Electronic theoretical study on sensing behaviors of defects and doping coexistence of black phosphorene to formaldehyde

Zhang Guo-Ying; Jiao Xing-Qiang; Liu Ye-Shu; Zhang An-Guo; Meng Chun-Xue

doi:10.7498/aps.69.20200990

Abstract

Black phosphorene (BP) has a high specific surface area due to its puckered honeycomb lattice structure, so it has great advantages in gas sensor applications. Doping and defects have a great effect on its sensitivity. Our aim is to obtain an insight into the sensing mechanism of black phosphorene towards CH₂O, a hazardous organic compound. Based on the first-principles method of density functional theory (DFT), the sensing behaviors of the BP system, with intrinsic, Al doped, P vacancy-defected and P-vacancy and Al doping coexistent, before and after CH₂O adsorption are studied. By establishing the structural models of four BP systems, the values of adsorption energy, energy band structure and charge transfer are calculated. Calculation results show that CH₂O molecule prefers to be adsorbed perpendicular to the P vacancy-defected BP nanosheet with oxygen atom on the top site and close to the sheet. For the intrinsic, Al doped, P-vacancy and Al doping coexisting BP nanosheet, the CH₂O molecule tilts towards the sheet surface. It is found that the CH₂O adsorption on intrinsic BP nanosheet (adsorption energy is 0.179 eV) is very weak. In contrast, the adsorption of CH₂O to the BP systems, with P vacancy-defected BP, Al doped, P-vacancy and Al doping coexistent, shows relatively high affinity (0.875, 0.542, 0.824 eV). Thus, Al doping, P vacancy or P-vacancy and Al-doping coexistence can substantially improve the adsorption ability of BP systems towards CH₂O. In order to investigate the sensing mechanism of BP systems, the electronic properties such as the density of states, energy band and charge transfer are calculated. The change of energy gap of intrinsic BP nanosheet before and after CH₂O adsorption is 0.024 eV, and that for P vacancy-defected BP nanosheet is zero. In addition, P atom vacancy has no effect on charge transfer. These suggest that the conductivity of intrinsic BP or P vacancy-defected BP nanosheet has not obviously changed, thereby, they are not suitable for sensor materials. For the BP system with Al doping or the coexistence of P vacancy and Al doping, it is obviously seen that an impurity level is generated in the energy band diagram, the effective band gap is significantly narrowed, indicating that the Al doping improves the sensitivity of BP. In addition, the charge transfer is significantly increased, which changes the carrier concentration and improves the electrical conductivity. Therefore, the BP system with Al doping or the coexistence of P vacancy and Al doping is expected to become a kind of new sensor material.

Keywords:

Authors and contacts

1.
College of Physics Science and Technology, Shenyang Normal University, Shenyang 110034, China
2.
College of Life and Health Sciences, Northeastern University, Shenyang 110819, China

Corresponding author: Zhang Guo-Ying, Gyzhang1965@sina.com

Funds: Project supported by the General Scientific Research Project of Education Bureau of Liaoning Province, China (Grant No. LZGD2019003)

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References

[1]	Su S, Wu W H, Gao J M, Lu J X, Fang C H 2012 J. Mater. Chem. 22 18101 Google Scholar
[2]	Schwierz F, Pezoldt J, Granzner R 2015 Nanoscale 7 8261 Google Scholar
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[8]	Liu S Y, Jiao X Q, Zhang G Y 2019 Chem. Phys. Lett. 726 77 Google Scholar
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[17]	Segall M D, Lndan P L D, Probert M J, Pickard C J, Hasnip P J, Clark S J, Payne M C 2002 J. Phy. Condens. Matter 14 2717 Google Scholar
[18]	Perdew J P, Chevary J A, Vosko S H, Jackson K A, Pederson M R, Singh D J, Fiolhais C 1992 Phys. Rev. B 46 6671 Google Scholar
[19]	Qiao J S, Kong X H, Hu Z X, Yang F, Ji W 2014 Nat. Commun. 5 4475 Google Scholar
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图 1 (a) 本征、(b) 掺杂Al、(c) 含P空位及(d) P空位与Al掺杂共存时BP烯甲醛吸附系统超原胞

Figure 1. The supercells of CH₂O/BP adsorption systems: (a) Intrinsic BP; (b) Al doped BP; (c) BP containing P vacancies; (d) BP with the coexistence of P-vacancies and Al doping.

