AVS 71 Session PS3-WeA: ICP Modelling 

Plasma etching for high aspect ratio vertical trenching in 3D-structured silicon-based devises is one of the most challenging steps in advanced semiconductor manufacturing. This process requires precise control of both ion and neutral fluxes to facilitate etching at the trench bottom while ensuring sidewall passivation to prevent lateral etching and feature distortion. As the range of chemical reactants used in industry continuous to expand, a deeper understanding of plasma-surface interactions and surface reaction mechanisms becomes increasingly critical. Over the past decade, quantum chemistry has played a growing role in elucidating these mechanisms, providing valuable insights for optimizing plasma etching processes.

Quantum chemistry is widely used to investigate reaction mechanisms at the atomic level. Within the framework of transition state theory, the reactivity of various fluorine-based reactants with semiconductor materials has been calculated, revealing how etching with these reactants can be catalyzed, enhanced, and accelerated through vibrational excitation. This ab-initio approach enables the calculation of rate constants for key surface reactions and allows for the integration of surface reactions kinetics with plasma chemistry models. These kinetic models predict the dependence of etching rates and selectivity on plasma parameters. For example, the reactivity of fluorine (F) atoms and hydrogen fluoride (HF) molecules – two of the most commonly used reactants in the semiconductor industry – has been studied on silicon-based materials such as Si, SiN, and SiO₂.

Another crucial challenge in plasma-assisted etching is the efficient delivery of ions to the trench bottom. Accelerated ions lose kinetic energy through the collisions with sidewalls, leading to feature damage without effectively contributing to bottom etching. Despite their high initial energies in the keV range, the normal component of ion energy at the grazing incident is only in tens of eV. As a result, relatively weak chemical interactions between sidewall materials and incident ions play a crucial role in determining etching efficiency and feature integrity. Using ab-initio molecular dynamics, it has been demonstrated that ammonia fluoride ionic salts – the most common etching by-products that coat the sidewalls – provide more effective protection against damage and help prevent ion energy loss at lower temperatures. This discovery sheds light on the mechanisms of cryogenic plasma-assisted etching and highlights the importance of by-product formation in sustaining etching process.

Electromagnetic simulation with an explicit algorithm has a severe limitation on the time step due to the large speed of light propagation resulting in the high numerical cost. Fully implicit electromagnetic algorithms do not have this limitation but are more complex to implement. Another option is the Darwin method omitting the electromagnetic wave propagation [1]. The Darwin method separates the electric field into solenoidal (electromagnetic) and irrotational (electrostatic) parts.

In this work, we propose a new Darwin scheme for simulation of low-frequency electromagnetic processes in laboratory plasmas. A two-dimensional particle-in-cell code in Cartesian geometry has been developed based on the direct implicit Darwin electromagnetic algorithm described in Ref. 1. The new code has several significant modifications compared to the original algorithm. First, the SDF is replaced by a new method based on the equation for the vorticity of the solenoidal electric field. Unlike the SDF, the linear system of equations in the vorticity method is reliably solved using a standard iterative solver. Second, the electromagnetic fields are defined on staggered grids convenient for electromagnetic simulation. Third, the contribution of collisional scattering is included in calculation of the solenoidal electric fields. Fourth, the code includes several solvers for the self-consistent magnetic field with different boundary conditions. Once one of these methods is selected for a particular simulation, the choice can be verified by checking the energy conservation.

A two-dimensional particle-in-cell code has been developed using the modified direct implicit Darwin electromagnetic algorithm described in Ref. 2. The code is a valuable tool for simulation of various electromagnetic effects, for example the inductively coupled plasmas and the electromagnetic plasma waves. The code can be used to design future plasma thrusters.

References:

[1] M. R. Gibbons and D. W. Hewett, “The Darwin Direct Implicit Particle-in Cell (DADIPIC) Method for Simulation of Low Frequency Plasma Phenomena,” J. Comput. Phys. 120, 231–247 (1995).

[2] Dmytro Sydorenko, Igor D. Kaganovich, Alexander V. Khrabrov, Stephane A. Ethier, Jin Chen, Salomon Janhunen, “Improved algorithm for a two-dimensional Darwin particle-in-cell code”, arXiv:2409.19559, submitted to Phys. Plasmas (2024).

Radio frequency (RF) hollow cathode discharges (HCD) are used in various semiconductor manufacturing processes such as material etching and deposition. HCD cathodes have cavities, and the plasma forms inside these cavities under the right conditions. In the HCD, RF sheath heating as well as secondary electron acceleration can lead to plasma production. In this work, plasma simulation results for argon and oxygen HCDs are compared with plasma diagnostics measurements using non-invasive methods. These measurements include the emission spectra of plasma discharge using Phase Resolved Optical Emission Spectroscopy (PROES), which provides the spatio-temporal excitation rate of important species in the discharge. We use both kinetic and hybrid plasma models in this work to understand the plasma dynamics and elucidate with the experimental observations. The Particle-In-Cell with Monte Carlo Collisions (PIC-MCC) model includes evolution of charged particles and electrostatic field along with charged particle collisions with the neutral species using a Monte Carlo approach. The hybrid model only treats the electrons as particles and includes a fluid model for the other charged species. In both models, the charged species’ densities are coupled with the Poisson’s equation to calculate the electric potential, enabling a self-consistent plasma simulation. Plasma simulations are performed for different pressures, voltages, and feed gases (Ar & O₂). Our simulation results show good agreement with the spatio-temporal experimental measurements of metastable argon excited state at low pressures. With increase in voltage, the excited species is found to penetrate further into the hollow cathode slot. The modeling results also indicate that the secondary electron emission coefficient from surfaces significantly influences the plasma behavior.

This work is partially supported by the Naval Research Laboratory base program.

Plasma enhanced chemical vapor deposition (PECVD) is an attractive method to deposit conformal coatings on surfaces without affecting bulk properties. Current literature showcases PECVD in conjunction with computational studies primarily focused on coating semiconductors with organometallic and semimetal-based films. Many PECVD systems utilize organic precursors to modify surfaces with the goal of interfacing with biological environments. This research seeks to fill the gap by studying the mechanism in which the thin films are deposited using two organic plasma precursors– acrylic acid and pentane. Computational modeling of these organic precursor fragments and how they recombine in the plasma will help in understanding key characteristics of the deposition of the thin film via the thickness of the film, deposition rate, and the chemical composition of the film.

Low-temperature kinetic plasma simulations using particle-in-cell (PIC) and Monte Carlo methods (DSMC/MCC) for the chemistry can provide many advantages over fluid simulations, including detailed information about the Ion Energy Distribution Function (IEDF) and Ion Angular Distribution Function (IADF) that are critical for plasma processing. In addition, a fully kinetic approach does not make common assumptions made in fluid models, such as local conductivity or Maxwellian distributions of the plasma species. In this talk we present kinetic modeling results of inductively coupled plasmas in a 2D cylindrically symmetric geometry. We demonstrate how implicit methods can make these challenging simulations feasible by reducing computing times by factors of 20-200. We also demonstrate a method of providing constant power to the plasma, which further decreases the runtime needed to achieve steady-state discharges. We then apply DC and/or RF bias voltage below the wafer, introducing capacitive coupling self-consistently into the model to enable better etch control, and explore how steady-state ion fluxes and IEDF/IADFs at the wafer surface vary as a function of RF bias frequency, amplitude, and waveform shape. We show, for example, that a low-frequency CCP bias couples more efficiently with the ions leading to an increase in the RF-averaged ion energy. We also demonstrate that improved IEDF uniformity can be achieved through careful choice of the shape of the bias waveform.