Figure 10. Electrical properties of low-temperature  $\mathrm{Al}_2\mathrm{O}_3$  ALD films grown using 300 reaction cycles on  $n\mathrm{-Si}(100)$ .

The chart displays the relationship between growth temperature and two properties: dielectric constant and breakdown field. The breakdown field shows a slight increase with increasing temperature, while the electric constant shows no correlation with temperature.

| Growth Temperature (°C) | Dielectric Constant, k | Breakdown Field (MV/cm) |
|---|---|---|
| 33 | 7.5 | 3.7 |
| 58 | 8.2 | 4.0 |
| 80 | 7.2 | 4.5 |
| 102 | 7.8 | 4.1 |
| 125 |  8.4 ; 7.5 | 4.2 |
| 177 |  7.5 | 4.4 |

Answer: There is no correlation.

Answer: There is a slight positive correlation.

Answer: Breakdown field.

Answer: The higher growth temperature range appears to produce the most electrically robust films, as the breakdown field increases with growth temperatures, while the dielectric constant remains stable. The breakdown field indicates the maximum electric field the film can withstand before electrical failure.  Therefore,  a higher breakdown field means the film is more resistant to damage under high voltage.


Figure 11. O/Al ratio and H concentrations for  $\mathrm{Al}_2\mathrm{O}_3$  ALD films as determined by RBS and FRS versus growth temperatures from 33 to  $177^{\circ}\mathrm{C}$ .

The chart shows the relationship between growth temperature and two variables: hydrogen content (in at.%) and oxygen-to-aluminum atom ratio (O/Al). Hydrogen content shows a negative correlation with growth temperature, and the O/Al ratio shows no correlation.

| Growth Temperature (°C) | H (atom %) | O/Al atom ratio |
|---|---|---|
| 32 | 21,86 | 1,66 |
| 57 | 19,37 | 1,29 |
| 79 | 15,99 | 1,41 |
| 101 | 14,51 | 1,37 |
| 124 | 10,80 | 1,36 |
| 177 | 7,09 | 1,42 |

Answer: There is a negative correlation.

Answer: There is no correlation.

Answer: ~ 1.34 to 1.70.

Answer: The O/Al ratio in the measured film is closest to that at 177 °C. The O/Al ratio in stoichiometric Al₂O₃ is 1.5. At  177 °C, the measured O/Al ratio of 1.42 is closer to 1.5 than the values at lower temperatures.


FIG. 5. (Color online) Ion-surface interactions during plasma processes with respect to ion flux and ion energy (Ref. 345). The typical operating windows for remote plasma ALD and other plasma-based processes are indicated. Reprinted with permission from T. Tagaki, J. Vac. Sci. Technol. A 2, 382 (1984). Copyright 1984 American Vacuum Society.

The auto summary accurately identifies that the chart relates ion flux density and ion energy and mentions key processes like film deposition, plasma chemistry, and ALD. However, it could be improved by noting that the axes are logarithmic, which affects the interpretation of spatial relationships between regions. It also does not mention the conceptual groupings (e.g., adatom migration, sputtering, implantation) marked across the top of the plot, which provide additional mechanistic context.

| Process           | Ion Energy Range (eV) | Ion Flux Density Range (cm⁻²s⁻¹)  |
|-------------------|------------------------|----------------------------------|
| ALD               | 1 – 10                 | 10⁹ – 10¹²                       |
| Plasma Chemistry  | 1 – 10³                | 10⁹ – 10¹⁵                       |
| Film Deposition   | 1 – 10⁴                | 10⁹ – 10¹⁸                       |
| Etching           | 10 – 10⁴               | 10¹¹ – 10¹⁷                      |
| Implantation      | 10² – 10⁵              | 10¹⁴ – 10¹⁷                      |

Answer: It maps typical ion energy and flux conditions for processes like ALD, etching, and implantation.

Answer: Atomic layer deposition (ALD) occurs in a region of low ion energy and moderate-to-low ion flux, reflecting its surface-limited, gentle chemistry. In contrast, processes like implantation and etching require higher ion energies and, in the case of implantation, significantly higher flux densities. This demonstrates that ALD is well-suited for precise, conformal coatings where minimal ion damage is critical.

Answer: Adatom migration, Desorption, Sticking, Lattice displacement, Sputtering, Implantation

Answer: Yes

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-deposition/experimental-usecase/10/H. B. Profijt et al.pdf


Fig. 6 Selected representative capacitance-voltage and dissipation-voltage curves of  $\mathrm{ZrO_2}$  thin films deposited from  $(\mathrm{CpMe})_2\mathrm{ZrMe}_2$  at  $350^{\circ}\mathrm{C}$  (upper panel) and  $(\mathrm{CpMe})_2\mathrm{Zr(OMe)Me}$  at  $300^{\circ}\mathrm{C}$  (lower panel).

The figure shows Capacitance–Voltage (C–V) and Dissipation–Voltage (D–V) curves for a ZrO₂ thin film (thickness: 13.1 nm) deposited using the (CpMe)₂ZrMe₂/O₃ process. Measurements were performed at three frequencies: 100 kHz, 500 kHz, and 1 MHz. The capacitance is high under negative bias (accumulation), decreases sharply near 0 V (depletion), and saturates at a lower value under positive bias (inversion), which is characteristic of a metal–oxide–semiconductor (MOS) structure.

The figure shows Capacitance–Voltage (C–V) and Dissipation–Voltage (D–V) curves for a ZrO₂ thin film (thickness: 11.9 nm) deposited using the (CpMe)₂Zr(OMe)Me₂/O₃ process. Measurements were performed at three frequencies: 100 kHz, 500 kHz, and 1 MHz. The capacitance and dissipation values showed almost similar behavior as the previous label.

| Bias voltage, V | C, 100 kHz | C, 500 kHz | C, 1 MHz | D, 100 kHz | D, 500 kHz | D, 1 MHz |
|---|---|---|---|---|---|---|
|-4 | 1.6e-09 | 1.6e-09 | 1.6e-09 | 0.02 | 0.1 | 0.2 |
|-3 | 1.5e-09 | 1.5e-09 | 1.5e-09 | 0.02 | 0.1 | 0.2 |
|-2 | 1.0e-09 | 1.0e-09 | 1.0e-09 | 0.01 | 0.0 | 0.1 |
|-1.5 | 0.2e-09 | 0.2e-09 | 0.2e-09 | 0.6 | 0.6 | 0.6 |
|-1 | 0.1e-09 | 0.1e-09 | 0.1e-09 | 0.0 | 0.0 | 0.0 |
| 0 | 0.1e-09 | 0.1e-09 | 0.1e-09 | 0.0 | 0.0 | 0.0 |
| 1 | 0.1e-09 | 0.1e-09 | 0.1e-09 | 0.0 | 0.0 | 0.0 |

| Bias voltage, V | C, 100 kHz | C, 500 kHz | C, 67, 1 MHz | D, 100 kHz | D, 500 kHz | D, 1 MHz |
|---|---|---|---|---|---|---|
|-5 | 1.8e-09 | 1.7e-09 | 1.6e-09 | 0.25 | 0.2 | 0.1 |
|-4 | 1.6e-09 | 1.5e-09 | 1.4e-09 | 0.1 | 0.2 | 0.1 |
|-3 | 1.4e-09 | 1.3e-09 | 1.2e-09 | 0.05 | 0.15 | 0.05 |
|-2 | 1.2e-09 | 1.1e-09 | 1.0e-09 | 0.0 | 0.1 | 0.0 |
|-1 | 1.0e-09 | 9.0e-10 | 8.0e-10 | 0.8 | 0.8 | 0.8 |
| 0 |  2.0e-10 | 2.0e-10 | 2.0e-10 | 0.0 | 0.0 | 0.0 |
| 1 | 2.0e-10 | 2.0e-10 | 2.0e-10 | 0.0 | 0.0 | 0.0 |

Answer: The "hump" is caused by the charging and discharging of interface trap states (D_it) at the ZrO₂/Si interface. As the DC bias sweeps through the depletion region, the Fermi level aligns with the energy levels of these traps. At lower measurement frequencies, carriers have enough time to respond to the AC signal by filling and emptying these traps, contributing an additional capacitance that appears as a hump. At very high frequencies, this response lags, and the hump diminishes.

