单层和双层二硫化钼化学气相沉积生长的动力学蒙特卡罗模拟研究

doi:10.3866/PKU.WHXB201812023

摘要/Abstract

摘要：

通过化学气相沉积方法，可控合成所需层数的二硫化钼仍然是一个挑战。因此，建立一个能够定量预测单层和多层二硫化钼生长的理论模型，并为实验制备提供指导，是十分必要的。在本文中，我们建立了一个动力学蒙特卡罗模型，来预测单层和双层二硫化钼的化学气相沉积生长。首先，我们提出了第一层和第二层的生长速率受吸附原子浓度分布的控制，以及紧凑三角形二硫化钼的生长过程为扭结成核和传播。其中，原子浓度是由吸附原子流量，吸附原子的有效寿命，生长温度，边的单位长度能量，单层和双层的单位面积结合能，成核准则决定的。扭结成核和传播是由锯齿边和扶手边附加原子所需的能量势垒决定的。然后，我们采用热力学理论准则对这些参数进行了标定。通过标定的动力学蒙特卡罗模型，我们发现第二层的生长速率与第一层的尺寸有很强的依赖性。随着第一层尺寸增加，第二层的生长速率呈单调递减趋势，甚至在第一层达到某个尺寸时，第二层的生长会被抑制。此外，我们还分析了不同生长温度和吸附原子流量下，双层二硫化钼的尺寸和形貌演化。在双层二硫化钼的整个生长过程中，第一层和第二层的形貌保持紧凑三角形，验证了扭结成核和传播模型的正确性。模拟结果表明，生长温度的升高或吸附原子流量的降低，促进了双层二硫化钼的生长，这与已报导的实验结果相吻合。生长温度升高使得第二层二硫化钼边缘的吸附原子浓度，随着远离第二层边缘的吸附原子浓度降低而相应降低，促进了双层二硫化钼的生长。同样，吸附原子流量降低减小了基体上的吸附原子浓度，降低了第一层远离边缘和靠近边缘的吸附原子浓度差，从而减缓了第一层的生长。第一层的生长减慢，减缓了第二层远离边缘和靠近边缘的吸附原子浓度差减小到零，从而促进双层二硫化钼的生长。为了更好地指导实验，我们进一步构建了双层二硫化钼生长的相图，可通过控制生长温度和吸附原子流量来实现或阻止双层二硫化钼的生长。因此，本工作不仅揭示了单层和双层二硫化钼生长所需的实验条件，而且为可控合成所需层数的二硫化钼提供了详细指导。

关键词: 二硫化钼, 单层生长, 双层生长, 化学气相沉积, 动力学蒙特卡罗

Abstract:

Controllable synthesis of MoS₂ with desired number of layers via chemical vapor deposition (CVD) remains challenging. Hence, it is highly desirable to develop a theoretical model that can be used to predict the single- and multilayer growth of MoS₂ quantitatively, and provide guidelines for experimental fabrication. Herein we have established a kinetic Monte Carlo (kMC) model to predict the CVD growth of mono- and bilayer MoS₂. First, we proposed that the growth rates of layer 1 and layer 2 were governed by the distribution of the adatom concentration, and the growth kinetics of compact triangular MoS₂ followed the kink nucleation-propagation mechanism. The adatom concentration was formulated in terms of adatom flux, effective lifetime of adatoms, growth temperature, binding energies, edge energies, and nucleation criterion. The kink nucleation and propagation were determined by energy barriers of the adatom attachments to the zigzag and armchair edges. We then employed an analytic thermodynamic criterion to extract these parameters. Using the calibrated model, we found that the growth rate of layer 2 strongly depended on the size of layer 1 and decreased monotonically with increasing size of layer 1, and might even become prohibited at the maximum size of layer 1. Furthermore, we analyzed the size and morphology evolutions of bilayer MoS₂ at different growth temperatures and adatom fluxes. Throughout the growth processes of bilayer MoS₂, the morphologies of layers 1 and 2 maintained triangular shapes with compact edges, consistent with the kink nucleation-propagation growth mechanism. Our simulations revealed that the growth of bilayer MoS₂ was promoted by increasing the growth temperature or decreasing the adatom flux, which corroborated the experimental observations. The increase in growth temperature led to reduced adatom concentration at the edge of layer 2 in accordance with the adatom concentration far from the edge of layer 2, resulting in a consistent difference in the adatom concentration to promote the growth of bilayer MoS₂. Similarly, the decrease in adatom flux lowered the difference between the adatom concentrations far from the edge and at the edge of layer 1, decelerating the growth of layer 1. The decelerated growth of layer 1 reduced the difference between the adatom concentrations far from the edge and at the edge of layer 2 to zero, permitting the growth of bilayer MoS₂. To guide the experimental synthesis, we constructed a phase diagram to delineate the permitted or prohibited growth of bilayer MoS₂ at different growth temperatures and adatom fluxes. Hence, this work not only unveils the conditions for the growth of mono- and bi-layer MoS₂, but also provides guidelines for controllable synthesis of MoS₂ with the desired number of layers.

