Fig. 8. Tungsten film thickness deposited after three AB cycles versus number of  $\mathrm{WF}_6$  pulses at  $425 \mathrm{K}$ . The  $\mathrm{Si}_2\mathrm{H}_6$  exposure of  $40 \mathrm{Si}_2\mathrm{H}_6$  pulses during each AB cycle was sufficient for a complete  $\mathrm{Si}_2\mathrm{H}_6$  half-reaction.

The line plot shows the tungsten film thickness obtained after three AB cycles as a function of the number of WF₆ pulses at 425 K. The thickness reaches saturation after about 10 WF₆ pulses, indicating that additional pulses do not increase growth. The data also confirms that using 40 Si₂H₆ pulses in each AB cycle is sufficient to complete the Si₂H₆ half-reaction.

| Number of WF6 Pulses | Tungsten Film Thickness (Å) |
|---|---|
| 0 | 0 |
| 1 | 3 |
| 5 | 7 |
| 10 | 7.2 |
| 15 | 7.2 |
| 20 | 7.2 |
| 25 | 6.5 |
| 30 | 7.2 |
| 40 | 7.2 |
| 50 | 7.2 |

Answer: To account for minor process variations, a safe setpoint would be slightly above the threshold, such as 12–15 pulses. Programming anything less than 10 pulses risks incomplete surface coverage, while significantly more (e.g., >20) wastes precursor without adding thickness.

Answer:
5 Pulses (Slope Region): High precursor efficiency (low waste), but high risk of non-uniformity because growth is sensitive to local gas flux.

50 Pulses (Deep Saturation): Confirms maximum uniformity and full coverage, but suffers from very low efficiency due to high precursor usage/waste.

Answer: The plateau signifies that all available reactive surface sites (specifically the Si-H bonds established in the previous step) have been consumed and replaced by W-F species. Since WF6 cannot react with itself or the fluorinated surface it creates, the reaction chemically terminates. This site-limitation factor ensures the film thickness is defined strictly by the number of cycles, not the total precursor gas exposure.

Answer: The GPC is ~2.5 Å/cycle, so 8 cycles are required for a 20 Å liner.

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/12/J.W. Klaus et al.pdf


Fig. 9. Tungsten film thickness deposited after three AB cycles versus number of  $\mathrm{Si}_2\mathrm{H}_6$  pulses at  $425 \mathrm{K}$ . The  $\mathrm{WF}_6$  exposure of nine  $\mathrm{WF}_6$  pulses during each AB cycle was sufficient for a complete  $\mathrm{WF}_6$  half-reaction.

This line  chart represents the tungsten(W) film thickness after 3 ALD- AB cycles as a function of the number of Si₂H₆ pulses per cycle (B-step), while the WF₆ exposure (A-step) is held constant at 9 pulses per cycle. It demonstrates that film growth requires a minimum number of Si₂H₆ pulses to complete the reaction cycle.

| Number of Si₂H₆ Pulses | Tungsten Film Thickness (Å) |
|---|---|
| 0 | 0 |
| 4 | 5 |
| 12 | 7.5 |
| 24 | 8.1 |
| 48 | 7.4 |
| 60 | 8.1 |

Answer:
WF₆ Pulse

Purge

Repeat steps 1-2 until 9 total WF₆ pulses are delivered.

Si₂H₆ Pulse

Purge

Repeat steps 4-5 a total of 30 times.
The 9 WF₆ pulses ensure the surface is saturated, guaranteeing a complete and reproducible A-step half-reaction regardless of the subsequent B-step condition, isolating the effect of the Si₂H₆ dose.

Answer: Diborane (B₂H₆) is likely better for minimizing oxygen. B₂H₆ is a stronger reducing agent that can getter trace oxygen and water more effectively than Si₂H₆. The trade-off is that boron itself can incorporate as an impurity in the W film, potentially altering its electrical resistivity and stability, whereas silicon incorporation from Si₂H₆ may form a more benign tungsten silicide.

Answer: Thickness increases with Si₂H₆ pulses, then saturates. From 0 to ~10 pulses, thickness rises sharply because each pulse provides more reductant to convert the W–F surface layer into a metallic W film and regenerate the Si–H sites needed for the next WF₆ pulse. Insufficient Si₂H₆ leaves the surface partially fluorinated, preventing full tungsten deposition in the next cycle.