Answer: The 11.9 nm film has a CET of 3.9 nm, while the 13.1 nm film has a CET of 4.3 nm. Although the physical thickness differs by 1.2 nm, the CET only increases by 0.4 nm. This reveals that the dielectric constant (κ) scales effectively, and the thicker film does not proportionally increase the equivalent electrical thickness, which is favorable for device scaling.

Answer: It maps directly to the density of interface trap states (D_it) at the ZrO₂/Si interface.

Answer: Both precursors yield films with comparable interface quality, so the decision would not be based on trap density. Selection would instead prioritize other factors like the precursor's thermal stability, growth rate, and compatibility with the thermal budget. The key inference is that either precursor can meet the baseline electrical requirement for gate dielectric applications.


Fig. 5 Average growth per cycle and lithium concentration of LLT films as a function of  $\mathrm{LiO}^{\prime}\mathrm{Bu}$  pulse time. The pulsing scheme was  $400 \times (1 \times \mathrm{TiO}_{2} + 3 \times \mathrm{La}_{2}\mathrm{O}_{3} + 1 \times \mathrm{Li}_{2}\mathrm{O})$ .

The chart shows the growth per cycle and lithium concentration in at% as a function of lithium tert-butoxide pulse time at a deposition temperature of 225°C. Both curves show saturation behavior.

| Lithium tert-butoxide pulse time (s)' | Growth per cycle (Å/cycle) | Lithium concentration (at.%) |
|---|---|---|
| 0 | 0.28 | 0.01 |
| 2 | 0.37 | 0.08 |
| 4 | 0.43 | 0.15 |
| 8 | 0.47 | 0.20 |
| 12 | 0.48 | 0.21 |

Answer: Yes

Answer: After approx. 8 s. pulse time.

Answer: After approx. 8 s. pulse time.

Answer: No. At 4 seconds, both the growth rate (~0.43 Å/cycle) and lithium concentration (~15 at.%) are still rising steeply and are clearly lower than the values observed at 8 and 12 seconds. This indicates that 4 seconds is insufficient.


Figure 2. Film thickness and film uniformity on a  $300~\mathrm{mm}$  wafer for different precursor pulse times. The error bars indicate the minimum and maximum thickness as measured by XRR. The half range is defined as the thickness range divided by two divided by the mean thickness.

The figure shows the saturation behavior of a Ti-based ALD process on a 300 mm wafer at 280 °C. The mean film thickness remains nearly constant at ~4.8–5.0 nm across pulse times, confirming self-limiting growth, while large error bars at short pulses indicate poor wafer-scale coverage. Uniformity improves from ~9% at 100 ms to below 1% at ~1000 ms, demonstrating that sufficient pulse time is required to achieve uniform deposition over large areas.

| Ti Precursor Pulse Time (ms) | Value | Parameter |
|-----------------------------|-------|-----------|
| 0                           |       | Mean film thickness (nm) |
| 0                           |       | Uniformity (%) |
| 100                         | 5.17  | Mean film thickness (nm) |
| 100                         | 8.7   | Uniformity (%) |
| 200                         | 4.95  | Mean film thickness (nm) |
| 200                         | 4.91  | Uniformity (%) |
| 300                         | 4.96  | Mean film thickness (nm) |
| 300                         | 5.63  | Uniformity (%) |
| 400                         | 4.89  | Mean film thickness (nm) |
| 400                         | 7.4   | Uniformity (%) |
| 500                         | 4.71  | Mean film thickness (nm) |
| 500                         | 5.36  | Uniformity (%) |
| 600                         | 4.86  | Mean film thickness (nm) |
| 600                         | 4.3   | Uniformity (%) |
| 700                         | 4.78  | Mean film thickness (nm) |
| 700                         | 2.09  | Uniformity (%) |
| 800                         | 4.88  | Mean film thickness (nm) |
| 800                         | 2.32  | Uniformity (%) |
| 900                         | 4.86  | Mean film thickness (nm) |
| 900                         | 1.4   | Uniformity (%) |
| 1000                        |       | Mean film thickness (nm) |
| 1000                        | 0.864 | Uniformity (%) |
| 1100                        |       | Mean film thickness (nm) |
| 1100                        | 0.66  | Uniformity (%) |
| 1200                        |       | Mean film thickness (nm) |
| 1200                        | 0.79  | Uniformity (%) |
| 1300                        |       | Mean film thickness (nm) |
| 1300                        |       | Uniformity (%) |
| 1400                        |       | Mean film thickness (nm) |
| 1400                        |       | Uniformity (%) |
| 1500                        | 4.96  | Mean film thickness (nm) |
| 1500                        | 1.17  | Uniformity (%) |
| 1600                        |       | Mean film thickness (nm) |
| 1600                        |       | Uniformity (%) |

Answer: The repeated sequence is: 1) Ti precursor pulse, 2) Purge, 3) Reactant pulse (e.g., H₂O), 4) Purge. A longer precursor pulse allows more time for the precursor to diffuse and fully saturate all reactive sites on the wafer surface, increasing the adsorbed amount per cycle and thus the growth per cycle (GPC) until saturation.

Answer: Both 1000 ms and 1500 ms yield <1% uniformity and ~5 nm thickness. The process result is identical.  Trade-off: Operating at 1500 ms is wasteful. The specific cost driver is Precursor consumption and throughput. The extra 500 ms per cycle adds up significantly over thousands of cycles (e.g., adding minutes to the process time) and wastes expensive Titanium precursor that is simply pumped out of the exhaust without reacting, increasing the cost.

Answer: Uniformity improves then slightly degrades. At short pulses, precursor depletion across the wafer causes center-to-edge non-uniformity. An intermediate pulse allows full, even saturation (best uniformity). Very long pulses may lead to parasitic CVD or desorption, reintroducing non-uniformity.

Answer: The optimal range is just beyond the knee where thickness saturates and uniformity is near its peak (~150-200 ms). This ensures reproducible thickness (controlled GPC) and excellent wafer-scale uniformity, both of which are critical for device performance and yield in integrated circuit manufacturing.


Figure 3. Growth per cycle and film density for substrate temperatures between 235 and  $350^{\circ}\mathrm{C}$ .

This figure represents how substrate temperature affects two key properties in an ALD process: Growth Per Cycle (GPC) increases monotonically with temperature, while Film Density peaks at an optimal temperature (~325°C) before decreasing.

| Substrate temperature (°C) | Value | Condition                     |
|---------------------------:|------:|-------------------------------|
| 225.0                      |       | Growth per cycle (Å)          |
| 225.0                      |       | Film density (g/cm³)          |
| 233.5                      | 0.21  | Growth per cycle (Å)          |
| 233.5                      | 3.89  | Film density (g/cm³)          |
| 245.31                     | 0.20  | Growth per cycle (Å)          |
| 245.31                     | 3.93  | Film density (g/cm³)          |
| 256.5                      | 0.21  | Growth per cycle (Å)          |
| 256.5                      | 3.97  | Film density (g/cm³)          |
| 268.0                      | 0.23  | Growth per cycle (Å)          |
| 268.0                      | 3.99  | Film density (g/cm³)          |
| 280.0                      | 0.23  | Growth per cycle (Å)          |
| 280.0                      | 4.00  | Film density (g/cm³)          |
| 291.8                      | 0.26  | Growth per cycle (Å)          |
| 291.8                      | 4.00  | Film density (g/cm³)          |
| 324.0                      | 0.28  | Growth per cycle (Å)          |
| 324.0                      | 4.18  | Film density (g/cm³)          |
| 350.0                      | 0.50  | Growth per cycle (Å)          |
| 350.0                      | 3.97  | Film density (g/cm³)          |

Answer: The loss of control is signaled by the simultaneous spike in Growth Per Cycle (rising to ~0.5 Å) and the sharp drop in Film Density (falling to <4.0 g/cm³). This divergence typically indicates precursor thermal decomposition (CVD component), where the reaction is no longer limited by surface sites but by the continuous supply of reactant, leading to rapid but porous growth.

Answer: 325°C is the superior choice. It maximizes the critical density metric for barrier performance. Furthermore, there is no throughput penalty; in fact, the growth rate is higher at 325°C, making it a "win-win" operating point compared to 275°C.

Answer: The increasing thermal energy enhances the surface diffusion of adsorbed species, allowing atoms to settle into thermodynamically favorable, tightly packed lattice positions. This structural ordering reduces voids and efficiently removes bulky ligands, resulting in the continuous densification observed up to the 325°C thermal stability limit.

