Kinetic Monte Carlo simulations of plasma-surface reactions on heterogeneous surfaces

doi:10.1007/s11705-019-1837-9

Front. Chem. Sci. Eng.

2019, Vol. 13

Issue (4) : 815-822 https://doi.org/10.1007/s11705-019-1837-9

RESEARCH ARTICLE

Kinetic Monte Carlo simulations of plasma-surface reactions on heterogeneous surfaces

Daniil Marinov(

)

IMEC, 3001 Leuven, Belgium

Download: PDF(255 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

Reactions of atoms and molecules on chamber walls in contact with low temperature plasmas are important in various technological applications. Plasma-surface interactions are complex and relatively poorly understood. Experiments performed over the last decade by several groups prove that interactions of reactive species with relevant plasma-facing materials are characterized by distributions of adsorption energy and reactivity. In this paper, we develop a kinetic Monte Carlo (KMC) model that can effectively handle chemical kinetics on such heterogenous surfaces. Using this model, we analyse published adsorption-desorption kinetics of chlorine molecules and recombination of oxygen atoms on rotating substrates as a test case for the KMC model.

Keywords plasma-surface interaction kinetic Monte Carlo plasma nano technology

Corresponding Author(s): Daniil Marinov

Just Accepted Date: 24 June 2019 Online First Date: 27 August 2019 Issue Date: 04 December 2019

Cite this article:

Daniil Marinov. Kinetic Monte Carlo simulations of plasma-surface reactions on heterogeneous surfaces[J]. Front. Chem. Sci. Eng., 2019, 13(4): 815-822.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1837-9
https://academic.hep.com.cn/fcse/EN/Y2019/V13/I4/815

Fig.1 Desorption flux of Cl₂ from rotating anodized alumina substrate as a function of the rotation (delay) time. Experimental data from [²³] measured at different Cl₂ gas pressures are depicted with open symbols. Results of KMC simulations are shown with solid lines.

Fig.2 Assumed Gaussian distribution of adsorption site density over binding energy (left y-axis) and the corresponding characteristic desorption time as a function of the binding energy (right y-axis). The hatched area indicates the interval of characteristic desorption times that can be covered by the spinning wall technique. The part of the distribution that contributes to experimentally measured desorption fluxes is highlighted in red.

Fig.3 Desorption flux of O₂ formed by recombination of oxygen atoms on silica-coated rotating substrate. Experimental data are taken from [³¹],

P O 2

= 1.5 mTorr, 400 W plasma power. KMC simulations were performed assuming the delayed desorption mechanism with two types of active sites (with O₂ desorption energies 0.798 and 0.715 eV).

Fig.4 Recombination probability of atomic oxygen on silica as a function of the reciprocal substrate temperature calculated using KMC with the standard model [¹⁶] and assuming the delayed desorption mechanism with two types of active sites.

Fig.5 KMC calculation of recombination probability of atomic oxygen on a model surface with an assumed Gaussian distribution of energy barriers for recombination (E_R) centered at 0.18 eV. Different curves correspond to different FWHM of the Gaussian distribution.

Fig.6 Distributions of recombination events among chemisorption sites caused by a distribution of energy barriers for recombination E_R. The assumed Gaussian distribution (FWHM= 0.06 eV) of surface site density over E_R is shown with a dotted line.