Answer: This implies the process must use a saturating Si₂H₆ dose (>20 pulses/cycle) to ensure complete surface reaction. To grow 100 Å, you would run the calculated number of full ALD cycles based on the saturated growth per cycle (~20 Å/3 cycles = ~6.7 Å/cycle). Consistency and conformality are achieved only when both half-reactions (9 WF₆ pulses, >20 Si₂H₆ pulses) are operated in their saturated regimes.


FIG. 5. Film growth rates as a function of  $\mathrm{Zr}$  precursor pulse length with ozone as the oxygen source. The pulsing sequence was  $\mathrm{x}$ $\mathrm{slx} + 0.5$  sl1.0 sl1.5 s for  $\mathrm{Zr}$  pulselpurgel  $\mathrm{O_3}$  pulselpurge.

The scatter plot shows the growth rate of a material, when ozone is used as a precursor, as a function of Zr pulse length at different temperatures: Zr(Me₅Cp)(TEA) at 375°C and 300°C, Zr(Cp)(ᵗBuDAD)(OⁱPr)  and Zr(MeCp)(TMEA) at 250°C. The growth rate for Zr(MeCp)(TMEA) continues to increase, others show self-limiting behaviour.

| Zr pulse length (s) | Growth rate (Å/cycle) | Reagent | Temperature (°C) |
|---|---|---|---|
| 0,5 | 0,28 | Zr(Me_5Cp)(TEA) | 300 |
| 1,0 | 0,30 | Zr(Me_5Cp)(TEA) | 300 |
| 1,5 | 0,30 | Zr(Me_5Cp)(TEA) | 300 |
| 2,0 | 0,31 | Zr(Me_5Cp)(TEA) | 300 |
| 2,5 | 0,32 | Zr(Me_5Cp)(TEA) | 300 |
| 3,0 | 0,32 | Zr(Me_5Cp)(TEA) | 300 |
| 0,5 | 0,34 | Zr(Me_5Cp)(TEA) | 375 |
| 1,0 | 0,37 | Zr(Me_5Cp)(TEA) | 375 |
| 1,5 | 0,39 | Zr(Me_5Cp)(TEA) | 375 |
| 2,0 | 0,41 | Zr(Me_5Cp)(TEA) | 375 |
| 2,5 | 0,42 | Zr(Me_5Cp)(TEA) | 375 |
| 3,0 | 0,43 | Zr(Me_5Cp)(TEA) | 375 |
| 3,5 | 0,43 | Zr(Me_5Cp)(TEA) | 375 |
| 1,0 | 0,40 | Zr(Cp)(tBuDAD)(O^iPr) | 250 |
| 1,5 | 0,43 | Zr(Cp)(tBuDAD)(O^iPr) | 250 |
| 2,0 | 0,50 | Zr(Cp)(tBuDAD)(O^iPr) | 250 |
| 2,5 | 0,49 | Zr(Cp)(tBuDAD)(O^iPr) | 250 |
| 3,0 | 0,48 | Zr(Cp)(tBuDAD)(O^iPr) | 250 |
| 1,0 | 0,57 | Zr(MeCp)(TMEA) | 250 |
| 2,0 | 0,66 | Zr(MeCp)(TMEA) | 250 |
| 2,5 | 0,69 | Zr(MeCp)(TMEA) | 250 |
| 3,0 | 0,71 | Zr(MeCp)(TMEA) | 250 |
| 3,5 | 0,74 | Zr(MeCp)(TMEA) | 250 |

Answer: No. The growth rate continues to rise as more precursor is dosed, the deposition is therefore  likely influenced by CVD-like  reactions or precursor decomposition. A self-limiting ALD growth would show a plateau.

Answer: 2 seconds.

Answer: The growth rate decreases by ~ 0.1 Å/cycle.

Answer: Zr(Cp)(ᵗBuDAD)(OⁱPr)  and Zr(Me₅Cp)(TEA).

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/16/Sanni Seppala et al.pdf


Figure 1. Dependence of the platinum film growth rate on the  $\mathrm{MeCpPtMe}_3$  and air pulse times. The air pulse time in the  $\mathrm{MeCpPtMe}_3$  experiments was  $1.5\mathrm{s}$  and the  $\mathrm{MeCpPtMe}_3$  pulse time in the air pulse experiments was  $0.5\mathrm{s}$ .