Answer: The sharp drop in density at 350°C indicates a porous, defect-rich microstructure likely containing trapped impurities from the decomposed precursor. For a gate dielectric, such defects act as leakage paths and charge traps. Consequently, this film would exhibit high leakage current and poor electrical reliability, failing to insulate the gate effectively despite the manufacturing speed advantage.


FIG. 3. (Color online) Growth rate per cycle as measured by SE at deposition temperatures of 70 and  $200^{\circ}\mathrm{C}$  as a function of the number of successive  $\mathrm{Al}(\mathrm{CH}_3)_3$  exposures used per ALD cycle. Also the mass gain determined by QCM measurements at  $70^{\circ}\mathrm{C}$  is given.

The chart shows the growth rate of SE (angstroms per cycle) at 70 and 200 °C and QCM mass gain (Hz) against the number of Al(CH₃)₃ exposures per cycle.

| Number of Al(CH₃)₃ exp. per cycle | SE: Growth rate (Å/cycle) 70 °C |SE: Growth rate (Å/cycle) 200 °C | QCM: Mass gain (Hz) 70 °C |
|---|---|---|---|
| 1 | 1.2 | 1.0 | 4.25 |
| 2 | 1.5 | 1.2 | 5.5 |
| 3 | 1.6 | 1.25 | 6.0 |
| 4 | 1.7 |  | 6.5 |
| 6 | 1.7 |  | 6.5 |
| 8 |  | 1.25 |  |
| 10 | 1.8 |  | 6.75 |
| 15 | 1.8 |  | 6.75 |

Answer: 1.27 Å/cycle.

Answer: 1.66 Å/cycle.

Answer: About 7 Hz.

Answer: At both 70 and 200 °C, the growth rate increases sharply and then plateaus. The final growth rates are 1.8 and 1.27 Å/cycle for 70 and 200 °C, respectively. Saturated growth is observed at both temperatures, which means the process meets the requirements of ALD.


FIG. 3. (Color online) Real  $(\epsilon_{1})$  and imaginary  $(\epsilon_{2})$  part of the dielectric function as a function of photon energy measured by ex situ SE. The sharp features at a growth temperature of  $400^{\circ}\mathrm{C}$  indicate the polycrystalline structure of the film. The transition from smooth to sharp dielectric function for films grown at  $400^{\circ}\mathrm{C}$  can be observed in the inset.

This figure compares the optical dielectric function of films grown at different temperatures (150–400 °C) as a function of photon energy. The left axis shows the real part ε₁, which increases  with photon energy and shows modest temperature-dependent shifts. The right axis shows the imaginary part, ε₂ (optical absorption), which is near zero at low energies and then rises sharply around ~5.5–6+ eV.

| Temperature, °C | Photon energy (eV) |  ε₁ |  ε₂  |
|---|---|---|---|
| 150 | 1.2 | 3.8 | 0.01 |
| 150 | 5 | 5.3| 0.01 |
| 150 | 6.4 | 8.2 | 1.7 |
| 200 | 1.2 | 3.9 | 0.01 |
| 200 | 5 | 5.6| 0.01 |
| 200 | 6.4 | 8.6 | 1.8 |
| 250 | 1.2 | 3.9 | 0.01 |
| 250 | 5 | 5.6| 0.01  |
| 250 | 6.4 | 8.9 | 1.8 |
| 300 | 1.2 | 3.9 | 0.01  |
| 300 | 5 | 5.9| 0.01  |
| 300 | 6.4 | 9.2 | 1.9 |
| 350 | 1.2 | 4 | 0.01 |
| 350 | 5 | 5.9|  0.01 |
| 350 | 6.4 | 9.1 | 1.9 |
| 400 | 1.2 | 4.0 | 0.01  |
| 400 | 5 | 5.8| 0.01 |
| 400 | 6.0 | 7.7 | 0.86 |
| 400 | 6.4 | 8.7 | 1.2 |

Answer: The film grown at 400 °C shows the highest refractive index. In the low-photon-energy region where ε₂ ≈ 0, the 400 °C curve has the highest ε₁. The higher value of ε₁ in this region corresponds to the higher refractive index.

Answer: The film grown at 400 °C

Answer: Yes

Answer: The film grown at 150 °C .


Fig. 5 Refractive index  $n$  and extinction coefficient  $k$  of the produced  $\mathrm{MoO}_x$  layer as determined from spectroscopic ellipsometry

The chart displays the refractive index n and extinction coefficient k of materials under different conditions of oxygen and argon exposure over a range of photon energies.

| Sample | refractive index n | extinction coefficient k |
|---|---|---|
| 2 second O2 | Exponential increase from (1.5 eV, n = 1.8) to (3.0 eV, n = 2.2) | Constant at k = 0 |
| 2 second O2 & Ar | Exponential increase from (1.5 eV, n = 1.9) to (3.0 eV, n = 2.3) | Constant at > 0 |
| 1 second O2 | Peak at 2 eV, trough at 2.5 eV | Peak at 2.25 eV, trough at 2.75 eV |

Answer: The three samples differed in plasma type and exposure time; 1 s O2 plasma, 2 s O2 plasma, 2 s O2 and 2 s Ar plasma.

Answer: 1 s oxygen plasma exposure caused the sample to still have a nonzero extinction index, whereas 2 s oxygen plasma exposure led to no extinction index. The additional argon plasma exposure led to a small and constant extinction index.

Answer: The 1 s oxygen has a clear peak and trough, whereas the samples exposed to 2 seconds of oxygen plasma only show an exponential increase (as a function of photon energy).

Answer: About 0.1.


FIG. 11. Calculated energy flux density delivered to the surface via ions (open circles) as well as ions and fast neutrals (squares) plotted as a function of pressure, power, and  $\mathrm{O}_2$  flow fraction. The dotted lines represent the estimated energy flux density from ions and fast neutrals necessary for the onset of crystallization ( $\approx 0.02\mathrm{W} / \mathrm{m}^2$ ) and saturation in crystalline character ( $\approx 0.04\mathrm{W} / \mathrm{m}^2$ ). The area of Mixed Crystalline Character showed weak evidence of the crystalline material. The boundaries for crystallization thresholds are estimated from thin film characterizations.

In panel (a), increasing pressure leads to a rapid decline in energy flux for both "Ions + fast neutrals" and "Ions only", with fast neutrals contributing significantly to overall flux.

Panel (b) demonstrates a sharp increase in energy flux with power in a CCP system, transitioning from amorphous to mixed, and eventually to crystalline film growth at high power.

Panel (c) displays a similar trend with increasing O₂ flow fraction, low fractions result in amorphous material, while higher flow promotes crystalline structure. The figure  shows how process parameters directly influence energy delivery and crystalline phase formation.

| Pressure (mTorr) | Energy Flux Density - Ions + Fast Neutrals (W/m²) | Energy Flux Density - Ions Only (W/m²) |
|------------------|---------------------------------------------------|----------------------------------------|
| 500              | 0.14                                              | 0.03                                   |
| 1000             | 0.10                                              | 0.02                                   |
| 1500             | 0.08                                              | 0.01                                   |
| 2000             | 0.06                                              | 0.007                                  |
| 3000             | 0.04                                              | 0.005                                  |
| 4000             | 0.03                                              | 0.004                                  |
| 5000             | 0.02                                              | 0.003                                  |

| Power (W) | Energy Flux Density (W/m²) | Crystallinity |
|-----------|-----------------------------|----------------|
| 100       | 0.1                         | Amorphous      |
| 200       | 0.2                         | Amorphous      |
| 300       | 0.4                         | Mixed          |
| 400       | 0.8                         | Mixed          |
| 500       | 1.2                         | Mixed          |
| 600       | 1.6                         | Crystalline    |
| 700       | 2.0                         | Crystalline    |
| 800       | 2.4                         | Crystalline    |
| 900       | 2.6                         | Crystalline    |
| 1000      | 2.8                         | Crystalline    |

| O₂ Flow Fraction | Energy Flux Density (W/m²) | Crystallinity |
|------------------|-----------------------------|----------------|
| 0.0              | 0.03                        | Amorphous      |
| 0.1              | 0.04                        | Amorphous      |
| 0.2              | 0.05                        | Mixed          |
| 0.3              | 0.06                        | Mixed          |
| 0.4              | 0.07                        | Mixed          |
| 0.5              | 0.08                        | Crystalline    |
| 0.6              | 0.09                        | Crystalline    |

Answer: As RF power increases from 100 W to 1000 W, the energy flux density rises sharply from approximately 0.1 W/m² to nearly 3 W/m². This dramatic increase correlates with a transition in material crystallinity—from amorphous at low power to mixed-phase, and ultimately crystalline at higher power levels. The figure clearly shows that there is a threshold energy flux beyond which crystalline growth becomes favored, highlighting the role of plasma energy input in driving film ordering and structure.

