Role of projectile ion mass in vacancy formation on muscovite mica

doi:10.21203/rs.3.rs-4190641/v1

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Role of projectile ion mass in vacancy formation on muscovite mica

https://doi.org/10.21203/rs.3.rs-4190641/v1

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This article investigates the impact of energetic projectile ion mass on defect/vacancy formation on muscovite mica. Utilizing low-energy bombardment (10 keV), the effects of two different projectile ions (Ar⁺, O⁺) irradiation on multi-elemental muscovite mica under normal and grazing incidence conditions, are examined theoretically. The findings reveal varying amounts of vacancy formation in the constituent elements of mica, with heavier Ar-ions inducing the maximum vacancy production compared to oxygen ions, owing to the greater energy available (T_dam) for vacancy formation. Despite of a similar energy transfer by each ion, the resulting damage and vacancy production differ across ions, is investigated here. Additionally, a shift in the ion distribution profile towards deeper penetration depths compared to the energy distribution profile (Bragg's peak), for different ions is observed for two different incidence angles. The qualitative explanation for vacancy formation and its dependence on projectile mass, is elucidated using the NRT displacement model and Monte Carlo simulations (SRIM) simulations. This study provides insights into the intricate interplay between projectile mass, energy transfer by projectile ions, and vacancy formation on muscovite mica.

Projectile ion mass

Energy transfer by ions

defect/vacancy formation

NRT displacement model

Naturally available 2D muscovite mica [KAl₂(Si₃Al)O₁₀(OH)₂] is an insulator with a large bandgap¹. The Muscovite mica is a significant material for like atomic force microscopy calibration², solid-state detector³, optoelectronic and electronic device fabrication^4,5. Muscovite mica shows important properties that proves to be an excellent material for biomolecule deposition^1,2. The most challenging task is to reduce the bandgap of mica by forming the defect at different layers. Several studies were reported regarding the formation of defects to reduce the bandgap such as thermoluminescence ^6–8, swift heavy ion irradiation^9,10, impurity incorporation¹¹, exfoliation² and introduction of defect ¹². The formation of defects changes the electronic density as well as configuration of the material, by altering the bandgap of the material¹³. Therefore, the creation of defects in the material is a subject of interest. The low energy ion bombardment is an important tool for the formation of defects in material using sputtering of constituent elements¹⁴. Recently, both inert and reactive ion bombardment have proven to be valuable methods for introducing defects without any chemical modification ^15,16. The formation of vacancy depends on several factors such as ion energy, bombardment angle and ion spices. By tuning this ion beam parameters, the damage /vacancy formation can be tuned at different layers of mica. However, the role of projectile ion mass on vacancy formation has not yet been explored in detail.

Here, in this article, the role of projectile ion mass on vacancy formation on muscovite mica is investigated using Monte Carlo simulation. To establish the role of projectile ion mass in vacancy formation, two ions with different masses, (Ar⁺ and O⁺) with energy 10 keV are chosen. The investigations were carried out at normal and grazing incidence. Moreover, the mass of the Ar ion is closest to potassium (K) atom of mica. It is seen from the simulation that the Ar⁺ ion can create more vacancies compared to other ions. The vacancy formation increases with the mass of the projectile ion, is highlighted here. Further, the shift in the distribution of ions inside mica and their energy transfer by the projectile ion on mica with ion incidence angle is also highlighted here.

The entire Monte Carlo simulation was performed using SRIM (Stopping and Range of Ions in Matter) and TRIM (Transport and Range of Ions in Matter in full cascade) freeware¹⁷. The quantum mechanical treatment of ion–matter interaction with binary collision approximation (BCA)was considered throughout the simulation. In the collision, the ion and atoms engage in a screened Coulomb interaction, classified as the Zeigler-Biersack-Littmark (ZBL) type¹⁸. During simulation, a single layer of mica was considered with proper stoichiometry [KAl₂(Si₃Al)O₁₀(OH)₂] and density (2.8 gm/cm³). The entire simulation was carried out using two projectile ions, Ar⁺ and O⁺. The reason for choosing such ions is mainly of two reasons; firstly, the mass of the Ar⁺ and O⁺ ions are similar to that of K and O atoms in mica respectively, and secondly, these ions can easily be developed by commonly used ion sources.