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图 2 本征、Al掺杂、含P空位、P空位和Al掺杂共存时吸附或未吸附CH₂O的BP态密度图　(a), (b) 各BP烯体系的总态密度和不同原子的局域态密度图; (c), (d) 各吸附CH₂O的BP烯体系的总态密度和不同原子的局域态密度图

Figure 2. The density of state of intrinsic, Al doped, P vacancy contained, P vacancy and Al doping coexisted BP with or without CH₂O adsorption: (a), (b) The total density of state and the local density of state of different atoms of each BP system; (c), (d) the total density of state and the local density of state of different atoms of each BP system with CH₂O adsorption.

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图 3 本征、Al掺杂、P空位、P空位和Al掺杂共存时吸附或未吸附CH₂O的BP的能带图　(a) 本征BP烯; (b) 本征BP烯吸附CH₂O; (c) 含P原子空位的BP烯; (d) 含P原子空位的BP烯吸附CH₂O; (e) Al掺杂的BP烯; (f) Al掺杂BP烯吸附CH₂O; (g) P空位和Al掺杂共存的BP烯; (h) P空位和Al掺杂共存BP烯吸附CH₂O

Figure 3. The energy band of intrinsic, Al doped, P vacancy contained, P vacancy and Al doping coexisted BP with or without CH₂O adsorption: (a) Intrinsic BP; (b) intrinsic BP after adsorption of CH₂O; (c) BP with P atom vacancy; (d) P atom vacancy contained BP after adsorption of CH₂O; (e) Al doped BP; (f) Al doped BP after adsorption of CH₂O; (g) P vacancy and Al doped coexisted BP; (h) P vacancy and Al doped coexisted BP after adsorption of CH₂O.

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表 1 考虑和不考虑自旋极化、取不同截断能和不同k点时计算的黑磷体材料的能隙和晶格参数

Table 1. Calculated energy gap and lattice parameters of bulk black phosphor using different cut-off energies and different k points considering or disregarding spin polarization.

截断能与k点/不加自旋	参数
截断能与k点/不加自旋	E_g/ eV	a/Å	b/Å	c/Å
300 eV/2 × 2 × 2	0.603	3.162	12.399	4.809
300 eV/3 × 3 × 3	0.358	3.348	11.195	4.549
320 eV/3 × 3 × 3	0.455	3.342	11.418	4.588
400 eV/3 × 3 × 3	0.490	3.340	11.466	4.598
300 eV/4 × 4 × 4	0.113	3.239	11.324	4.597
截断能与k点/加自旋	参数
截断能与k点/加自旋	E_g/eV	a/Å	b/Å	c/Å
280 eV/3 × 3 × 3	0.178	3.350	11.137	4.485
300 eV 3 × 3 × 3	0.343	3.370	11.103	4.515
320 eV/3 × 3 × 3	0.239	3.346	11.277	4.501

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表 2 BP或CH₂O/BP中存在P空位、Al掺杂或P空位-Al掺杂对时的缺陷形成能

Table 2. Defect formation energies of P vacancy, Al impurity, or P-vacancy and Al impurity pair in BP or CH₂O/BP.

E_f/eV	Al_P	P_V	Al_P + P_V
BP	0.256	2.325	0.878
CH₂O/BP	–0.107	1.631	0.234

DownLoad: CSV

表 3 本征、P空位、Al掺杂、P空位与Al掺杂共存时BP烯吸附甲醛的优化结构参数

Table 3. The optimal structure parameters of intrinsic, P-vacancy contained, Al doping, P-vacancy and Al doping coexisted BP systems adsorbed formaldehyde molecule.

基底	E_ad/eV	D(CH₂O—BP) /Å	L(C—O)/Å
本征	0.179	3.180	1.221
P空缺	0.875	4.007	1.223
Al掺杂	0.542	1.840	1.247
Al掺杂P空缺共存	0.824	1.886	1.265

DownLoad: CSV

表 4 甲醛分子及各原子的电荷得失

Table 4. The charge gain or loss of formaldehyde molecule and its atoms.