Answer: Pressure (mTorr), RF Power (W), O₂ flow fraction

Answer: Yes

Answer: Approx. 600 W

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-deposition/experimental-usecase/67/P. M. Litwin et al.pdf


FIG. 12. Ion energies derived from the measured plasma potential (squares) and from the calculated average ion energy (circles) plotted as a function of pressure, power, and  $\mathrm{O}_2$  flow fraction. The dotted lines represent the estimated ion energy necessary for the onset of crystallization ( $\approx 11\mathrm{eV}$ ) and fully developed crystalline character ( $\approx 17\mathrm{eV}$ ). The area of Mixed Crystalline Character showed weak evidence of the crystalline material. The boundaries for crystallization thresholds are estimated from thin film characterizations.

Panel (a) shows that increasing pressure reduces both plasma potential and ion energy.

Panel (b) reveals that increasing RF power leads to a steady rise in ion energy.

Panel (c) illustrates that higher O₂ flow fractions also result in increased ion energy, with a transition from amorphous to crystalline film regimes indicated in the central panel.

| Pressure (mTorr) | Plasma Potential (eV) | Mean Ion Energy (eV) |
|------------------|------------------------|------------------------|
| 830              | ~42                    | ~22                    |
| 1600             | ~38                    | ~20                    |
| 2400             | ~34                    | ~18                    |
| 3000             | ~31                    | ~15                    |
| 4300             | ~27                    | ~13                    |
| 5000             | ~25                    | ~10                    |

| Power (W) | Ion Energy (eV) |
|-----------|-----------------|
| 100       | ~22             |
| 200       | ~24             |
| 300       | ~26             |
| 400       | ~28             |
| 500       | ~30             |
| 600       | ~33             |
| 700       | ~36             |
| 800       | ~38             |
| 900       | ~40             |
| 1000      | ~42             |

| O₂ Flow Fraction | Ion Energy (eV) |
|------------------|------------------|
| 0.0              | ~25              |
| 0.1              | ~27              |
| 0.2              | ~30              |
| 0.3              | ~33              |
| 0.4              | ~36              |
| 0.5              | ~40              |
| 0.6              | ~43              |

Answer: Power results in the steepest increase in ion energy

Answer: As pressure increases, both the plasma potential and mean ion energy decrease. This is attributed to the enhanced collisionality in higher-pressure regimes, which leads to energy loss through collisions, reducing the kinetic energy of ions reaching the surface. Lower plasma potentials also indicate a reduced driving force for ion acceleration. These combined effects diminish the energy transferred to the surface, influencing film growth and etching behaviour.

Answer: No

Answer: Prevents ion damage, Controls crystallinity, Optimizes selectivity and anisotropy, Maintains uniform growth and interface quality


Capacitively coupled FIG. 4. (a) Atomic O density vs plasma power measured with OES. (b) Ion flux and plasma potential as a function of plasma power. Gray regions of each plot represent processing space in which the plasma operated in a capacitively coupled mode.

This figure plots both ion flux and plasma potential as functions of power in an inductively coupled plasma (ICP) system. As RF power increases from 0 to 1000 W, both plasma potential (red circles) and ion flux (black squares) show upward trends. The plasma potential increases gradually and linearly from 0 V to 100 V, indicating a smooth energising of the plasma. In contrast, ion flux demonstrates a sharper, more nonlinear rise, particularly beyond the 600 W mark, indicating a threshold above which ion generation increases rapidly. This suggests that higher RF power significantly boosts the energy and quantity of charged species, which is critical for surface modification processes like etching or deposition

| Power (W) | Ion Flux (m⁻²·s⁻¹) × 10¹⁷ | Plasma Potential (V) |
|-----------|-----------------------------|------------------------|
| 0         | 0.0                         | 0                      |
| 50        | 2.0                         | 10                     |
| 100       | 2.0                         | 10                     |
| 150       | 3.0                         | 20                     |
| 200       | 3.0                         | 20                     |
| 250       | 4.0                         | 30                     |
| 300       | 4.0                         | 30                     |
| 350       | 5.0                         | 40                     |
| 400       | 5.0                         | 40                     |
| 450       | 6.0                         | 50                     |
| 500       | 6.0                         | 50                     |
| 550       | 7.0                         | 60                     |
| 600       | 7.0                         | 60                     |
| 650       | 8.0                         | 70                     |
| 700       | 8.0                         | 70                     |
| 750       | 9.0                         | 80                     |
| 800       | 9.0                         | 80                     |
| 850       | 10.0                        | 90                     |
| 900       | 10.0                        | 90                     |
| 950       | 11.0                        | 100                    |
| 1000      | 11.0                        | 100                    |

Answer: Both ion flux and plasma potential increase as the power rises from 0 W to 1000 W. However, their rates of increase differ. Plasma potential exhibits a relatively linear progression, climbing steadily from 0 V to 100 V. In contrast, ion flux remains low until approximately 500–600 W, after which it increases steeply, more than quadrupling in value. This disparity suggests a threshold behavior in ion production, where power beyond a critical value significantly enhances ion generation. This information is crucial for tuning plasma parameters in applications requiring high-density ion bombardment.

Answer: 50 V

Answer: RF Power (W), Ion flux (m⁻²·s⁻¹), Plasma potential (V)

Answer: Yes


This multi-axis chart shows how ion flux and plasma potential vary with changes in O₂ flow fraction. As O₂ flow increases from 0.0 to 0.3, ion flux initially decreases, reaching a minimum, before increasing again at 0.5. In contrast, plasma potential exhibits a steady upward trend, rising from 20 V at 0.0 O₂ flow to 45 V at 0.5. This divergence suggests that while plasma potential becomes stronger with more oxygen, the ion flux behaviour is non-monotonic and may be influenced by other plasma chemistry factors.

| O₂ Flow Fraction | Ion flux (m⁻² s⁻¹) | Plasma Potential (V) |
|------------------|------------------|---------------------|
| 0.0              | 3×10¹⁶          | 20                  |
| 0.1              | 2×10¹⁶          | 25                  |
| 0.3              | 1.5×10¹⁶        | 30                  |
| 0.5              | 3×10¹⁶          | 45                  |

Answer: Ion flux does not follow a monotonic trend. It decreases between 0.0 and 0.3 O₂ flow fraction, reaching its lowest value at 0.3, then rises again at 0.5. In contrast, plasma potential steadily increases with increasing O₂ flow fraction, starting at 20 V and reaching 45 V at the highest flow rate. This indicates that oxygen affects ion energy and flux through different plasma mechanisms, likely involving electron density and ionisation efficiency

Answer: 0.3 O₂ flow fraction

Answer: No

Answer: Plasma potential controls ion energy, Ion flux sets reactive species count, Balance optimizes efficiency


This multi-axis chart displays how ion flux and plasma potential change with increasing pressure for two plasma coupling modes. The ion flux decreases sharply between 500 mTorr and 2000 mTorr, then levels off, while the plasma potential steadily drops with pressure, stabilising around 10 V. The figure visually separates regions of capacitive coupling and inductive coupling, highlighting their different ion delivery characteristics in plasma processing.

| Pressure (mTorr) | Ion flux (m⁻² s⁻¹) | Plasma potential (V) |
|------------------|---------------------|-----------------------|
| 500              | 4.0 × 10¹⁶          | 50                    |
| 1000             | 2.5 × 10¹⁶          | 25                    |
| 2000             | 1.5 × 10¹⁶          | 20                    |
| 3000             | 1.2 × 10¹⁶          | 15                    |
| 4000             | 1.0 × 10¹⁶          | 12                    |
| 5000             | 1.0 × 10¹⁶          | 10                    |

Answer: The figure shows that at low pressure (around 500 mTorr), capacitive coupling leads to a much higher plasma potential and significantly greater ion flux compared to inductive coupling. As pressure increases, ion flux drops steeply and levels off, while plasma potential also decreases. This indicates that capacitive coupling is more effective at delivering energetic ions to the surface in low-pressure conditions, while inductive coupling provides more moderate plasma potentials and ion fluxes across a broader pressure range.