1	V M Donnelly, A Kornblit. Plasma etching: Yesterday, today, and tomorrow. Journal of Vacuum Science & Technology. A, Vacuum, Surfaces, and Films, 2013, 31(5): 050825–050872 https://doi.org/10.1116/1.4819316
2	D Zhang, M J Kushner. Investigations of surface reactions during C2F6 plasma etching of SiO2 with equipment and feature scale models. Journal of Vacuum Science & Technology. A, Vacuum, Surfaces, and Films, 2001, 19(2): 524–538 https://doi.org/10.1116/1.1349728
3	P Brichon, E Despiau-Pujo, O Mourey, O Joubert. Key plasma parameters for nanometric precision etching of Si films in chlorine discharges. Journal of Applied Physics, 2015, 118(5): 053303–053312 https://doi.org/10.1063/1.4928294
4	M E Barone, D B Graves. Molecular-dynamics simulations of direct reactive ion etching of silicon by fluorine and chlorine. Journal of Applied Physics, 1995, 78(11): 6604–6617 https://doi.org/10.1063/1.360482
5	J Benedikt, R V Woen, S L M van Mensfoort, V Perina, J Hong, M C M van de Sanden. Plasma chemistry during the deposition of a-C:H films and its influence on film properties. Diamond and Related Materials, 2003, 12(2): 90–97 https://doi.org/10.1016/S0925-9635(03)00008-6
6	D G Tsalikis, C Baig, V G Mavrantzas, E Amanatides, D Mataras. A hybrid kinetic Monte Carlo method for simulating silicon films grown by plasma-enhanced chemical vapor deposition. Journal of Chemical Physics, 2013, 139(20): 204706–204719 https://doi.org/10.1063/1.4830425
7	M Crose, J Sang-Il Kwon, M Nayhouse, D Ni, P D Christofides. Multiscale modeling and operation of PECVD of thin film solar cells. Chemical Engineering Science, 2015, 136: 50–61 https://doi.org/10.1016/j.ces.2015.02.027
8	I Zyulkov, M Krishtab, S De Gendt, S Armini. Selective Ru ALD as a catalyst for sub-seven-nanometer bottom-up metal interconnects. ACS Applied Materials & Interfaces, 2017, 9(36): 31031–31041 https://doi.org/10.1021/acsami.7b07811
9	A von Keudell, W Möller. A combined plasma-surface model for the deposition of C:H films from a methane plasma. Journal of Applied Physics, 1994, 75(12): 7718–7727 https://doi.org/10.1063/1.356603
10	E C Neyts. PECVD growth of carbon nanotubes: From experiment to simulation. Journal of Vacuum Science & Technology. B, Microelectronics and Nanometer Structures : Processing, Measurement, and Phenomena : An Official Journal of the American Vacuum Society, 2012, 30: 030803–030819
11	E C Neyts, K Ostrikov, M K Sunkara, A Bogaerts. Plasma catalysis: Synergistic effects at the nanoscale. Chemical Reviews, 2015, 115(24): 13408–13446 https://doi.org/10.1021/acs.chemrev.5b00362
12	H H Kim. Nonthermal plasma processing for air-pollution control: A historical review, current issues, and future prospects. Plasma Processes and Polymers, 2004, 1(2): 91–110 https://doi.org/10.1002/ppap.200400028
13	E C Neyts, A Bogaerts. Understanding plasma catalysis through modelling and simulation—a review. Journal of Physics. D, Applied Physics, 2014, 47(22): 224010–224027 https://doi.org/10.1088/0022-3727/47/22/224010
14	R Meana-Pañeda, Y Paukku, K Duanmu, P Norman, T E Schwartzentruber, D G Truhlar. Atomic oxygen recombination at surface defects on reconstructed (0001) α-quartz exposed to atomic and molecular oxygen. Journal of Physical Chemistry C, 2015, 119(17): 9287–9301 https://doi.org/10.1021/acs.jpcc.5b00120
15	E C Neyts, P Brault. Molecular dynamics simulations for plasma-surface interactions. Plasma Processes and Polymers, 2017, 14(1-2): 1600145–1600164 https://doi.org/10.1002/ppap.201600145
16	D Marinov, C Teixeira, V Guerra. Deterministic and Monte Carlo methods for simulation of plasma-surface interactions. Plasma Processes and Polymers, 2017, 14(1-2): 1600175–1600192 https://doi.org/10.1002/ppap.201600175
17	V Guerra, D Marinov. Dynamical Monte Carlo methods for plasma-surface reactions. Plasma Sources Science & Technology, 2016, 25(4): 045001–045016 https://doi.org/10.1088/0963-0252/25/4/045001
18	H M Cuppen, L J Karssemeijer, T Lamberts. The kinetic Monte Carlo method as a way to solve the master equation for interstellar grain chemistry. Chemical Reviews, 2013, 113(12): 8840–8871 https://doi.org/10.1021/cr400234a
19	P Norman, T E Schwartzentruber, H Leverentz, S Luo, R Meana-Paneda, Y Paukku, D G Truhlar. The structure of silica surfaces exposed to atomic oxygen. Journal of Physical Chemistry C, 2013, 117(18): 9311–9321 https://doi.org/10.1021/jp4019525
20	M Stamatakis. Kinetic modelling of heterogeneous catalytic systems. Journal of Physics Condensed Matter, 2015, 27(1): 013001–013028 https://doi.org/10.1088/0953-8984/27/1/013001
