Wang, Appl. Phys. Lett., vol.102, no. 5, 2013] is studied using molecular dynamic simulation.

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1 Molecular dynamic simulation study of plasma etching L1 0 FePt media in embedded mask patterning (EMP) process Jianxin Zhu, P. Quarterman and Jian-Ping Wang Dept. of Electrical and Computer Engineering, University of Minnesota Keller Hall, 200 Union St. SE, Minneapolis, MN 55455, USA Plasma etching process of single-crystal L1 0 -FePt media [H. Wang, H. Zhao, P. Quarterman, and J.-P. Wang, Appl. Phys. Lett., vol.102, no. 5, 2013] is studied using molecular dynamic simulation. Embedded-Atom Method [M. S. Daw and M. I. Baskes, Phy. Rev. B 29, 6443 (1984); X. W. Zhou, R. A. Johnson and H. N. G. Wadley, Phy. Rev. B 69, (2004)] (EAM) is used to calculate the interatomic potential within atoms in FePt alloy, and ZBL potential [J.F. Ziegler, J. P. Biersack and U. Littmark, The Stopping and Range of Ions in Matter, Volume 1, Pergamon,1985] in comparison with conventional Lennard-Jones 12-6 potential is applied to interactions between etching gas ions and metal atoms. It is shown the post-etch structure defects can include amorphized surface layer and lattice interstitial point defects that caused by etchant ions passed through the surface layer. We show that the amorphized or damaged FePt lattice surface layer (or magnetic dead-layer ) thickness after etching increases with ion energy for Ar ion impacts, but significantly small for He ions at up to 250eV ion energy. However, we showed that He sputtering creates more interstitial defects at lower energy levels and defects are deeper below the surface compared to Ar sputtering. We also calculate the interstitial defect level and depth as dependence on ion energy for both Ar and He ions. Media magnetic property loss due to these defects is also discussed. 1

2 I. Introduction EMP process is proposed to enable ultra-small HAMR media grains by defining isolated L10-FePt grains through a granular hard-mask layer using ion-assisted methanol plasma etch process 1. In our previous modeling of EMP process, we applied a levelset analytic model with Langmuir surface kinetics to study ion and neutral effect in patterning Ru hard-mask and FePt media grains 2,3. We also found that it is critical to minimize the hard-mask erosion by reduce the ion sputtering yield on the hard-mask and to maximize the chemical etch selectivity between hard-mask and FePt media, in order to successfully define the nano-meter scaled FePt grains. For example, we showed that using He etch gas would reduce the hard-mask erosion by 1-2 orders of magnitude than using Ar gas, giving the promise to improve the etch process capability to nanometer scale. Furthermore, we would like to study the magnetic property change of remaining material that has been exposed to energetic particles (ions) and neutral etchants, which the analytic continuum model is unable to answer. Classical Molecular Dynamics (MD) simulation has been used to understand the ion sputtering and surface reaction kinetics during etching process 9, In MD model of etch process, substrate atoms, etchant particles (ions) and neutrals (molecules) are constructed in one ensemble with defined interatomic potentials. The time evolution of these particles are tracked and updated via solution of Newton s equation of motions. MD simulation has been used extensively in semiconductor research. Okada et al. have applied MD simulation to study plasma induced defects (PID) in reactive ion etch process in Ar-Si/SiO 2 system 13. They found the damaged layer thickness inside Si substrate is proportional to ion energy level to the 0.3 power. Barone et al. performed MD study of Si etch of F+ as well as Cl+ ions 14 and characterized both physical sputtering and chemical sputtering process. Nakazaki et al. also performed MD simulation in study Si etching in Cl 2 and Br based plasma etch process 12, with both Cl+/Br+ ions as well as Cl and Br neutrals in the same simulation process. Many-body Stillinger-Weber interatomic potential, which takes the form of summation of total 2-body and 3-body interatomic potential, is used in Si/SiO 2 etch process with halogen etch gas Moliere-type repulsive pair potential has been employed to account for Ar-Si 9,12,13 interactions. Recently Brault et al. 2