Answer: No

Answer: 2000 mTorr

Answer: Reduced ion acceleration , Lower surface etch rates , Gentler plasma–material interactions


TMA and water concentrations at position B (water side) over time for three wafer temperatures (150°C, 200°C, 250°C). Higher temperature increases TMA (foreign precursor) concentration, with 250°C reaching approximately 1.5×10⁻⁵ mol/m³ compared to 0.8×10⁻⁵ mol/m³ at 150°C. Water (home precursor) reaches steady state faster at higher temperatures but achieves lower final concentration.

TMA and water concentrations at position C (TMA side) over time for three wafer temperatures. Higher temperature increases water intermixing, with 250°C yielding approximately 2×10⁻⁴ mol/m³ water compared to 1.7×10⁻⁴ mol/m³ at 150°C. TMA (home precursor) shows slightly lower steady-state values at higher temperatures.

| Time (s) | TMA 150°C (mol/m³) | TMA 200°C (mol/m³) | TMA 250°C (mol/m³) | Water 150°C (mol/m³) | Water 200°C (mol/m³) | Water 250°C (mol/m³) |
|---|---|---|---|---|---|---|
| 0.000 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| 0.005 | 0.01E-5 | 0.01E-5 | 0.01E-5 | 1.9E-3 | 1.5E-3 | 1.0E-3 |
| 0.010 | 0.05E-5 | 0.05E-5 | 0.08E-5 | 5.8E-3 | 4.8E-3 | 3.5E-3 |
| 0.015 | 0.20E-5 | 0.25E-5 | 0.35E-5 | 6.7E-3 | 5.8E-3 | 5.1E-3 |
| 0.020 | 0.45E-5 | 0.50E-5 | 0.65E-5 | 6.9E-3 | 6.1E-3 | 5.5E-3 |
| 0.025 | 0.70E-5 | 0.75E-5 | 0.90E-5 | 6.9E-3 | 6.1E-3 | 5.6E-3 |
| 0.030 | 0.82E-5 | 0.88E-5 | 1.05E-5 | 6.9E-3 | 6.2E-3 | 5.6E-3 |
| 0.040 | 0.85E-5 | 0.92E-5 | 1.10E-5 | 6.9E-3 | 6.2E-3 | 5.6E-3 |

| Time (s) | TMA 150°C (mol/m³) | TMA 200°C (mol/m³) | TMA 250°C (mol/m³) | Water 150°C (mol/m³) | Water 200°C (mol/m³) | Water 250°C (mol/m³) |
|---|---|---|---|---|---|---|
| 0.000 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| 0.005 | 0.25E-3 | 0.15E-3 | 0.10E-3 | 0.00 | 0.00 | 0.00 |
| 0.010 | 1.20E-3 | 0.80E-3 | 0.60E-3 | 0.15E-4 | 0.20E-4 | 0.10E-4 |
| 0.015 | 2.50E-3 | 1.90E-3 | 1.40E-3 | 0.90E-4 | 1.00E-4 | 1.10E-4 |
| 0.020 | 3.60E-3 | 2.80E-3 | 2.20E-3 | 1.40E-4 | 1.60E-4 | 1.80E-4 |
| 0.025 | 4.10E-3 | 3.50E-3 | 2.80E-3 | 1.70E-4 | 1.90E-4 | 2.20E-4 |
| 0.030 | 4.30E-3 | 3.80E-3 | 3.10E-3 | 1.80E-4 | 2.10E-4 | 2.40E-4 |
| 0.040 | 4.40E-3 | 4.00E-3 | 3.30E-3 | 1.90E-4 | 2.20E-4 | 2.60E-4 |

Answer: Temperature has a moderate effect on intermixing, increasing foreign precursor concentrations at both monitoring positions as temperature rises from 150°C to 250°C. However, gap size has the strongest influence on intermixing (Figure 4 shows an 8-fold difference between 1 mm and 2 mm gaps), while pumping pressure has an intermediate effect. Temperature uniquely affects both intermixing and deposition kinetics, creating a trade-off since higher temperatures improve film growth rate but worsen precursor separation.

Answer: At higher temperatures, the gas expands and has lower density, and enhanced diffusion distributes water molecules more broadly, resulting in slightly lower local concentrations at the monitoring position.

Answer: 200°C offers a reasonable compromise, providing good deposition rate (approximately 1.2 Å/cycle) while maintaining moderate intermixing levels, compared to 250°C which has higher intermixing or 150°C which has slower deposition kinetics.

Answer: Higher temperature accelerates diffusive mass transport by increasing molecular kinetic energy, which enhances the movement of precursor molecules across the separating gas barriers into neighboring zones.


Fig. 3. The effects of gap size on precursor intermixing with ideal pumping condition (0.22 torr) and  $200^{\circ}$ C deposition temperature: (a) TMA and water concentration in  $\mathrm{mol} / \mathrm{m}^3$  at water side (position B) with gap size 1, 1.5, and  $2 \mathrm{mm}$ , and (b) at TMA side (position C) with gap size 1, 1.5, and  $2 \mathrm{mm}$ .

TMA and water concentrations at position B (water side) over time for three gap sizes. The left axis shows TMA (the foreign precursor at this location) reaching steady state concentrations of approximately 3×10⁻⁵ mol/m³ for 1 mm gap versus less than 1×10⁻⁵ mol/m³ for larger gaps. The right axis shows water (home precursor) concentration, which reaches steady state faster for larger gaps.

TMA and water concentrations at position C (TMA side) over time for three gap sizes. TMA (home precursor, left axis) reaches approximately 4×10⁻³ mol/m³ at steady state for all gaps, while water (foreign precursor, right axis) shows higher intermixing levels, particularly for 1 mm gap where water concentration reaches approximately 5×10⁻⁴ mol/m³.

| Time (s) | TMA-1mm (mol/m³) | TMA-1.5mm (mol/m³) | TMA-2mm (mol/m³) | Water-1mm (mol/m³) | Water-1.5mm (mol/m³) | Water-2mm (mol/m³) |
|---|---|---|---|---|---|---|
| 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| 0.01 | 0.00 | 0.10E-5 | 0.10E-5 | 0.10E-3 | 3.8E-3 | 5.5E-3 |
| 0.02 | 0.05E-5 | 0.50E-5 | 0.30E-5 | 0.20E-3 | 5.8E-3 | 6.5E-3 |
| 0.03 | 0.10E-5 | 0.80E-5 | 0.30E-5 | 1.0E-3 | 6.2E-3 | 6.6E-3 |
| 0.04 | 0.40E-5 | 0.90E-5 | 0.30E-5 | 3.5E-3 | 6.3E-3 | 6.6E-3 |
| 0.06 | 1.40E-5 | 0.90E-5 | 0.30E-5 | 4.9E-3 | 6.3E-3 | 6.6E-3 |
| 0.08 | 2.30E-5 | 0.90E-5 | 0.30E-5 | 5.4E-3 | 6.3E-3 | 6.6E-3 |
| 0.10 | 3.10E-5 | 0.90E-5 | 0.30E-5 | 5.8E-3 | 6.3E-3 | 6.6E-3 |

| Time (s) | TMA-1mm (mol/m³) | TMA-1.5mm (mol/m³) | TMA-2mm (mol/m³) | Water-1mm (mol/m³) | Water-1.5mm (mol/m³) | Water-2mm (mol/m³) |
|---|---|---|---|---|---|---|
| 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| 0.01 | 0.10E-3 | 0.80E-3 | 2.0E-3 | 0.00 | 0.50E-4 | 1.0E-4 |
| 0.02 | 0.20E-3 | 2.20E-3 | 3.8E-3 | 0.10E-4 | 1.20E-4 | 1.5E-4 |
| 0.03 | 0.30E-3 | 3.20E-3 | 3.9E-3 | 0.30E-4 | 1.80E-4 | 1.5E-4 |
| 0.04 | 0.50E-3 | 3.60E-3 | 4.0E-3 | 0.80E-4 | 2.00E-4 | 1.5E-4 |
| 0.06 | 1.00E-3 | 3.60E-3 | 4.0E-3 | 2.20E-4 | 2.00E-4 | 1.5E-4 |
| 0.08 | 1.60E-3 | 3.60E-3 | 4.0E-3 | 3.60E-4 | 2.00E-4 | 1.5E-4 |
| 0.10 | 2.10E-3 | 3.60E-3 | 4.0E-3 | 4.60E-4 | 2.00E-4 | 1.5E-4 |

Answer: The 1 mm gap produces the highest intermixing levels at both monitoring positions. This occurs because the narrow gap restricts convective gas flow, making mass transport dominated by diffusion. In the high vacuum system (0.22 torr), diffused precursor molecules accumulate in the exhaust regions due to insufficient convective forces to purge them, resulting in higher foreign precursor concentrations compared to larger gaps where convection is more effective.