The scatter plot compares the ALD growth rate of Pt as a function of pulse duration for two independent series: varying MeCpPtMe₃ pulse time at fixed air exposure and varying air pulse time at fixed MeCpPtMe₃ exposure. The MeCpPtMe₃-pulse series shows a modest increase from ~0.44 to ~0.50 Å/cycle with longer precursor pulses, while the air-pulse series shows growth rates in the ~0.36–0.46 Å/cycle range, largely insensitive to air pulse duration beyond ~1.5 s. Error bars highlight the experimental variation for each condition.

| Pulse time (s) | MeCpPtMe₃ pulse series (Å cycle⁻¹) | Air pulse series (Å cycle⁻¹)  |
|----------------|-----------------------------------|-------------------------------|
| 0.0            | ~0.44                             | -                             |
| 0.5            | ~0.45                             | -                             |
| 1.0            | ~0.50                             | ~0.36                         |
| 1.5            | ~0.49                             | ~0.45                         |
| 2.0            | -                                 | ~0.45                         |
| 2.5            | -                                 | ~0.42                         |
| 3.0            | -                                 | ~0.46                         |

Answer: Increasing the MeCpPtMe₃ pulse duration increases the likelihood that all available surface reactive sites are exposed to the Pt precursor before purging. This reduces precursor starvation and moves the system toward surface saturation, which is reflected by the gradual increase in growth rate from ~0.44 to ~0.50 Å/cycle. Once saturation is approached, further increases in pulse time yield diminishing returns, consistent with self-limiting ALD behavior.

Answer: The MeCpPtMe₃ pulse-time series shows a stronger dependence, implying that precursor adsorption is more rate-limiting than the air oxidation step under these conditions.

Answer: The relatively small and overlapping error bars indicate that the observed changes in growth rate are systematic rather than dominated by experimental noise. This strengthens confidence that the plateaus correspond to true saturation behavior rather than statistical scatter, particularly for the air-pulse series where growth rates remain nearly constant over a wide pulse-time range.

Answer: By identifying the minimum pulse durations required to achieve saturation—about 1.0 s for MeCpPtMe₃ and 1.5 s for air—process engineers can avoid unnecessarily long pulses that increase cycle time without increasing growth per cycle. Operating at these saturation thresholds maximizes throughput while maintaining precise thickness control and film uniformity.


Figure 3. Thickness profiles of platinum films grown with short and long  $\mathrm{MeCpPtMe_3}$  pulses of 0.2 and  $1.5\mathrm{s}$ , respectively. The profile is measured along the gas flow direction at various distances from the leading edge of the substrate, that is, the edge closest to the precursor inlet.

Figure shows film thickness profiles for platinum ALD using short (0.2 s) and long (1.5 s) MeCpPtMe₃ precursor pulses as a function of substrate position along the gas-flow direction. Long precursor pulses yield consistently thicker films, reflecting greater precursor availability across the surface. Both profiles show a mild decrease in thickness with distance from the leading edge, indicating precursor depletion during transport. The small error bars suggest good reproducibility for both pulse conditions.

| Distance from leading edge (cm) | Long-pulse thickness (nm) | Short-pulse thickness (nm) |
|---------------------------------|---------------------------|----------------------------|
| 1                               | ~78 ± 5                   | ~66 ± 5                    |
| 2                               | ~76 ± 5                   | ~64 ± 5                    |
| 3                               | ~72 ± 5                   | ~63 ± 5                    |
| 4                               | ~68 ± 5                   | ~60 ± 5                    |

Answer: Longer MeCpPtMe₃ pulses increase the total precursor dose delivered to the substrate, allowing surface saturation to be reached over a larger downstream distance before precursor depletion occurs. This leads to higher and more uniform film thickness along the gas-flow direction. Shorter pulses provide insufficient precursor flux, causing earlier depletion and reduced surface coverage downstream, which manifests as thinner films and a stronger spatial gradient.

Answer: The short-pulse condition shows a stronger thickness decay.

Answer: The consistently greater thickness implies more complete surface saturation during each ALD cycle when long pulses are used. This suggests that the process is less transport-limited and that adsorption kinetics dominate over precursor delivery limitations, resulting in a higher effective growth per cycle across the substrate.

Answer: The figure demonstrates that longer precursor pulses improve thickness uniformity by overcoming transport limitations. For large-area wafers or high-aspect-ratio features, pulse durations must be sufficiently long to ensure uniform precursor delivery throughout the structure. These insights guide pulse-time optimization to balance throughput against uniformity requirements in industrial ALD reactors.