Fig 1: Schematic diagram of a single layer of mica

Fig 1 shows the schematic diagram of a single layer of muscovite mica. Muscovite mica consists of five elements, i.e., potassium (K), Aluminium (Al), Silicon (Si), Oxygen(O), and Hydrogen (H). The thickness of the one monolayer is approximately 10 Å (1nm). The upper bound positively charged K atoms form an electrostatic bond with the negatively charged alumino-silicate layer. During ion bombardment, the loosely bound K atoms are mostly sputtered out along with other constituent elements and the negatively charged aluminosilicate attracts environmental hydrocarbon, as reported earlier ¹.

Fig 2: (a) 10keV Ar⁺ ion distribution (b) Energy transferred by Ar⁺ ions (c) Energy absorbed and (d) vacancy formation of constituent elements of mica.

Fig 3: (a) 10keV O⁺ ion distribution (b) Energy transferred by O⁺ ions (c) Energy absorbed and (d) Vacancy formation of constituent elements of mica.

In Fig 2, the intricacies of energy transfer and vacancy formation corresponding to 10 keV Ar-ion bombarded on mica at normal incidence are investigated. Fig 2(a) reveals that the penetration depth of Ar⁺ ion in mica extends up to approximately 12 nm (full width at half maximum of the distribution), indicating the potential for damage creation across 12 layers of mica from the top surface. Notably, the ion distribution exhibits a maximum (peak) at 12 nm, suggesting the maximum population of the ions at this position. However, Fig 2(b) unveils the maximum energy transfer by the ion at 10 nm. Therefore, the difference between the peak position of the Ar-ion distribution and the energy transfer by the Ar-ion possesses a shift of 2 nm. This indicates that the Ar-ions are populated at 12 nm from the top surface while the maximum energy deposited by ions is at 10 nm from the surface. Hence, this 2.5 nm can be treated as the slowing down distance of Ar-ion on mica.

Further analysis in Fig 2(c) and (d) demonstrate that oxygen atoms play a pivotal role in the Ar-ion-mica interaction, absorbing much of the transferred energy. Although the surface binding energy of silicon atoms are higher compared to other atoms, the oxygen vacancy is higher compared to other atoms. Further, it is evident that the vacancy formation is maximum at shorter distance compared to the energy deposition by ions. In addition, the energy absorbed by the oxygen atoms is largest among other constituent elements. This results in the maximum vacancy formation observed for oxygen atoms. The current findings shed light on the interplay between ion penetration (ion energy loss), energy transfer, and subsequent vacancy formation, offering key insights into the underlying mechanisms of material damage induced by Ar⁺ ion irradiation on mica.

Fig 4: (a) 10keV Ar⁺ ion distribution at 85º (b) Energy transferred by Ar⁺ ions (c) Energy absorbed and (d) Vacancy formation of constituent elements of mica.

Fig 5: (a) 10keV O⁺ ion distribution at 85º (b) Energy transferred by O⁺ ions (c) Energy absorbed and (d) Vacancy formation of constituent elements of mica.

Fig 6: (a) Phonon energy produced by (a) 10 keV Ar-ion at normal incidence (b) 10 keV O⁺ ion at normal incidence (c) 10 keV Ar-ion at grazing incidence (85º) (d) 10 keV O⁺ ion at grazing incidence(85º).

Fig 7: Ionisation and recoil ionisation energy produced by (a) 10 keV Ar-ion at normal incidence (b) 10 keV O⁺ ion at normal incidence (c) 10 keV Ar-ion at grazing incidence (85º) (d) 10 keV O⁺ ion at grazing incidence(85º).

In the case of O⁺ ion bombardment on mica, a notable shift of 5 nm in peak positions between ion distribution and energy transfer is observed (Fig 3). The penetration depth of oxygen ions reaches approximately 26.92 nm, suggesting damage or defects in nearly 27 layers of mica. Interestingly, in this case also oxygen atoms absorb most of the energy, while hydrogen atoms absorb the least, as depicted in Fig 3(c). The observed vacancy formation by the O-ion is less compared to Ar⁺ ion bombardment, as illustrated in Fig 3(d).