3 studied the atomic processes of Pt sputtering with high energy Ar ions (500-1Kev range) 9 in LAMMPS 8 simulator, using embedded-atom method (EAM) 4 potential (for Pt-Pt bond energy) and Moliere pairpotential (for Ar-Ar and Ar-Pt interactions). Their study found that sputter yield of Pt increases with Ar ion energy and the slope is in a good agreement with results from the Yamamura analytic model 10,11. II. Simulation Description Our objectives are to construct a plasma etch MD model to study the interaction mechanism between gas ions (i.e. Ar or He ions) or neutral radicals (i.e. CH 3, H, CO in methanol plasma) and Fe-Pt media atoms including sputtering yield and etch rate, and material changes including amorphized surface layer and interstitial defects inside FePt lattice. We also want to compare the MD results with the conclusions made earlier with our analytic model 2,3, particularly on the difference of Ar and He effect on sputter yield. In this report, we will focus on ion-metal impact (physical sputtering) study and we will update our research progress on neutral etch model in future publication. We use MD simulation tool LAMMPS to carry the modeling. LAMMPS stands for Large-scale Atomic/Molecular Massively Parallel Simulator. It is a classical MD code originally developed and maintained by Sandia National Labs. 1. Atomic Structure The initial structure contains 20 mono layers (MLs) of atoms stacking alternatively of Fe and Pt layers with (002) planes in c-axis. Lattice parameters are a=3.861a and c=3.788a 7. as shown in Figure 1. Total number of atoms is 3800 (1900 each for Fe and Pt). The X-Y atomic footprint is 38nm x 38nm, or 1444nm 2 of top surface area. The bottom 4 layers are fixed to prevent these atoms translating into free space from the bottom direction. Atoms in the next 6 layers upwards are thermostated to maintain the system at the set temperature 300K 12. The 10 MLs above the thermostat layer are mobile layers that are only constrained through interatomic metallic bonds. The source of etch ion particles is confined in a 3D slab about 5A above the top surface. In the sputter simulation with Helium ions we constructed a deeper structure with 20 mobile layers instead 10 used in simulation with Ar ion, considering He ions 3

4 could travel deeper into crystal as the nuclear stopping power is lower for He ions. This will be discussed in more details later in section III. 2. Interatomic Potential Selection Many-body Embedded-Atom Method 4 (EAM) interatomic potential is used for modeling metallic Fe- Fe, Pt-Pt and Fe-Pt interactions. Compared to pair potential, EAM provides better description on metallic bonds and it includes both pair-potential energy term and the embedding energy from the surrounding atoms. EAM defined as 4 : E EAM h, i 1 2 j( i) i a ( R j j ij ( R ) ij ) i F i ( h, i ) (1) Where ( R ij ) is the atom i to atom j pair potential, F i ( h,i ) is the embedding energy of atom i into the a background electron density, and j is the electron density contributed by atom j. EAM potential for single metal elements are readily available from first-principle DFT calculations 4 but difficult to obtain for metal alloys. Johnson 5 and later, Zhou 6 have developed a fitting method to determine EAM potentials for binary alloy atomic interactions directly from their mono-atomic potentials. The detailed method of creating EAM function on binary alloy can be found in reference 5 and 6. Figure 2 shows the computer generated EAM potential values as function of interatomic distance for Fe-Fe, Pt-Pt and Fe-Pt atoms using Johnson-Zhou alloy EAM model. It should be noticed that because EAM solution for L1 0 -phase FePt is not readily available, we applied Johnson-Zhou EAM model only as a close mathematical approximation of Fe-Pt interatomic interactions in a 1:1 atomic ratio alloy form, instead of actual representation of L1 0 -phase FePt lattice. For instance, with Johnson-Zhou EAM model, the calculated equilibrium atomic distances between the nearest neighboring Fe and Pt atom model is nm, 4