10.3866/PKU.WHXB201809013.F009

Key words: MoS₂, Monolayer growth, Bilayer growth, Chemical vapor deposition, Kinetic Monte Carlo

MSC2000:

O641

陈帅,高峻峰,SRINIVASAN Bharathi M.,张永伟. 单层和双层二硫化钼化学气相沉积生长的动力学蒙特卡罗模拟研究[J]. 物理化学学报, 2019, 35(10): 1119-1127.

Shuai CHEN,Junfeng GAO,Bharathi M. SRINIVASAN,Yong-Wei ZHANG. A Kinetic Monte Carlo Study for Mono- and Bi-layer Growth of MoS₂ during Chemical Vapor Deposition[J]. Acta Physico-Chimica Sinica, 2019, 35(10): 1119-1127.

图/表 6

Fig 1

Fig 2

Fig 3

Fig 4

Fig 5

Fig 6

参考文献 44

1	Liu Y. ; Weiss N. O. ; Duan X. ; Cheng H. C. ; Huang Y. ; Duan X. Nat. Rev. Mater. 2016, 1, 16042. doi: 10.1038/natrevmats.2016.42
2	Lin L. ; Liu Z. Nat. Mater. 2016, 15, 9. doi: 10.1038/nmat4498
3	Zhu S. ; Geng X. ; Han Y. ; Benamara M. ; Chen L. ; Li J. ; Bilgin I. ; Zhu H. NPJ Comput. Mater. 2017, 3, 41. doi: 10.1038/s41524-017-0041-z
4	Xie G. ; Ju Z. ; Zhou K. ; Wei X. ; Guo Z. ; Cai Y. ; Zhang G. NPJ Comput. Mater. 2018, 4, 21. doi: 10.1038/s41524-018-0076-9
5	Yoon Y. ; Ganapathi K. ; Salahuddin S. Nano Lett. 2011, 11, 3768. doi: 10.1021/nl2018178
6	Qiu H. ; Xu T. ; Wang Z. ; Ren W. ; Nan H. ; Ni Z. ; Chen Q. ; Yuan S. ; Miao F. ; Song F. ; et al Nat. Commun. 2013, 4, 2642. doi: 10.1038/ncomms3642
7	Yu Z. ; Pan Y. ; Shen Y. ; Wang Z. ; Ong Z. Y. ; Xu T. ; Xin R. ; Pan L. ; Wang B. ; Sun L. ; et al Nat. Commun. 2014, 5, 5290. doi: 10.1038/ncomms6290
8	Mak K. F. ; Lee C. ; Hone J. ; Shan J. ; Heinz T. F. Phys. Rev. Lett. 2010, 105, 136805. doi: 10.1103/PhysRevLett.105.136805
9	Chu T. ; Ilatikhameneh H. ; Klimeck G. ; Rahman R. ; Chen Z. Nano Lett. 2015, 15, 8000. doi: 10.1021/acs.nanolett.5b03218
10	Tang D. M. ; Kvashnin D. G. ; Najmaei S. ; Bando Y. ; Kimoto K. ; Koskinen P. ; Ajayan P. M. ; Yakobson B. I. ; Sorokin P. B. ; Lou J. ; et al Nat. Commun. 2014, 5, 3631. doi: 10.1038/ncomms4631
11	Ottaviano L. ; Palleschi S. ; Perrozzi F. ; D'Olimpio G. ; Priante F. ; Donarelli M. ; Benassi P. ; Nardone M. ; Gonchigsuren M. ; Gombosuren M. ; et al 2D Mater. 2017, 4, 045013. doi: 10.1088/2053-1583/aa8764
12	Coleman J. N. ; Lotya M. ; O'Neill A. ; Bergin S. D. ; King P. J. ; Khan U. ; Young K. ; Gaucher A. ; De S. ; Smith R. J. ; et al Science 2011, 331, 568. doi: 10.1126/science.1194975