21	M Rutigliano, C Zazza, N Sanna, A Pieretti, G Mancini, V Barone, M Cacciatore. Oxygen adsorption on β-cristobalite polymorph: ab initio modeling and semiclassical time-dependent dynamics. Journal of Physical Chemistry A, 2009, 113(52): 15366–15375 https://doi.org/10.1021/jp9066026
22	J Guha, P Kurunczi, L Stafford, V M Donnelly, Y K Pu. In-situ surface recombination measurements of oxygen atoms on anodized aluminum in an oxygen plasma. Journal of Physical Chemistry C, 2008, 112(24): 8963–8968 https://doi.org/10.1021/jp800788a
23	V M Donnelly, J Guha, L Stafford. Critical review: Plasma-surface reactions and the spinning wall method. Journal of Vacuum Science & Technology. A, Vacuum, Surfaces, and Films, 2011, 29(1): 010801–010825 https://doi.org/10.1116/1.3517478
24	J Guha, V M Donnelly. Studies of chlorine-oxygen plasmas and evidence for heterogeneous formation of ClO and ClO2. Journal of Applied Physics, 2009, 105(11): 113307–113316 https://doi.org/10.1063/1.3129543
25	D Marinov, O Guaitella, A Rousseau, Y Ionikh. Production of molecules on a surface under plasma exposure: Example of NO on pyrex. Journal of Physics. D, Applied Physics, 2010, 43(11): 115203–115209 https://doi.org/10.1088/0022-3727/43/11/115203
26	V Guerra, D Marinov, O Guaitella, A Rousseau. NO oxidation on plasma pretreated Pyrex: The case for a distribution of reactivity of adsorbed O atoms. Journal of Physics. D, Applied Physics, 2014, 47(22): 224012–224023 https://doi.org/10.1088/0022-3727/47/22/224012
27	O Guaitella, C Lazzaroni, D Marinov, A Rousseau. Evidence of atomic adsorption on TiO2 under plasma exposure and related C2H2 surface reactivity. Applied Physics Letters, 2010, 97(1): 011502–011504 https://doi.org/10.1063/1.3462295
28	D Marinov, O Guaitella, T de los Arcos, A von Keudell, A Rousseau. Adsorption and reactivity of nitrogen atoms on silica surface under plasma exposure. Journal of Physics. D, Applied Physics, 2014, 47(47): 475204–475214 https://doi.org/10.1088/0022-3727/47/47/475204
29	Y C Kim, M Boudart. Recombination of oxygen, nitrogen, and hydrogen atoms on silica: Kinetics and mechanism. Langmuir, 1991, 7(12): 2999–3005 https://doi.org/10.1021/la00060a016
30	V Guerra. Analytical model of heterogeneous atomic recombination on silicalike surfaces. IEEE Transactions on Plasma Science, 2007, 35(5): 1397–1412 https://doi.org/10.1109/TPS.2007.902028
31	L Stafford, J Guha, R Khare, S Mattei, O Boudreault, B Clain, V M Donnelly. Experimental and modeling study of O and Cl atoms surface recombination reactions in O2 and Cl2 plasmas. Pure and Applied Chemistry, 2010, 82(6): 1301–1315 https://doi.org/10.1351/PAC-CON-09-11-02
32	V Guerra, F M Dias, J Loureiro, P A Sá, P Supiot, C, Dupret T Popov. Time-dependence of the electron energy distribution function in the nitrogen afterglow. IEEE Transactions on Plasma Science, 2003, 31(4): 542–552 https://doi.org/10.1109/TPS.2003.815485
33	D T Gillespie. A general method for numerically simulating the stochastic time evolution of coupled chemical reactions. Journal of Computational Physics, 1976, 22(4): 403–434 https://doi.org/10.1016/0021-9991(76)90041-3
34	P F Kurunczi, J Guha, V M Donnelly. Recombination reactions of oxygen atoms on an anodized aluminum plasma reactor wall, studied by a spinning wall method. Journal of Physical Chemistry B, 2005, 109(44): 20989–20998 https://doi.org/10.1021/jp054190h
35	L Stafford, J Guha, V M Donnelly. Recombination probability of oxygen atoms on dynamic stainless steel surfaces in inductively coupled O2 plasmas. Journal of Vacuum Science & Technology. A, Vacuum, Surfaces, and Films, 2008, 26(3): 455–461 https://doi.org/10.1116/1.2902953
36	J Guha, R Khare, L Stafford, V M Donnelly, S Sirard, E A Hudson. Effect of Cu contamination on recombination of O atoms on a plasma-oxidized silicon surface. Journal of Applied Physics, 2009, 105(11): 113309–113316 https://doi.org/10.1063/1.3143107
37	C Janssen, B Tuzson. Isotope evidence for ozone formation on surfaces. Journal of Physical Chemistry A, 2010, 114(36): 9709–9719 https://doi.org/10.1021/jp1017899
38	D Marinov, O Guaitella, J P Booth, A Rousseau. Direct observation of ozone formation on SiO2 surfaces in O2 discharges. Journal of Physics. D, Applied Physics, 2013, 46(3): 032001–032004 https://doi.org/10.1088/0022-3727/46/3/032001
39	D V Lopaev, E M Malykhin, S M Zyryanov. Surface recombination of oxygen atoms in O2 plasma at increased pressure: II. Vibrational temperature and surface production of ozone. Journal of Physics. D, Applied Physics, 2010, 44(1): 015202–015217 https://doi.org/10.1088/0022-3727/44/1/015202

Viewed

Full text

Abstract

Cited

Shared

Discussed