5 compared to experimental L1 0 -phase lattice parameters nm between Fe and Pt atoms. The solution of more accurate EAM potential specifically for L1 0 -phase FePt will be addressed in our future study. Ziegler-Biersack-Littmark (ZBL) screened nuclear repulsion is chosen for description of ion-metal interactions. ZBL potential is commonly used to describe high-energy collisions between atoms. In LAMMPS, ZBL potential form defined below as the product of Coulombic repulsion and screening function. Values of parameters are A=0.4685, B=0.23, C 1 = , C 2 =0.509, C 3 = , C 4 = , D 1 =3.1998, D 2 = , D 3 = and D 4 = E ZBL i, j a Z 2 ZiZ je Ri j ( ) 4 a A Z B i 4 i1 B j ( x) Cie Di X (2) R ij is the interatomic distance between atoms i and j, Zi, Zj are atomic numbers of the two interacting atom types, i.e. 2 for He, 18 for Ar, 26 for Fe and 78 for Pt. ZBL potential for He-Fe, He-Pt, Ar-Fe and Ar-Pt are plotted in Figure 3 in log-scale. To compare to ZBL potential to other pair potential forms, 12-6 Lennard-Jones (LJ) pair potential functions for ion-ion and ion-metal interactions. LJ has been used to describe van der Waals non-bonding potential in inert gases and molecular systems 15. LJ 12-6 pair potential is expressed as the following formula with two material-dependent LJ parameters: LJ E, 4 i j Rij 12 6 Rij (3) Where is often referred as bond energy and equals to interatomic distance R ij when potential diminishes to zero. Using Lorentz-Berthelot combining rule shown in Equation (4) below, we can obtain LJ potential function on binary interaction from their mono-atomic LJ parameters. 5

6 ij ij ij ij ii 2 (4) jj LJ parameters for mono-atomic interaction and binary interactions are listed in Table 1. Table 1 Lennard-Jones potential parameters for various atomic interactions Bond Sigma (nm) Epsilon (ev) Ref. Fe-Fe Pt-Pt Ne-Ne Ar-Ar He-He Ar-Fe Ar-Pt He-Fe He-Pt LAMMPS Simulation Procedure Simulation scripts were run on a 64-bit Windows LAMMPS simulator under non-mpi computing mode. Ion flux density is assumed to be larger than 10mA/cm 2 or no more than one ion impact onto the FePt top surface area per nanosecond. Brendesen temperature control is used in thermostated layer for heat removal with coupling time constant set to 300 femtoseconds. To ensure enough time thermal relaxation and reasonable computation speed, we set up total 500 ion injection at rate of one in every 500 time-steps with each time-step size is one femtosecond. Observed temperature readings in the thermostated layer range about +/-5K around the set value of 300K. Hybrid pair potential option in LAMMPS is used to incorporate many-body EAM potentials between metal atoms and ZBL or LJ potentials for ion-metal atoms. Ion injections along normal incidence (-Z direction) are initiated from the 6

7 3D box source placed above the surface. Specific kinetic energies are given to these ion particles. Range of ion velocities are given as set value of V 2* Ek where E k is chosen at 50ev, 100eV,150eV, 200eV m and 250eV respectively, and with 10% variation range. m is the atomic mass for injected Ar or He ions. Ejected parts are allowed to go out of the simulation space so that the number of atoms remained in the FePt lattice and number of atoms sputtered off can both be clearly counted. Snapshots of entire ensemble atom positions during the run are saved to data dump file for post-run analysis in MATLAB. Ovito 19 and VMD 20 are used for post-run visualization. III. Results and Discussion The main results of simulation are shown in Fig Fig. 4 shows the cross-section view of the FePt lattice structure after 500 Ar ion impacts and Fig. 5 shows that after 500 He ion impacts, both under different kinetic energy ranges from 50 to 200 ev. Cross-sections of lattice under 250eV ion impacts are not included in the figures. Fig. 6 shows that number of amorphized atom layers increases significantly with Ar ion kinetic energy. The amorphous layer thickness reaches from 4 mono-layers (or ~7.6A) at 50eV to 14 mono-layer (or ~2.7nm) under Ar ion energy at 250eV. This amorphous layer will be considered losing almost all magneto-crystalline anisotropy (MCA). However, with He ions there are only one amorphized surface layer shown within the same energy range. Sputter yields are shown in Fig. 7 and Fig. 8 respectively for both Ar and He with eV kinetic energy using LJ 12-6 potential and KBL potential for ion-metal interactions. With ZBL potential, it is shown a reasonable increasing trend of sputter yield vs. ion energy for both Ar and He. The sputter yield numbers can be seen closely matched to empirical model results 10,11 on Ar-Pt and He-Pt impact, shown in Fig.9. On the contrary, calculation with LJ 12-6 potential shows unrealistically high sputter yield (0.57 for He and 0.9 for Ar) even at 50eV, compared to the experimental results. Therefore, LJ potential function cannot be used to accurately represent the interactions between ions and metal atoms. 7

