M.; Arafune, R.; Takagi, N., Structural Evolution of Bi Thin Films on Au(111) Revealed by Scanning Tunneling Microscopy. Phys. Rev. B 2017, 96, 205402.



TOC

HT

2 nm

2 nm


Page 20 of 20

Defects Generation and Surface Functionalization on Epitaxial Blue

Recommend Documents