Figure 6. Thickness of ALD ITO films versus number of cycles determined using VASE for films deposited on Si(100) at  $275^{\circ}C$  using  $5\%$ $\mathrm{SnO_2}$  cycles.

The line chart displays a direct linear relationship between the number of ALD cycles and ITO film thickness, demonstrating consistent film growth per cycle.

| ALD Cycles | ITO Thickness (Å) |
|------------|-------------------|
| 0          | 0                 |
| 100        | 200               |
| 200        | 400               |
| 300        | 600               |
| 400        | 800               |
| 500        | 1000              |
| 600        | 1200              |
| 700        | 1400              |
| 800        | 1600              |
| 900        | 1800              |
| 1000       | 2000              |

Answer: The ITO thickness increases linearly with the number of ALD cycles, indicating a consistent growth rate.

Answer: Yes

Answer: Number of ALD cycles, ITO Thickness.

Answer: Yes

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/26/Jeffrey W. Elam et al.pdf


Figure 8. Resistivity of ALD ITO films prepared on glass using  $5\%$ $\mathrm{SnO_2}$  cycles measured by four-point probe versus (a) number of cycles at  $275^{\circ}C$  and (b) deposition temperature using 300 cycles.

The scatter plot shows a sharp initial decrease in resistivity with increasing ALD cycles and ITO film thickness, plateauing at around 0.002 Ω·cm beyond 500 Å.

The scatter plot shows a gradual decrease in resistivity with increasing deposition temperature, reaching a minimum at 350 °C

| ALD Cycles | ITO Thickness (Å) | Resistivity (Ohm·cm) |
|------------|-------------------|-----------------------|
| 0          | 0                 | 0.015                 |
| 100        | 100               | 0.002                 |
| 200        | 200               | 0.002                 |
| 300        | 300               | 0.002                 |
| 400        | 400               | 0.002                 |
| 500        | 500               | 0.002                 |
| 600        | 600               | 0.002                 |
| 700        | 700               | 0.002                 |
| 800        | 800               | 0.002                 |
| 900        | 900               | 0.002                 |
| 1000       | 1000              | 0.002                 |

| Deposition Temperature (°C) | Resistivity (Ohm·cm) |
|-----------------------------|----------------------|
| 150                         | 0.01                 |
| 200                         | 0.005                |
| 250                         | 0.003                |
| 300                         | 0.002                |
| 350                         | 0.001                |

Answer: Yes

Answer: 350 °C

Answer: Resistivity decreases rapidly during early cycles and plateaus at ~0.002 Ω·cm after 500 Å film thickness.

Answer: ALD cycle number, ITO thickness, Depostion temperature


Figure 9. Optical transmittance for ALD ITO films prepared on glass using 300 ALD cycles with  $5\%$ $\mathrm{SnO_2}$  cycles versus deposition temperature. Optical transmittance is given as the average transmission over the wavelength range  $370 - 1000\mathrm{nm}$ .

The chart shows that optical transmission increases with a higher percentage of Sn cycles, rising steeply at first before plateauing around 92%

| % of Sn Cycles | Optical Transmission (%) |
|----------------|--------------------------|
| 0              | 80                       |
| 1              | 82                       |
| 3              | 87                       |
| 5              | 88                       |
| 10             | 92                       |
| 15             | 92                       |

Answer: As the percentage of Sn cycles increases, the optical transmission initially rises sharply. This rapid improvement occurs up to approximately 5–10% Sn cycles, indicating a significant enhancement in transparency with minimal Sn incorporation. Beyond this point, the curve begins to plateau, and further increases in Sn content do not yield substantial gains. The optical transmission stabilizes near 92%, suggesting a saturation point where additional Sn cycles have a negligible impact on optical performance. This trend implies that optimal transparency can be achieved with a relatively low Sn cycle percentage.

Answer: Yes

Answer: Optical transmission (%)

Answer: Yes


Figure 12. Experimental and simulated  $I - V$  curves of the OTS device. (a)  $I - V$  characteristics by plotting  $I_{\mathrm{DUT}} - V_{\mathrm{DUT}}$ . (b)  $I - V$  characteristics for the  $I_{\mathrm{off}}$  region by voltage sweep. Both experiments were performed using devices fabricated via the ALD-DFM process.

The figure shows a scatter plot of current versus voltage, indicating a non-linear relationship where current increases exponentially with voltage.