8 Interstitial defects also important as embedded ion particles travel into the FePt lattice and causes lattice displacement or vacancy defects. These defects can significant change the local MCA, as MCAof L1 0 -FePt strongly depends on the consistent lattice parameters such as a, c and c/a ratio. Maximum depth measurement of ions found inside the lattice vs. ion energy is shown in Fig. 10 for both Ar and He impacts. It shows defect depth of He ions is significantly higher than Ar within the ion energy range. This can be understood as the ZBL potential shown in Figure 3 also indicates the nuclear stopping power of FePt crystal to injected particles. ZBL potential of Fe or Pt for He is almost one order of magnitude lower than that for Ar, giving the result of higher depth of embedded He ions inside FePt lattice. Fig.11 shows the number of embedded particles after 500 ion impacts. For Ar, this number increases with ion energy. However, for He the counts is in the opposite direction from Ar ions. This is likely an artifact related to the limited simulation X-Y-Z space as He ions are more likely to escape from the sides and uncounted from the lattice structure due to their low stopper power. IV. Summary and Future Work A L1 0 -phase FePt-ion MD simulation model is constructed in LAMMPS to simulate energetic Ar and He ion impacts to FePt media using EAM interatomic potentials generated from Johnson-Zhou s alloy EAM model. Sputter yield results showed in close agreement with result from empirical model with ZBL potential to describe the ion-metal interactions. We found within energy range from eV, He ions cause almost no amorphized (i.e. magnetically damaged) surface layer while Ar ions can cause significant surface amorphous layer (or magnetic dead layer ), from ~7.6 A at 50eV to as much as ~2.7nm at 250eV in thickness only after 500 ion impacts. Simulation also shows that He ions can readily travel into FePt lattice as the nuclear stopper power of He ions is far smaller than that of Ar ions, results in deeper and likely more embedded He ions inside FePt lattice. Such interstitial defects can still cause more pinning 8

9 sites and local MCA and magnetization loss. In the future research, we will study and integrate the neutral-ion and neutral-metal interactions to the existing MD model. V. Figures FIG. 1. LAMMPS atomic structure for L1 0 -FePt lattice (Red-Fe atoms, Blue-Pt atoms, Yellow-Ions) FIG.2. Calculated EAM potential as function of interatomic distance using Johnson-Zhou alloy EAM model 5,6 FIG.3. Calculated LAMMPS ZBL potential for ion-metal interaction. FIG.4. Cross-section of FePt lattice after 500 Ar ion impacts under various ion energy levels. FIG.5. Cross-section of FePt lattice shown after 500 He ion impacts under various ion energy levels. Note the lattice structure is intentionally constructed "taller" due to the low nuclear stopping power of He ions. FIG.6. Number of surface layers becomes amorphized from 500 ion impacts. Note that He ions caused about one surface damaged layers compared to Ar from 4 layers at 50eV to about 14 layers at 250eV. FIG.7. Computed sputter yield with Lennard-Jones "12-6" potential for ion-metal interactions. FIG.8. Computed sputter yield with ZBL potential for ion-metal interactions. FIG.9. Computed sputter yield using Yamamura empirical sputter yield model 10,11. FIG.10. Maximum depth of embedded ions (interstitial defects) found inside FePt lattice. FIG.11. Number of embedded ions (interstitial defects) found inside FePt lattice. Note the decreasing number of He ions found inside FePt is likely an "artifact" related to the limited simulation space, as He ions with small stopping power can travel through the simulation boundary and to be uncounted in the simulation space. 9