13	Liu Y. ; He X. ; Hanlon D. ; Harvey A. ; Coleman J. N. ; Li Y. ACS Nano 2016, 10, 8821. doi: 10.1021/acsnano.6b04577
14	Mohiuddin M. ; Wang Y. ; Zavabeti A. ; Syed N. ; Datta R. S. ; Ahmed H. ; Daeneke T. ; Russo S. P. ; Rezk A. R. ; Yeo L. Y. ; et al Chem. Mater. 2018, 30, 5593. doi: 10.1021/acs.chemmater.8b01506
15	Najmaei S. ; Liu Z. ; Zhou W. ; Zou X. ; Shi G. ; Lei S. ; Yakobson B. I. ; Idrobo J. C. ; Ajayan P. M. ; Lou J. Nat. Mater. 2013, 12, 754. doi: 10.1038/NMAT3673
16	Lee Y. H. ; Yu L. ; Wang H. ; Fang W. ; Ling X. ; Shi Y. ; Lin C. T. ; Huang J. K. ; Chang M. T. ; Chang C. S. ; et al Nano Lett. 2013, 13, 1852. doi: 10.1021/nl400687n
17	Shi J. ; Ma D. ; Han G. F. ; Zhang Y. ; Ji Q. ; Gao T. ; Sun J. ; Song X. ; Li C. ; Zhang Y. ; et al ACS Nano 2014, 8, 10196. doi: 10.1021/nn503211t
18	Wang S. ; Rong Y. ; Fan Y. ; Pacios M. ; Bhaskaran H. ; He K. ; Warner J. H. Chem. Mater. 2014, 26, 6371. doi: 10.1021/cm5025662
19	Chen W. ; Zhao J. ; Zhang J. ; Gu L. ; Yang Z. ; Li X. ; Yu H. ; Zhu X. ; Yang R. ; Shi D. ; et al J. Am. Chem. Soc. 2015, 137, 15632. doi: 10.1021/jacs.5b10519
20	Yu H. ; Liao M. ; Zhao W. ; Liu G. ; Zhou X. J. ; Wei Z. ; Xu X. ; Liu K. ; Hu Z. ; Deng K. ; et al ACS Nano 2017, 11, 12001. doi: 10.1021/acsnano.7b03819
21	Chen S. ; Gao J. ; Bharathi M. S. ; Zhang G. ; Sorkin V. ; Ramanarayan H. ; Zhang Y. W. 2D Mater. 2019, 6, 015031. doi: 10.1088/2053-1583/aaf59c
22	Gao J. ; Xu Z. ; Chen S. ; Bharathi M. S. ; Zhang Y. W. Adv. Theory Simul. 2018, 1, 1800085. doi: 10.1002/adts.201800085
23	Gao J. ; Yip J. ; Zhao J. ; Yakobson B. I. ; Ding F. J. Am. Chem. Soc. 2011, 133, 5009. doi: 10.1021/ja110927p
24	Yuan Q. ; Gao J. ; Shu H. ; Zhao J. ; Chen X. ; Ding F. J. Am. Chem. Soc. 2012, 134, 2970. doi: 10.1021/ja2050875
25	Niu T. ; Zhou M. ; Zhang J. ; Feng Y. ; Chen W. J. Am. Chem. Soc. 2013, 135, 8409. doi: 10.1021/ja403583s
26	Wu P. ; Zhang Y. ; Cui P. ; Li Z. ; Yang J. ; Zhang Z. Phys. Rev. Lett. 2015, 114, 216102. doi: 10.1103/PhysRevLett.114.216102
27	Gao J. ; Zhao J. ; Ding F. J. Am. Chem. Soc. 2012, 134, 6204. doi: 10.1021/ja2104119
28	Artyukhov V. I. ; Liu Y. ; Yakobson B. I. Proc. Natl. Acad. Sci. USA 2012, 109, 15136. doi: 10.1073/pnas.1207519109