The figure displays a scatter plot comparing experimental and simulated currents against voltage, highlighting a exponential increase in current with voltage.

| Voltage (V) | Current (A) |
|---|---|
|0.5| 10^-4 |
|0.7| 10^-3 |
|0.9| 10^-2 |
|1.1| 2*10^-2 |
|1.3| 2.5*10^-2 |
|1.5| 2.5*10^-2 |
|1.7| 10^-4 |
|1.9| 10^-4 |

| Voltage (V) | Current (A) |
|---|---|
|0| 10^-8 |
|0.5| 4*10^-7 |
|1| 10^-6 |
|1.5| 4*10^-6 |
|2| 10^-5 |
|2.5| 10^-3 |

Answer: slightly below 1 V

Answer: There seem to be a lot of datapoints where just noise is measured resulting in a huge spread in datapoints.

Answer: Yes mostly for low voltages the different types of data overlap, however the switching current is less accurately simulated.

Answer: 10^-3 ampere

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/28/Woohyun Kim et al.pdf


Figure 9. Resistivity-temperature experiments (top) and GAXRD patterns (bottom) of the as-deposited and annealed GeSe films grown through (a), (c) the conventional ALD process and (b), (d) the ALD-DFM process to verify the crystallization temperature.

The sheet resistance of ALD grown GeSe is plotted against temperature. There is a sharp decrease in resistance at around 337°C.

The sheet resistance of DFM-ALD grown GeSe is plotted against temperature. There is a sharp decrease in resistance at around 348°C.

X-ray diffraction patterns are shown for different temperatures, indicating changes in crystallinity for 340 and 350 degrees for ALD grown GeSe.

X-ray diffraction patterns are shown for different temperatures, indicating changes in crystallinity for 350 degrees for ALD grown GeSe.

| Temperature (°C) | Sheet resistance (Ω/□) |
|---|---|
| 0 | 3*10^7 |
| 50 | 3*10^7 |
| 100 | 3*10^7 |
| 150 | 3*10^7 |
| 200 | 3*10^7 |
| 250 | 3*10^7 |
| 300 | 3*10^7 |
| 350 | 10^4 |

| 2θ (°) | Intensity (A.U.) |
|---|---|
| 20 | - |
| 25 | - |
| 30 | - |
| 32 | Peak for 340 and 350 degrees|
| 40 | - |
| 45 | - |
| 50 | - |

| 2θ (°) | Intensity (A.U.) |
|---|---|
| 20 | - |
| 25 | - |
| 30 | - |
| 32 | Peak for 350 degrees|
| 40 | - |
| 45 | - |
| 50 | - |

Answer: The material is more conductive in crystalline state, at higher temperatures the material is more crystalline. Also for these high temperatures lower sheet resistances are measured.

Answer: There are two peaks

Answer: By putting a sample in a RTA or rapid thermal anneal tool.

Answer: 348 degrees Celcius


Figure 6. Ellipsometric measurements of the tungsten nitride film thickness deposited by three AB cycles vs.  $\mathrm{NH}_3$  exposure at  $600~\mathrm{K}$ . A  $\mathrm{WF}_6$  exposure of  $4300~\mathrm{L}$  was sufficient for a complete  $\mathrm{WF}_6$  half- reaction at  $600~\mathrm{K}$ .

The graph shows the relationship between NH₃ exposure and film thickness at 600 K with 3 AB cycles. The film thickness increases rapidly initially and then plateaus.

| NH₃ Exposure (L) | Film Thickness (Å) |
|---|---|
| 0 | 0 |
| 1000 | 1 |
| 2000 | 2 |
| 3000 | 3 |
| 4000 | 4 |
| 5000 | 6 |
| 6000 | 7 |
| 7000 | 8 |
| 8000 | 8 |
| 9000 | 8 |
| 10000 | 8 |
| 11000 | 8 |
| 12000 | 8 |
| 13000 | 8 |
| 14000 | 8 |
| 15000 | 8 |
| 16000 | 8 |
| 17000 | 8 |
| 18000 | 8 |
| 19000 | 8 |
| 20000 | 8 |
| 21000 | 8 |
| 22000 | 8 |
| 23000 | 8 |

Answer: 3.

Answer: After about 10,000 L.

Answer: 7 Å.