基底	电荷/e
基底	H	H	C	O	ΔQ
本征	0.28	0.28	–0.06	–0.50	0
P空缺	0.27	0.27	–0.06	–0.48	0
Al掺杂	0.34	0.33	–0.13	–0.58	–0.04
Al掺杂与P空缺	0.31	0.34	–0.19	–0.61	–0.15

DownLoad: CSV

map

[1]	Su S, Wu W H, Gao J M, Lu J X, Fang C H 2012 J. Mater. Chem. 22 18101 Google Scholar
[2]	Schwierz F, Pezoldt J, Granzner R 2015 Nanoscale 7 8261 Google Scholar
[3]	Perkins F K, Friedman A L, Cobas E, Campbell P M, Jernigan G G, Jonker B T 2013 Nano. Lett. 13 668 Google Scholar
[4]	Schedin F, Geim A K, Morozov S V, Hill E W, Blake P, Katsnelson M I, Novoselov K S 2007 Nat. Mater. 6 652 Google Scholar
[5]	陈浩, 彭同江, 刘波, 孙红娟, 雷德会 2017 66 080701 Google Scholar Chen H, Peng T J, Liu B, Sun H J, Lei D H 2017 Acta Phys. Sin. 66 080701 Google Scholar
[6]	孙建平, 缪应蒙, 曹相春 2013 62 036301 Google Scholar Sun J P, Liao Y M, Cao X C 2013 Acta Phys. Sin. 62 036301 Google Scholar
[7]	Samadizadeh M, Peyghan A A, Rastegar S F 2015 Chin. Chem. Lett. 26 1042 Google Scholar
[8]	Liu S Y, Jiao X Q, Zhang G Y 2019 Chem. Phys. Lett. 726 77 Google Scholar
[9]	Li L C, Yu Y J, Ye G J, Ge Q Q, Ou X D, Wu H, Fang D L, Chen X H, Zhang Y B 2014 Nat. Nanotechnol. 9 372 Google Scholar
[10]	Yang A J, Wang D W, Wang X H, Zhang D Z, Koratkar N, Rong M Z 2018 Nano Today 20 13 Google Scholar
[11]	Kou L Z, Frauenheim T, Chen C F 2014 Phys. Chem. Lett. 5 2675 Google Scholar
[12]	Sun X L, Luan S, Shen H Y, Lei S Y 2018 Superlattices Microstruct. 124 168 Google Scholar
[13]	王晶儒, 岑超, 蔡绍洪 2016 贵州师范学院学报 32 17 Google Scholar Wang J R, Cen C, Cai S H 2016 J. Guizhou Norm. Coll. 32 17 Google Scholar
[14]	Xu Y, Gao W L 2018 J. Alloys and Compd. 737 365 Google Scholar
[15]	张国英, 焦兴强, 刘贵立 2020 沈阳师范大学学报 38 23 Google Scholar Zhang G Y, Jiao X Q, Liu G L 2020 J. Shenyang Norm. Univ. (Nat. Sci. Ed.) 38 23 Google Scholar
[16]	原卫华, 毕世华, 曹茂盛 2015 材料导报 29 156 Google Scholar Yuan W H, Bi S H, Cao M S 2015 Mate. Rep. 29 156 Google Scholar
[17]	Segall M D, Lndan P L D, Probert M J, Pickard C J, Hasnip P J, Clark S J, Payne M C 2002 J. Phy. Condens. Matter 14 2717 Google Scholar
[18]	Perdew J P, Chevary J A, Vosko S H, Jackson K A, Pederson M R, Singh D J, Fiolhais C 1992 Phys. Rev. B 46 6671 Google Scholar
[19]	Qiao J S, Kong X H, Hu Z X, Yang F, Ji W 2014 Nat. Commun. 5 4475 Google Scholar
[20]	Brown A, Rundqvist S 1965 Acta Cryst. 19 684 Google Scholar
[21]	Fei R X, Yang L 2014 Nano Lett. 14 2884 Google Scholar
[22]	Henkelmzn G, Arnaldsson A, Jonsson H 2006 Comput. Mater. Sci. 36 354 Google Scholar
[23]	Peyghan A A, Hadipour N L, Bagheri Z 2013 J. Phys. Chem. C 117 2427
[24]	Zhang Y H, Han L F, Xiao Y H, Jia D Z 2013 Comput. Mater. Sci. 69 222 Google Scholar

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