Answer: In (a), water is the home precursor at position B so its concentration is high (10⁻³ to 10⁻² mol/m³). In (b), water is the foreign precursor at position C, so only small amounts from intermixing are detected (10⁻⁴ mol/m³ scale).

Answer: Position B is located at the water side (under the exhaust between water and nitrogen zones) and position C is at the TMA side (under the exhaust between nitrogen and TMA zones), used to monitor precursor concentrations and intermixing.

Answer: Intermixing is more severe at the TMA side, with a relative intermixing ratio of approximately 1:4 (water to TMA), compared to weaker intermixing at the water side, due to water's higher inlet vapor pressure driving stronger diffusion.


Fig. 5. The effects of relative pumping pressure (0, 0.05, to 0.1 torr) on the precursor intermixing with gap size and wafer temperature fixed at  $1.5 \mathrm{mm}$  and  $200^{\circ}$ C: (a) TMA and water concentration in  $\mathrm{mol} / \mathrm{m}^3$  at water side (position B), and (b) at TMA side (position C). The simulation time is  $0.04 \mathrm{s}$  with  $1.5 \mathrm{mm}$  gap size.

TMA and water concentrations at position B (water side) over time for three relative pumping pressures (0, 0.05, 0.1 torr above base pressure). Higher pumping pressure results in higher TMA intermixing, with 0.1 torr yielding approximately 2.2×10⁻⁵ mol/m³ TMA compared to less than 1×10⁻⁵ mol/m³ at 0 torr. Water (home precursor) shows similar steady state levels across all pressures.

TMA and water concentrations at position C (TMA side) over time for three relative pumping pressures. Higher pumping pressure increases water intermixing, with steady state water concentration approximately doubling from 2×10⁻⁴ mol/m³ at 0 torr to 5×10⁻⁴ mol/m³ at 0.1 torr. TMA (home precursor) reaches similar levels across all pressures.

| Time (s) | TMA-0 torr (mol/m³) | TMA-0.05 torr (mol/m³) | TMA-0.1 torr (mol/m³) | Water-0 torr (mol/m³) | Water-0.05 torr (mol/m³) | Water-0.1 torr (mol/m³) |
|---|---|---|---|---|---|---|
| 0.000 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| 0.005 | 0.00 | 0.00 | 0.00 | 2.5E-3 | 3.2E-3 | 4.0E-3 |
| 0.010 | 0.10E-5 | 0.20E-5 | 0.20E-5 | 4.8E-3 | 5.5E-3 | 6.2E-3 |
| 0.020 | 0.50E-5 | 0.80E-5 | 0.85E-5 | 6.1E-3 | 6.4E-3 | 6.7E-3 |
| 0.030 | 0.80E-5 | 1.40E-5 | 1.60E-5 | 6.3E-3 | 6.5E-3 | 6.8E-3 |
| 0.040 | 0.95E-5 | 1.70E-5 | 2.20E-5 | 6.3E-3 | 6.5E-3 | 6.9E-3 |

| Time (s) | TMA-0 torr (mol/m³) | TMA-0.05 torr (mol/m³) | TMA-0.1 torr (mol/m³) | Water-0 torr (mol/m³) | Water-0.05 torr (mol/m³) | Water-0.1 torr (mol/m³) |
|---|---|---|---|---|---|---|
| 0.000 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| 0.010 | 0.80E-3 | 1.00E-3 | 1.20E-3 | 0.50E-4 | 0.80E-4 | 1.20E-4 |
| 0.020 | 2.40E-3 | 2.70E-3 | 2.90E-3 | 1.90E-4 | 2.60E-4 | 3.50E-4 |
| 0.030 | 3.20E-3 | 3.60E-3 | 3.70E-3 | 2.00E-4 | 3.00E-4 | 4.90E-4 |
| 0.040 | 3.60E-3 | 4.10E-3 | 4.30E-3 | 2.10E-4 | 3.10E-4 | 5.30E-4 |

Answer: It means the pumping pressure equals the base vacuum pressure of 0.22 torr, representing the ideal pumping condition with maximum pressure difference driving convective flow.

Answer: The 0 torr relative pumping pressure (equal to the base pressure of 0.22 torr) minimizes intermixing, as it maintains the maximum pressure gradient for effective convective gas removal.

Answer: The home precursor is continuously supplied directly above each monitoring position, maintaining its concentration regardless of pumping efficiency, while foreign precursor levels depend on how effectively the exhaust system prevents cross-contamination through convective purging.

Answer: Higher relative pumping pressure increases precursor intermixing at both monitoring positions. At the water side (a), TMA concentration roughly doubles from 0 torr to 0.1 torr. At the TMA side (b), water concentration increases from approximately 2×10⁻⁴ to 5×10⁻⁴ mol/m³. This occurs because higher pumping pressure reduces the pressure difference between inlets and outlets, weakening convective mass transport and allowing more diffusive mixing of precursors.


FIG. 6. (Color online) Correlations of surface deposition rate of  $\mathrm{O(s)}$  and TMA molar fraction with coverage of  $\mathrm{^*Al(CH_3)_2(s)}$  for TMA pulsing step at 100, 150, 200, and  $250^{\circ}\mathrm{C}$ , respectively. The gray dotted lines show the temperature effect on surface deposition. Surface deposition rate of  $\mathrm{O(s)}$  in mass per area per second is achieved by substituting Eq. (14) into Eq. (10).

TMA pulse at 100°C: Correlates surface deposition rate of O⟨s⟩ (red), TMA mole fraction (black), and *Al(CH₃)₂ surface coverage (blue). Deposition rate peaks around 5 ms then drops as surface coverage saturates to 50%, despite continued TMA concentration increase.

TMA pulse at 150°C: Faster surface saturation than 100°C, with peak deposition occurring earlier. The dotted line at t=0.004s shows temperature comparison across panels.

TMA pulse at 200°C: Surface saturation occurs even earlier. Peak deposition rate remains similar but is reached more quickly.

TMA pulse at 250°C: Fastest saturation; surface coverage reaches 50% before 0.004s. At this point, deposition rate at 250°C is slightly lower than 200°C because surface is already saturated.

| Flow time (ms) | Surface Deposition Rate of O ( kg/m2-s ) | *Al(Me)2 Surface Coverage | TMA Mole Fraction |
|---|---|---|---|
| 2 | 0.15e-04 | 0.10 | 0.00 |
| 3 | 0.60e-04 | 0.30 | 0.01 |
| 4 | 1.65e-04 | 0.50 | 0.05 |
| 5 | 0.10e-04 | 0.50 | 0.18 |
| 6 | 0.01e-04 | 0.50 | 0.30 |
| 8 | 0.00 | 0.50 | 0.50 |
| 10 | 0.00 | 0.50 | 0.65 |
| 12 | 0.00 | 0.50 | 0.75 |
| 14 | 0.00 | 0.50 | 0.80 |
| 20 | 0.00 | 0.50 | 0.90 |

| Flow time (ms) | Surface Deposition Rate of O ( kg/m2-s ) | *Al(Me)2 Surface Coverage | TMA Mole Fraction |
|---|---|---|---|
| 2 | 0.05e-04 | 0.00 | 0.00 |
| 3 | 0.35e-04 | 0.10 | 0.02 |
| 4 | 1.05e-04 | 0.35 | 0.05 |
| 5 | 1.65e-04 | 0.50 | 0.15 |
| 6 | 0.10e-04 | 0.50 | 0.30 |
| 8 | 0.00 | 0.50 | 0.55 |
| 10 | 0.00 | 0.50 | 0.70 |
| 12 | 0.00 | 0.50 | 0.80 |
| 20 | 0.00 | 0.50 | 0.95 |

| Flow time (ms) | Surface Deposition Rate of O ( kg/m2-s ) | *Al(Me)2 Surface Coverage | TMA Mole Fraction |
|---|---|---|---|
| 2 | 0.05e-04 | 0.00 | 0.00 |
| 3 | 0.55e-04 | 0.15 | 0.02 |
| 4 | 1.70e-04 | 0.50 | 0.10 |
| 5 | 0.15e-04 | 0.50 | 0.25 |
| 6 | 0.00 | 0.50 | 0.45 |
| 8 | 0.00 | 0.50 | 0.70 |
| 10 | 0.00 | 0.50 | 0.82 |
| 12 | 0.00 | 0.50 | 0.90 |
| 20 | 0.00 | 0.50 | 0.98 |

| Flow time (ms) | Surface Deposition Rate of O ( kg/m2-s ) | *Al(Me)2 Surface Coverage | TMA Mole Fraction |
|---|---|---|---|
| 2 | 0.05e-04 | 0.00 | 0.00 |
| 3 | 0.75e-04 | 0.20 | 0.05 |
| 4 | 1.55e-04 | 0.50 | 0.25 |
| 5 | 0.10e-04 | 0.50 | 0.45 |
| 6 | 0.00 | 0.50 | 0.60 |
| 8 | 0.00 | 0.50 | 0.82 |
| 10 | 0.00 | 0.50 | 0.90 |
| 12 | 0.00 | 0.50 | 0.95 |
| 20 | 0.00 | 0.50 | 0.98 |

Answer: The deposition rate drops drastically once surface coverage saturates at 50% (the other half is occupied by *AlCH₃). Even though TMA concentration continues to increase, no further deposition occurs because all reactive *OH surface sites have been consumed. This demonstrates the self-limiting nature of ALD.