29	Wu P. ; Jiang H. ; Zhang W. ; Li Z. ; Hou Z. ; Yang J. J. Am. Chem. Soc. 2012, 134, 6045. doi: 10.1021/ja301791x
30	Zhang X. ; Wang L. ; Xin J. ; Yakobson B. I. ; Ding F. J. Am. Chem. Soc. 2014, 136, 3040. doi: 10.1021/ja405499x
31	Lee G. D. ; Wang C. Z. ; Yoon E. ; Hwang N. M. ; Kim D. Y. ; Ho K. M. Phys. Rev. Lett. 2005, 95, 205501. doi: 10.1103/PhysRevLett.95.205501
32	Wang L. ; Zhang X. ; Chan H. L. ; Yan F. ; Ding F. J. Am. Chem. Soc. 2013, 135, 4476. doi: 10.1021/ja312687a
33	Ma T. ; Ren W. ; Zhang X. ; Liu Z. ; Gao Y. ; Yin L. C. ; Ma X. L. ; Ding F. ; Cheng H. M. Proc. Natl. Acad. Sci. USA 2013, 110, 20386. doi: 10.1073/pnas.1312802110
34	Bharathi M. S. ; Hao Y. ; Ramanarayan H. ; Rywkin S. ; Hone J. C. ; Colombo L. ; Ruoff R. S. ; Zhang Y. W. ACS Nano 2018, 12, 9372. doi: 10.1021/acsnano.8b04460
35	Artyukhov V. I. ; Hu Z. ; Zhang Z. ; Yakobson B. I. Nano Lett. 2016, 16, 3696. doi: 10.1021/acs.nanolett.6b00986
36	Hong S. ; Krishnamoorthy A. ; Rajak P. ; Tiwari S. ; Misawa M. ; Shimojo F. ; Kalia R. K. ; Nakano A. ; Vashishta P. Nano Lett. 2017, 17, 4866. doi: 10.1021/acs.nanolett.7b01727
37	Ye H. ; Zhou J. ; Er D. ; Price C. C. ; Yu Z. ; Liu Y. ; Lowengrub J. ; Lou J. ; Liu Z. ; Shenoy V. B. ACS Nano 2017, 11, 12780. doi: 10.1021/acsnano.7b07604
38	Nie Y. ; Liang C. ; Zhang K. ; Zhao R. ; Eichfeld S. M. ; Cha P. R. ; Colombo L. ; Robinson J. A. ; Wallace R. M. ; Cho K. 2D Mater. 2016, 3, 025029. doi: 10.1088/2053-1583/3/2/025029
39	Rajan A. G. ; Warner J. H. ; Blankschtein D. ; Strano M. S. ACS Nano 2016, 10, 4330. doi: 10.1021/acsnano.5b07916
40	Yue R. ; Nie Y. ; Walsh L. A. ; Addou R. ; Liang C. ; Lu N. ; Barton A. T. ; Zhu H. ; Che Z. ; Barrera D. ; et al 2D Mater. 2017, 4, 045019. doi: 10.1088/2053-1583/aa8ab5
41	Chang C. H. ; Fan X. ; Lin S. H. ; Kuo J. L. Phys. Rev. B 2013, 88, 195420. doi: 10.1103/PhysRevB.88.195420
42	Shu H. ; Chen X. ; Tao X. ; Ding F. ACS Nano 2012, 6, 3243. doi: 10.1021/nn300726r
43	Gao Y. ; Hong Y. L. ; Yin L. C. ; Wu Z. ; Yang Z. ; Chen M. L. ; Liu Z. ; Ma T. ; Sun D. M. ; Ni Z. ; et al Adv. Mater. 2017, 29, 1700990. doi: 10.1002/adma.201700990
44	Xue X. X. ; Feng Y. ; Chen K. ; Zhang L. J. Chem. Phys. 2018, 148, 134704. doi: 10.1063/1.5010996