Answer: Yes

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/29/J. W. Klaus et al.pdf


Figure 7. Ellipsometric measurements of the tungsten nitride film thickness deposited by three AB cycles vs.  $\mathrm{WF}_6$  exposure at  $600~\mathrm{K}$ . A  $\mathrm{NH}_3$  exposure of  $12,000~\mathrm{L}$  was sufficient for a complete  $\mathrm{NH}_3$  half- reaction at  $600~\mathrm{K}$ .

The line chart shows the relationship between the exposure of WF₆ and film thickness at 3 AB cycles and a temperature of 600 K.

| WF₆ Exposure (L) | Film Thickness (Å) |
|---|---|
| 0 | 0 |
| 1000 | 1 |
| 2000 | 2 |
| 3000 | 3 |
| 6000 | 8 |
| 12000 | 8 |

Answer: 12,000 L.

Answer: Around 4 Å.

Answer: After about 3,000 L.

Answer: About 8 Å.


Figure 1. Growth rates of thermal ALD  $\mathrm{Ta_2O_5}$  as a function of PDMAT exposure time  $(t_{\mathrm{s}})$  on  $\mathrm{Si(001)}$  substrate at  $T_{\mathrm{s}} = 250^{\circ}\mathrm{C}$ .

The figure shows growth rate of thermal ALD Ta₂O₅ as a function of PDMAT exposure time at 250°C. The growth rate increases rapidly at short exposure times and saturates at approximately 0.85 Å/cycle for t_s ≥ 1 s, demonstrating self-limiting adsorption characteristic of ideal ALD behavior.

| t_s (s) | Growth rate (Å/cycle) |
|---|---|
| 0 | 0 |
| 0.5 | 0.7 |
| 1 | 0.8 |
| 1.5 | 0.8 |
| 2 | 0.8 |
| 2.5 | 0.8 |
| 3 | 0.8 |
| 3.5 | 0.8 |
| 4 | 0.8 |
| 4.5 | 0.8 |
| 5 | 0.8 |

Answer: The growth rate increases steeply at short PDMAT exposure times, rising from near zero to about 0.7 Å/cycle at 0.5 s. Beyond 1 s of exposure, the growth rate plateaus at approximately 0.85 Å/cycle. This saturation behavior demonstrates self-limiting adsorption of the PDMAT precursor, which is the defining characteristic of an ideal ALD process.

Answer: Approximately 1 second.

Answer: Yes. The 0.85 Å/cycle growth rate is almost twice that reported for ethoxide or chloride precursors (both ~0.45 Å/cycle).

Answer: Purge time (t_p = 3 s), water reactant exposure time (t_r = 3 s), substrate temperature (T_s = 250°C).

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/32/W. J. Maeng et al.pdf


Figure 4. Growth rates of  $\mathrm{TiO_2}$  as a function of TDMAT exposure time on Si(001) substrate at  $T_{\mathrm{s}} = 200^{\circ}\mathrm{C}$ .

The figure shows growth rate of thermal ALD TiO₂ as a function of TDMAT exposure time at 200°C. Unlike Ta₂O₅ from PDMAT, the growth rate does not saturate but continues to increase with exposure time, indicating incomplete self-limiting behavior. This non-ideal ALD characteristic is attributed to the low thermal decomposition temperature of TDMAT (~180°C).

| t_S (s) | Growth rate (Å/cycle) |
|---|---|
| 0 | 0 |
| 1 | 1.5 |
| 2 | 2 |
| 3 | 2.5 |
| 4 | 3 |

Answer: No. Unlike Ta₂O₅ ALD from PDMAT, which shows clear saturation above 1 s exposure time, the TiO₂ growth rate from TDMAT continues to increase throughout the tested range up to 7 s. Although some slowdown occurs above 1 s, true saturation is never achieved. This indicates that TDMAT does not adsorb with perfect self-limitation at this temperature.

Answer: The low thermal decomposition temperature of TDMAT, reported to be approximately 180°C, which is below the growth temperature of 200°C used in this experiment.

Answer: At t_s = 2 s, the growth rate is approximately 2.1 Å/cycle. This is significantly higher than values reported for other precursors such as titanium methoxide (0.5 Å/cycle) and titanium chloride (0.75 Å/cycle). However, the higher rate partly reflects the non-ideal CVD contribution rather than pure ALD growth.

Answer: The TDMAT precursor exposure time in seconds.


Figure 5 Dependence of the saturated ALD cobalt (a) and copper (b) thicknesses per cycle, as a function of the substrate temperature.