The energy transfer of an energetic projectile ion remains independent of the incidence angle. However, the penetration depth, or ion range, is influenced by the implantation angle. Consequently, during ion bombardment at grazing incidence, the projectile ions lose the same amount of energy over a shorter distance. This phenomenon leads to a more concentrated defect formation in a narrow region, emphasizing the significance of incidence angle in modulating the spatial distribution of defects induced by ion bombardment. To verify this the distribution and the energy transfer of Ar⁺ and O⁺ ions bombarded at near-grazing incidence are presented in Fig 4 and 5, respectively.

Fig 4(a) investigates the distribution of the 10keV Ar-ions bombarded at an angle of 85º. The population of Ar-ions is maximum up to 8 layers, which is 5 layers less compared to normal incidence. The distribution (Fig 4(a)) shows a peak at 3nm, which is much less compared to Ar-ion bombardment at normal incidence (Fig 2(a)). The maximum energy deposited by Ar-ions during grazing incidence, shows a maximum at 0.8 nm, indicating a shift of between the peak of these two distributions (as seen from Fig 4(b)), lesser than the previous case. Like the previous case, the maximum vacancy formation occurred for oxygen atoms is larger due to maximum energy absorbed by oxygen atoms (Fig 4(c) and (d)). However, the amount of vacancy formation is less compared to previous case (Fig 2(c) and (d)).

Further, the distribution of 10keV O-ions indicate that the O-ions are mostly populated over 18 layers of mica (as seen from FHHM of Fig 5(a)). On the other hand, the maximum energy transfer by O-ions occurs upto 4 layers of mica (Fog 5(b)). In similar to other cases, the oxygen vacancy is larger, owing to maximum energy absorbed by O -atoms (Fig 5(c) and (d)). The energy absorbed by the individual atoms and the corresponding vacancy formation is less compared to Ar-ion (Fig 4(c) and (d)).

The formation of vacancy in the solid surface by ion beam irradiation was theoretically proposed by Norgett -Robinson and Torrens, namely the NRT displacement model¹⁹. Within the NRT model, no vacancy production occurs under the threshold of T_dam = E_d, where T_damis the damage energy available after the primary knock of atoms and E_dis the damage energy required to create one Frenkel pair (vacancy-interstitial atom pairs). In case of damage energies above 2.5 E_d, the number of stable Frenkel pairs produced by a PKA with damage energy T_dam is proposed by the NRT model as ν_NRT= 0.8 T_dam/ 2E_d. ……………………………………(1)

The displacement energy is different for different materials and also different for different atoms in a compound. In the case of full cascade SRIM simulation, the T_dam can be estimated by T_dam= E_recoil - E_ioniz. These two parameters can easily be obtained by the “E2recoil. Text” and “ionization. Text” file generated by SRIM^20–22. Therefore, the damage energy

T_dam = E_tot - E_ionizi - E_ionizr - E_phi = E_phr- E_phi ………………………………………(2)

Here, E_tot is the total energy loss, or the energy transferred by the incident ion beam, E_ionizi is the ionization energy lost by the incident ion, E_phi is the phonon energy produced by the incident ion, and E_phr is the phonon energy generated by recoil ions. This approximation was proposed by Stoller et.al ²³. It is therefore clear that the amount of vacancy formation depends on phonon energy and recoil ionisation energy generated during energy momentum transfer by the projectile ions.