Answer: Red circles (left axis): mass deposition rate of bulk oxygen species O⟨s⟩; black squares (right axis): TMA gas-phase mole fraction; blue diamonds (right axis): *Al(CH₃)₂ surface species coverage.

Answer: No. The peak deposition rate values are nearly identical (~1.6×10⁻⁴ kg/m²·s) across all four temperatures; only the time to reach the peak changes.

Answer: Higher temperature accelerates saturation. The dotted lines show saturation is reached at approximately t=0.004s for 100°C but progressively earlier at higher temperatures, with 250°C saturating fastest.


FIG. 7. (Color online) Relation of surface deposition rate of  $\mathrm{Al}(\mathrm{s})$ ,  $\mathrm{H}_2\mathrm{O}$  molar fraction and coverage of species  $\mathrm{^*OH}$  for water pulsing step at 100, 150, 200, and  $250^{\circ}\mathrm{C}$ , respectively. The gray dotted lines show the process temperature effect on surface deposition. Surface deposition rate of  $\mathrm{Al}(\mathrm{s})$  in mass per area per second is achieved by substituting Eq. (14) into Eq. (10).

Water pulse at 100°C: Shows surface deposition rate of Al⟨s⟩ (red), H₂O mole fraction (black), and *OH surface coverage (purple). Deposition rate peaks then declines as *OH coverage saturates to ~100%.

Water pulse at 150°C: Faster *OH saturation than 100°C. Peak deposition rate is slightly higher and reached earlier.

Water pulse at 200°C: Surface saturates around t=0.003s. Deposition becomes hindered once *OH fully covers the surface.

Water pulse at 250°C: Fastest saturation with highest peak deposition rate. However, after ~0.003s, deposition rate at 250°C falls below that at 200°C because reactive *Al(CH₃)₂ and *AlCH₃ sites are consumed more quickly.

| Flow time (ms) | Surface Deposition Rate ( kg/m2-s ) | *OH Surface Coverage | H2O Mole Fraction |
|---|---|---|---|
| 1 | 0.55e-04 | 0.15 | 0.02 |
| 2 | 1.05e-04 | 0.70 | 0.05 |
| 3 | 0.45e-04 | 0.92 | 0.20 |
| 4 | 0.15e-04 | 0.98 | 0.55 |
| 5 | 0.02e-04 | 1.00 | 0.85 |
| 6 | 0.00 | 1.00 | 0.95 |
| 7 | 0.00 | 1.00 | 1.00 |

| Flow time (ms) | Surface Deposition Rate ( kg/m2-s ) | *OH Surface Coverage | H2O Mole Fraction |
|---|---|---|---|
| 1 | 0.70e-04 | 0.35 | 0.02 |
| 2 | 1.15e-04 | 0.90 | 0.10 |
| 3 | 0.35e-04 | 0.99 | 0.38 |
| 4 | 0.05e-04 | 1.00 | 0.78 |
| 5 | 0.00 | 1.00 | 0.95 |
| 6 | 0.00 | 1.00 | 1.00 |

| Flow time (ms) | Surface Deposition Rate ( kg/m2-s ) | *OH Surface Coverage | H2O Mole Fraction |
|---|---|---|---|
| 1 | 0.85e-04 | 0.55 | 0.02 |
| 2 | 1.20e-04 | 0.95 | 0.20 |
| 3 | 0.25e-04 | 1.00 | 0.60 |
| 4 | 0.02e-04 | 1.00 | 0.90 |
| 5 | 0.00 | 1.00 | 0.98 |
| 6 | 0.00 | 1.00 | 1.00 |

| Flow time (ms) | Surface Deposition Rate ( kg/m2-s ) | *OH Surface Coverage | H2O Mole Fraction |
|---|---|---|---|
| 1 | 1.30e-04 | 0.50 | 0.05 |
| 2 | 0.40e-04 | 0.95 | 0.30 |
| 3 | 0.05e-04 | 1.00 | 0.80 |
| 4 | 0.00 | 1.00 | 0.98 |
| 5 | 0.00 | 1.00 | 1.00 |

Answer: The water pulse shows more complex temperature behavior. While higher temperature initially increases deposition rate (similar to TMA), after about 0.003s the deposition at higher temperatures becomes hindered. At 250°C, *OH saturates so quickly that the deposition rate drops below that at 200°C. This contrasts with TMA pulse where peak rates were temperature-independent.

Answer: No. Higher temperature increases the peak rate and accelerates saturation, but after ~0.003s the deposition rate at 250°C falls below that at 200°C due to faster consumption of reactive surface sites.

Answer: *OH (hydroxyl groups), which serve as reactive sites for the subsequent TMA pulse.

Answer: Once *OH fully covers the surface, all reactive *Al(CH₃)₂ and *AlCH₃ sites from the TMA pulse have been consumed, so no further reaction can occur.


Fig. 4. Adsorption energy and reaction energy barrier as a function of the number of DMA ligands. The effect of temperature is considered for the adsorption energy.

The figure shows how adsorption energy and reaction energy barrier change with the number of dimethylamino ligands. Adsorption strength increases monotonically, while reaction barriers show a parabolic trend, highlighting an optimal ligand range balancing stability and reactivity.

Entropy-corrected adsorption energies at 600 K are presented, showing a downward shift in adsorption energies under ALD conditions and a narrower window of viable precursors, explaining the preference for intermediate ligand numbers.

| Number of dimethylamino ligands | Adsorption energy (eV) | Reaction energy barrier (eV) |
|---|---|---|
| 0 (Silane) | 0.16 | 1.42 |
| 1 (DMAS) | 0.59 | 0.65 |
| 2 (BDMAS) | 0.69 | 0.28 |
| 3 (TDMAS) | 0.74 | 0.75 |
| 4 (TeDMAS) | 0.84 | 1.81 |

Answer: The figure identifies an optimal ligand-number window where adsorption energy is sufficient to prevent desorption while reaction barriers remain low enough for efficient surface chemistry under ALD conditions. By incorporating temperature effects and defining an acceptable adsorption-energy range, the analysis explains why precursors with intermediate DMA ligand numbers exhibit superior ALD performance.

Answer: Adsorption energy increases monotonically, while the reaction energy barrier decreases up to two DMA ligands and then increases, forming a parabolic trend.

Answer: Yes

Answer: Number of dimethylamino ligands bonded to Si, Strength of N···H–OH interactions, Steric crowding around the Si center, Ligand-induced strain at the transition state, Entropy loss upon adsorption at elevated temperature


Fig. 5. Variation of bond lengths as a function of the number of DMA ligands.  $\sum d_{\mathrm{Si - Si}}$  indicates the sum of the variation of the Si-Si bond lengths near the reaction site on the surface and  $\sum d_{\mathrm{Si - L}}$  indicates the sum of the variation of the Si-ligand bond lengths in the Si precursors.


Fig. 2. The etch depth per cycle  $(\mathrm{A / cycle})$  of  $\mathrm{Al}_2\mathrm{O}_3$  and the rms roughness of the etched  $\mathrm{Al}_2\mathrm{O}_3$  surface measured as a function of  $\mathrm{BCl}_3$  gas flow rate from 0 to 100 sccm at 1st grid voltage of  $100\mathrm{V}$  for the  $\mathrm{Ar}^+$  ion beam in the 3rd desorption step.