10 References 1 H. Wang, H. Zhao, P. Quarterman, and J.-P. Wang, Embedded mask patterning: A nanopatterning process to fabricate FePt magnetic media, Appl. Phys. Lett., vol. 102, no. 5, p , J. Zhu, P. Quarterman and J. P. Wang, Effect of Mask Erosion on Patterning of FePt for Heat-Assisted Magnetic Recording Media Using Embedded Mask Patterning, IEEE TRANSACTIONS ON MAGNETICS, VOL. 52, NO. 7, JULY J. Zhu, P. Quarterman, and J.-P. Wang, Ion-assisted plasma etch modeling of L1 0 phase FePt magnetic media fabrication with embedded mask patterning method, IEEE TRANSACTIONS ON MAGNETICS, vol. 51, no. 11, Nov. 2015, Art. ID M. S. Daw and M. I. Baskes, Phy. Rev. B 29, 6443 (1984) 5 R. A. Johnson, Alloy models with the embedded-atom method, Phy. Rev. B., Vol.39, No.17, (1989) 6 X. W. Zhou, R. A. Johnson and H. N. G. Wadley, Phy. Rev. B 69, (2004) 7 M. H. Hong et al, Microstructure of FePt/Pt magnetic thin film with high perpendicular coercivity, J. Appl. Phy., Vol.84, No.8, 4403 (1998) 8 S. Plimpton, Fast Parallel Algorithms for Short-Range Molecular Dynamics, J. Comp. Phys., 117, 1-19 (1995) 9 P. Brault et al., Molecular Dynamics Simulations of Platinum Plasma Sputtering: A Comparative Case Study, Front. Phys., 10 May Yamamura Y., Tawara H., Energy dependence of ion-induced sputtering yields from monoatomic solids at normal incidence. At. Data Nucl. Data Tables (1996) 62: N. Matsunam et al., in Energy Dependence of the Yields of Ion-Induced Sputtering of Monatomic Solids, IPPJ-AM-32 (Institute of Plasma Physics, Nagoya University, Japan, 1983) 12 N.Nakazaki et al., Molecular dynamics simulation of Si etching in C1- and Br-based plasmas, J.App. Phy. 118, (2015) 13 Yukimasa Okada, Koji Eriguchi*, and Kouichi Ono, Surface Orientation Dependence of Ion Bombardment Damage during Plasma Processing, 2015 International Conference on IC Design & Technology (ICICDT) 14 M. E. Barone and D. B. Grave, Chemical and physical sputtering of fluorinated silicon, J.Appl. Phy. 77, 1263 (1995) 15 D. V. Matyushov, R. Schmid, J. Chem. Phy.10 (1996), Seung-Kyo Oh, Modified Lennard-Jones Potentials with a Reduced Temperature-Correction Parameter for Calculating Thermodynamic and Transport Properties: Noble Gases and Their Mixtures (He, Ne, Ar, Kr, and Xe) 17 V. P. Filippova et al., Constructing the Pair Interaction Potentials of Iron Atoms with Other Metals, Inorganic Materials: Applied Research, 2015, Vol. 6, No. 4, pp Fernando D. Vila et al., Molecular Dynamics Simulations of Supported Pt Nanoparticles with a Hybrid Sutton Chen Potential, J. Phys. Chem. C, 2016, 120 (27), pp

11 19 A. Stukowski, Visualization and analysis of atomistic simulation data with OVITO - the Open Visualization Tool Modelling Simul. Mater. Sci. Eng. 18 (2010), Humphrey, W., Dalke, A. and Schulten, K., "VMD - Visual Molecular Dynamics", J. Molec. Graphics, 1996, vol. 14, pp

Supporting Information Tuning Local Electronic Structure of Single Layer MoS2 through Defect Engineering

Supporting Information Tuning Local Electronic Structure of Single Layer MoS2 through Defect Engineering Yan Chen, 1,2,,$, * Shengxi Huang, 3,6, Xiang Ji, 2 Kiran Adepalli, 2 Kedi Yin, 8 Xi Ling, 3,9 Xinwei