[1]	刘芳,张鲁凤,董倩,陈卓. 小尺寸金石墨纳米颗粒的合成与表征[J]. 物理化学学报, 2019, 35(6): 651 -656 .
[2]	王琴,薛珉敏,张助华. 硼烯化学合成进展与展望[J]. 物理化学学报, 2019, 35(6): 565 -571 .
[3]	王可心,史刘嵘,王铭展,杨皓,刘忠范,彭海琳. 生物质羟基磷灰石作为模板制备三维石墨烯[J]. 物理化学学报, 2019, 35(10): 1112 -1118 .
[4]	张驰,吴志娇,刘建军,朴玲钰. MoS₂/TiO₂复合催化剂的制备及其在紫外光下的光催化制氢活性[J]. 物理化学学报, 2017, 33(7): 1492 -1498 .
[5]	王辉,邹德春. 硫粉为硫源,多元醇辅助合成硫化钼纳米片[J]. 物理化学学报, 2017, 33(5): 1027 -1032 .
[6]	赵立平,孟未帅,王宏宇,齐力. 二硫化钼-碳复合材料用作钠离子电容电池负极材料[J]. 物理化学学报, 2017, 33(4): 787 -794 .
[7]	邢垒,焦丽颖. 二硫化钼二维原子晶体化学掺杂研究进展[J]. 物理化学学报, 2016, 32(9): 2133 -2145 .
[8]	刘庆彬,蔚翠,何泽召,王晶晶,李佳芦,伟立,冯志红. 蓝宝石衬底上化学气相沉积法生长石墨烯[J]. 物理化学学报, 2016, 32(3): 787 -792 .
[9]	陈旭东,陈召龙,孙靖宇,张艳锋,刘忠范. 石墨烯玻璃：玻璃表面上石墨烯的直接生长[J]. 物理化学学报, 2016, 32(1): 14 -27 .
[10]	乔治, 解新建, 薛俊明, 刘辉, 梁李敏, 郝秋艳, 刘彩池. nc-Si:H/c-Si硅异质结太阳电池中本征硅薄膜钝化层的优化[J]. 物理化学学报, 2015, 31(6): 1207 -1214 .
[11]	邵妍,欧阳方平,彭盛霖,刘琦,贾治安,邹慧. 扶手椅型缺陷硫化钼纳米带电子性质的第一性原理计算[J]. 物理化学学报, 2015, 31(11): 2083 -2090 .
[12]	杨志雄, 杨金新, 刘琦, 谢禹鑫, 熊翔, 欧阳方平. 扶手椅型二硫化钼纳米带的电子结构与边缘修饰[J]. 物理化学学报, 2013, 29(08): 1648 -1654 .
[13]	汤鹏, 肖坚坚, 郑超, 王石, 陈润锋. 类石墨烯二硫化钼及其在光电子器件上的应用[J]. 物理化学学报, 2013, 29(04): 667 -677 .
[14]	常大磊, 李小松, 赵天亮, 朱爱民. 大气压射频等离子体化学气相沉积TiO₂体系的发射光谱诊断[J]. 物理化学学报, 2013, 29(03): 625 -630 .
[15]	张艳锋, 高腾, 张玉, 刘忠范. 金属衬底上石墨烯的控制生长和微观形貌的STM表征[J]. 物理化学学报, 2012, 28(10): 2456 -2464 .