The chart shows the relationship between gas flow rate and etch rate and surface roughness. As the gas flow rate increases, the etch rate increases while the surface roughness decreases.

| Gas Flow Rate (sccm) | Etch Rate (Å / cycle) | Surface Roughness (Å) |
|---|---|---|
| 0 | 0.10 | 5.0 |
| 25 | 0.80 | 7.0 |
| 50 | 0.85 | 5.0 |
| 75 | 1.00 |  |
| 100 | 1.00 | 4 |

Answer: 100 V.

Answer: 1.0 Å/cycle.

Answer: Roughly 7.0 Å.

Answer: As the sccm increases, so too does the etch rate, until it reaches a value of 1.0 Å/cycle at 75 sccm. In this range, the surface roughness first increases until 25 sccm, after which it decreases. Below 75 sccm, the surface is only partially covered, which leads to partial etching. This partial etching is the cause of the increased roughness. At full surface coverage, one monolayer is etched per cycle, which leads to values of roughness comparable to the reference.

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-etching/experimental-usecase/27/Atomic layer etching of Al2O3 using BCl3Ar.pdf


Fig. 3. The etch depth  $(\mathrm{\AA})$ , etch depth per cycle  $(\mathrm{\AA / cycle})$  of  $\mathrm{Al}_2\mathrm{O}_3$ , and the rms roughness of the etched  $\mathrm{Al}_2\mathrm{O}_3$  surface measured as a function of the number of ALET etch cycles at  $\mathrm{BCl}_3$  gas flow rate of  $100~\mathrm{sccm}$  during the 1st adsorption step and at 1st grid voltage of  $100\mathrm{V}$  during the 3rd desorption step as the  $\mathrm{Al}_2\mathrm{O}_3$  ALET condition.

The chart shows the relationship between etch depth, etch rate, and surface roughness against the number of ALET cycles.

| Number of ALET Cycles | Etch Depth (Å) | Etch Rate (Å/cycles) | Surface Roughness (Å) |
|---|---|---|---|
| 50 | 50 | 1.00 | 4.0 |
| 100 | 100 | 1.00 |  |
| 150 | 150 | 1.10 | 4.5 |
| 250 | 260 | 1.10 | 5.0 |

Answer: 250.

Answer: About 220 Å.

Answer: The etch rate remained practically constant at 1.0 Å/cycle.

Answer: The surface roughness only changed slightly from 4.0 to 5.0 Å over 250 ALET cycles.


Figure 2. (a) Change of the  $\mathrm{S / Mo}$  ratio and the relative Cl atomic percentage on the  $\mathrm{MoS}_2$  surface that was measured as a function of the  $\mathrm{Ar^{+}}$  -ion exposure time (15-200 s) using XPS during the desorption step of  $\mathrm{MoS}_2$  ALE for the bilayer  $\mathrm{MoS}_2$  b) Change of the  $\mathrm{S / Mo}$  ratio and the relative Cl atomic percentage on the  $\mathrm{MoS}_2$  surface that was measured as a function of the  $\mathrm{Ar^{+}}$  -ion exposure time up to  $30~\mathrm{s},$  similar to (a).A further exposure to the  $\mathrm{Ar^{+}}$  ion of  $200~\mathrm{s}$  was performed after the annealing TA); after  $30~\mathrm{s}$  of  $\mathrm{Ar^{+}}$  ion exposure time (at  $30~\mathrm{s},$  it appeared that the top S of the  $\mathrm{MoS}_2$  had been removed), a further  $\mathrm{Ar^{+}}$  ion desorption was carried out after the  $\mathrm{MoS}_2$  sample was annealed at  $250^{\circ}C$  for  $45\mathrm{min}$  in a vacuum to remove the Cl radical on the  $\mathrm{MoS}_2$  surface. The experiment was repeated seven times, and the data were averaged. P indicates the pristine  $\mathrm{MoS}_2$  state, and Cl represents  $\mathrm{MoS}_2$  after Cl-radical adsorption.

The chart shows the relative atomic percentage of chlorine (Cl at %) and the ratio of sulfur to molybdenum (S/Mo) against exposure time in seconds. The data points are labeled with 'Sulfur removed' and 'Molybdenum removed' indicating specific conditions, to explain the trends in the ratio of S/Mo.

The chart shows the relative atomic percentage of chlorine (Cl at %) and the ratio of sulfur to molybdenum (S/Mo) against exposure time in seconds. A red arrow indicates 'Annealing (250°C, 45min)' s.

| Exposure time (sec) | P | Cl | 15 | 30 | 45 | 60 | 90 | 120 | 200 |
|---|---|---|---|---|---|---|---|---|---|
| Relative atomic percentage (%) | 0 | 60 | 45 | 30 | 20 | 10 | 5 | 0 | 0 |
| Ratio of S/Mo | 2.0 | 2.0 | 1.8 | 1.65 | 1.9 | 2.3 | 2.2 | 2.0 | 2.0 |

| Exposure time (sec) | P | Cl | 15 | 30 | TA | 60 | 90 | 120 | 200 |
|---|---|---|---|---|---|---|---|---|---|
| Relative atomic percentage (%) | 0 | 60 | 45 | 30 | 0 | 0 | 0 | 0 | 0 |
| Ratio of S/Mo | 2.0 | 2.0 | 1.8 | 1.7 | 1.7 | 1.7 | 1.7 | 1.7 | 1.7 |

Answer: The ideal ratio is 2.0, as the oxidation state of Mo is +4 and that of sulfer is -2.

Answer: 120 s.

Answer: No, this will not happen as the annealing fixes the S/Mo ratio 1.7, which should be 2.0 for high quality MoS2.

Answer: Argon ions bombard the surface and remove Cl from the surface together with sulfur.

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-etching/experimental-usecase/3/Atomic Layer Etching Mechanism of MoS2 for Nanodevices.pdf


FIG. 5. Thickness of  $\text{TiO}_2$  and EPC for ten cycles of TiN during the oxidation step as (a) a function of temperature, with a constant RF power of 15 W and (b) a function of RF power, with a constant temperature of  $100^{\circ}C$  The standard process conditions for the oxidation step used  $O_2$  at 5 SCCM, 0.05 Torr,  $100^{\circ}C$  and 15 W, and the fluorination step used  $\mathbb{CF}_4$  at 2 SCCM, 0.03 Torr,  $100^{\circ}C$  and 15 W. At the removal step, the temperature was increased to  $150^{\circ}C$  with an Ar of 50 SCCM for 30 s without RF power.

The subfigure plots estimated TiO₂ thickness and etch per cycle (EPC) of TiN versus oxidation temperature at 15 W RF power. Both quantities increase with temperature, showing that stronger oxidation produces thicker TiO₂ and higher EPC.

The subfigure plots estimated TiO₂ thickness and EPC versus RF power at 100 °C. Increasing RF power leads to larger TiO₂ thickness and EPC, indicating a close correlation between oxide growth and etch-per-cycle performance.

| Temperature (°C) | Estimated TiO₂ thickness (nm) | TiN Etch per cycle (nm/cycle) |
|------------------|-------------------------------|---------------------------|
| 50               | 0.30                          | 0.25                      |
| 100              | 0.50                          | 0.45                      |
| 150              | 0.80                          | 0.75                      |
| 200              | 1.20                          | 1.10                      |

| RF power (W) | Estimated TiO₂ thickness (nm) | TiN Etch per cycle (nm/cycle) |
|--------------|-------------------------------|---------------------------|
| 10           | 0.25                          | 0.25                      |
| 15           | 0.50                          | 0.50                      |
| 25           | 0.90                          | 0.85                      |
| 50           | 1.95                          | 1.75                      |

Answer: In (a), both quantities rise with temperature: TiO₂ thickness increases from ~0.30 nm (50 °C) to ~1.2–1.25 nm (200 °C), and EPC increases from ~0.25 to ~1.1 nm/cycle. The two curves follow similar upward trends, indicating a strong positive association between oxide growth and EPC under the tested oxidation conditions

Answer: At 200 °C.

Answer: The EPC of TiN increases steadily with RF power(approximately ~0.2–0.25 at 10 W up to ~1.7–1.8 nm/cycle at 50 W).

Answer: Yes. EPC is consistently slightly below (or very close to) the TiO₂ thickness at each power setting.

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-etching/experimental-usecase/41/Plasma atomic layer etching for titanium nitride.pdf