Atomic Layer Etching Physics
Langmuir Self-Limiting Adsorption
The foundation of ALE is self-limiting surface chemistry:
Surface coverage (fractional):
θ = (K × P) / (1 + K × P)
K: Equilibrium constant = k_ads / k_des
P: Precursor partial pressure (mTorr)
At saturation: θ → 1 (100% coverage)
Kinetic form:
dθ/dt = k_ads × P × (1 - θ) - k_des × θ
Solution:
θ(t) = θ_sat × [1 - exp(-t/τ)]
τ = 1/(k_ads × P + k_des)
Etch Per Cycle (EPC)
Fundamental ALE metric:
EPC = θ_sat × d_monolayer × Y_removal
θ_sat: Saturated coverage (ideally 1.0)
d_monolayer: Atomic layer thickness
Al₂O₃: ~2.8 Å/layer
Si: ~3.1 Å
SiO₂: ~3.2 Å
Y_removal: Removal yield (ideally 1.0)
Typical values:
Thermal ALE: 0.3-1.5 Å/cycle
Plasma ALE: 0.5-3.0 Å/cycle
Precision: 3σ < 0.1-0.3 Å
Sequential Ligand Exchange
Example: Al₂O₃ ALE with TMA/HF:
Step 1: Modification
Al₂O₃-OH + Al(CH₃)₃ → Al₂O₃-O-Al(CH₃)₂* + CH₄(g)
Self-limiting: All -OH sites consumed
Step 2: Purge (Ar/N₂)
Remove excess TMA and byproducts
Step 3: Removal
Al₂O₃-O-Al(CH₃)₂* + 2HF → AlF₃(g) + CH₄(g)
Self-limiting: Only modified layer removed
Step 4: Purge
Net: ~2.8 Å Al₂O₃ removed per cycle
Thermal vs Plasma ALE
THERMAL ALE:
- Modification: Chemical adsorption
- Removal: Chemical reaction
- Temperature: 200-400°C
- Damage: None (purely chemical)
- Anisotropy: Isotropic
- EPC control: Excellent (0.05 Å σ)
- Rate: 0.5-2 nm/min
PLASMA ALE:
- Modification: Chemi/physisorption
- Removal: Ion bombardment (20-100 eV)
- Temperature: 20-300°C
- Damage: Minimal (below threshold)
- Anisotropy: Directional
- EPC control: Good (0.1-0.3 Å σ)
- Rate: 2-10 nm/min
Saturation Curve Characterization
Vary t_dose: 0.5 to 20 s
Measure EPC vs t_dose
Fit: EPC(t) = EPC_sat × [1 - exp(-t/τ_sat)]
Extract:
- EPC_sat: Maximum EPC
- τ_sat: Time constant
Criteria: t_dose > 3τ_sat for 95% saturation
Optimize: Balance speed vs uniformity
Uniformity and Conformality
Wafer uniformity: σ/μ < 1% (3σ)
Mechanism: Self-limiting → rate independent of flux
Conformality:
Thermal ALE: AR > 100:1 (neutral diffusion)
Plasma ALE: AR ≈ 10-20:1 (ion limitations)
High AR optimization:
- Longer dose times
- Pulsed removal
- Lower pressure (longer λ_mfp)
Process Window Optimization
Key parameters:
1. t_mod: 3-5 × τ_sat (saturation)
2. t_rem: Just enough for removal
3. t_purge: 3-5 × volume replacement
4. T: Material dependent (200-400°C)
Multi-objective optimization:
Maximize: EPC, uniformity, selectivity, throughput
Minimize: Damage, roughness, cost
Selectivity Mechanisms
Infinite selectivity:
Material A: Modified → etches
Material B: Not modified → no etch
Examples:
1. Al₂O₃ vs TiO₂ (TMA/HF): >100:1
2. Si vs SiO₂ (Cl₂/Ar): 20-50:1
3. SiGe vs Si: Tunable by Ge%
Applications:
- Gate oxide trim
- Fin reveal
- Spacer recess
- Self-aligned contacts
Damage Characterization
ALE advantages:
Physical damage: 10-100× lower than RIE
E_ion: 20-100 eV (vs 100-500 eV)
Roughness: RMS < 3 Å (atomic smooth)
Mechanism: Layer-by-layer vs stochastic
Sidewall damage: Minimal
RIE: 1-3 nm damaged layer
Electrical: D_it < 10^10 cm⁻²eV⁻¹
RIE: 10^11-10^12
Characterization:
AFM, TEM, XPS, electrical testing