Elements	Displacement Energy (eV)	Binding Energy(eV)	Surface Energy (eV)	Sputtering Yield at normal Incidence (atoms/ion)	Sputtering Yield at grazing incidence (atoms/ion)
Potassium (K)	25	3.0	0.93	0.71	4.19
Aluminium (Al)	25	3.0	3.36	0.37	2.75
Silicon (Si)	25	2.0	4.7	0.32	2.49
Oxygen (O)	28	3.0	2.0	2.20	14.63
Hydrogen (H)	10	3.0	2.0	0.21	1.56

Table 1: Displacement energy, binding energy, surface energy and sputtering yield of the constituent elements of mica

To quantify the effect of ionisation and phonon energy developed by these two energetic ions, Figs 6 and 7 are presented. In Fig 6, the phonon energy and recoil phonon energy generated by 10keV Ar and O ions at normal and grazing incidence are presented. The phonon energy refers to the energy associated with phonons generated directly by the passage of the projectile ion through the material. Generally, when an energetic ion traverses a material, it creates a trail of excitations, including phonons, electron-hole pairs, and lattice defects. On contrary, the recoil phonon energy refers to the energy transferred to the crystal lattice of a material when an ion collides with an atom within the lattice. The atom recoils due to the collision, leading to the generation of phonons, which are quantized mechanical vibrations of the lattice. The energy associated with these phonons is termed recoil phonon energy. It represents the energy imparted to the lattice by the recoiling atom. It is clear from Fig 6(a)-(d) that during both normal and grazing incidence the recoil phonon energy is greater compared to phonon energy produced by these ions. This implies that E_phr is much greater compared to E_phi, indicating large magnitude of T_dam available for vacancy formation. Furthermore, in compared to oxygen ion the E_phr for Ar-ion is larger for both normal and grazing incidence (From Fig 6), ensuring a more vacancy formation compared to oxygen-ion.

Further, the distribution of ionisation energy and recoil ionisation energy are presented in Fig 7. The ionisation energy refers to the energy required to remove an electron from an atom or molecule by the impact of an incoming ion. When an energetic ion collides with an atom or molecule in a material, it can transfer sufficient energy to remove one or more electrons from the target atom or molecule, leading to ionization. The energy required for this process is known as the ionization energy. The ionization energy depends on factors such as the ionization potential of the target material and the velocity and charge of the incident ion. On the other hand, the recoil ionisation occurs when an energetic ion collides with an atom in a material, transferring energy to the target atom and causing it to recoil. The recoiling atom may acquire sufficient energy to ionize another atom upon collision. This secondary ionization, induced by the recoil of the primary ion, is termed recoil ionization. It contributes to the overall ionization process in ion-solid interactions and can play a significant role, especially in materials with low ionization potentials. In case of normal incidence, the quantity (E_ionizi -E_ionizr) is less for oxygen-ion compared to Ar-ion. However, in case of grazing incidence the reverse phenomenon occurs. This ensures that Ar-ion is more effective in creating vacancy on mica according to equation no 2.

In a nutshell, the Ar⁺ ion is heavier compared to other ions. The mass of the Ar⁺ ions is like that of K atoms. Also, the penetration depth of the Ar⁺ ions is less compared to others. This indicates the transferred energy E_tot is confined to a lesser number of layers compared to the other ions. Moreover, due to heavier mass, the recoil ionisation energy (E_ionizr) is also less. Due to this, the available energy for creating damage (T_dam) is greater for Ar⁺ ion bombardment compared to other ions (since the displacement energy is almost similar for all the constituent elements of mica, as seen from table 1). This leads to more vacancy formation compared to other ions. Moreover, the displacement energy for the oxygen atom is larger (28 eV as estimated from SRIM). Hence oxygen vacancy in muscovite mica is greater compared to other elements.

There is no such theoretical or experimental model exists that can accurately predict the vacancy formation of elements and compound materials. Here, in this manuscript, a qualitative idea is discussed about the vacancy formation in the compound. The above discussion clarifies that the vacancy formation on multi-elemental muscovite mica depends on the projectile ion mass. The heavier mass is more effective in vacancy formation on mica. The displacement energy is maximum for oxygen atoms and minimum for hydrogen atoms, indicating the oxygen vacancy is larger compared to other atoms.

Author Contribution

Joy Mukherjee: Conceptualization, Original research work, methodology, simulation, manuscript writing, and review.Sudip Bhowmik: Simulation and manuscript check,

Acknowledgement:

The author is thankful to the Department of Atomic Energy (DAE), Govt. of India for financial support.

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No competing interests reported.

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Role of projectile ion mass in vacancy formation on muscovite mica

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