The figure compares the dependence of ALD growth rate on substrate temperature for two different processes or materials. In subfigure (a), the growth rate increases steadily from approximately 0.01 Å/cycle at 260 °C to 0.12 Å/cycle at 340 °C, suggesting a thermally activated process with relatively linear behavior in this temperature range.

In subfigure (b), the growth rate follows a sigmoidal trend, increasing more sharply between 200 °C and 280 °C, indicating a possible transition from a kinetically limited regime to a more saturated or efficient growth regime. Both plots highlight the strong influence of temperature on film growth dynamics, with potential implications for process window optimisation.

| Substrate temperature (°C) | Growth rate (Å per cycle) |
|----------------------------|----------------------------|
| 260                        | 0.01                       |
| 280                        | 0.03                       |
| 300                        | 0.06                       |
| 320                        | 0.09                       |
| 340                        | 0.12                       |

| Substrate temperature (°C) | Growth rate (Å per cycle) |
|----------------------------|----------------------------|
| 160                        | 0.0                        |
| 200                        | 0.1                        |
| 220                        | 0.2                        |
| 240                        | 0.35                       |
| 280                        | 0.5                        |

Answer: No

Answer: The plots suggest that different ALD processes or chemistries have distinct thermal activation behaviors. In (a), the steady increase in growth rate with temperature implies a broad and controllable window, which is advantageous for uniform deposition. In contrast, the sigmoidal trend in (b) indicates that below a certain threshold (~200 °C), the process is kinetically limited, but rapidly becomes efficient above this temperature. This means that process engineers may need to operate within a narrower high-temperature window for maximum efficiency, potentially requiring more precise thermal control. Understanding these trends helps optimize reactor conditions for consistent film quality and throughput

Answer: 320 °C.

Answer: Higher temperatures enhance precursor reactivity, improve byproduct desorption

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/33/BOOYONG S. LIM et al.pdf


Figure 2. Growth rate as a function of (a)  $\mathrm{SbCl}_3$  and (b)  $(\mathrm{Et}_3\mathrm{Si})_2\mathrm{Te}$  pulse length for  $\mathrm{Sb}_2\mathrm{Te}_3$  films deposited at  $60^{\circ}\mathrm{C}$ . The other precursor pulse lengths were kept at  $1.0~\mathrm{s}$  and all the purge lengths at  $2.0~\mathrm{s}$ .

The growth rate of a material increases with increasing SbCl₃ pulse length up to a certain point and then plateaus.

The growth rate of a material increases gradually with increasing (Et₃Si)₂Te pulse length, but shows subsaturation.

| SbCl₃ pulse length (s) | Growth rate (Å/cycle) |
|---|---|
| 0.0 | 0.0 |
|0.2|0.3|
| 0.5 | 0.6 |
| 1.0 | 0.6 |
| 2.0 | 0.6 |

| (Et₃Si)₂Te pulse length (s) | Growth rate (Å/cycle) |
|---|---|
| 0.0 | 0.0 |
|0.2|0.0|
| 0.5 | 0.45 |
| 1.0 | 0.6 |
| 1.5 | 0.7 |
| 2.0 | 0.6 |
| 3.0 | 0.65 |
| 4.0 | 0.7 |

Answer: 0.6 angstrom per cycle.

Answer: Yes

Answer: No it does not, there seems to be a form of softsaturation, where there is still an increase in growth rate for ever increasing pulse length.

Answer: 0.6 angstrom per cycle

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/35/Viljami Pore et al.pdf


Figure 3. ALD saturation curve for 1 as the pulse length of 1 was varied.

The scatter plot image represents the growth rate (in A/cycle) against pulse length (in seconds). There seems to be no growth till 2 secs and it  seems to increase only after 3 secs and reaches a peak at 5 secs and slightly decreases.  This saturation is the identity of a self-limiting ALD process, where increasing the exposure time beyond a certain point no longer increases thickness, confirming complete surface reaction.

| pulse length (s) | growth rate (A/cycle) |
|---|---|
| 1 | 0 |
| 2 | 0 |
| 3 | 0.15 |
| 4 | 0.2 |
| 5 | 0.22 |
| 6 | 0.21 |

Answer:
Step 1: Pulse of Compound 1 (vapor) onto the hot substrate
Step 2: 3 s purge with N₂
Step 3: 6 s pulse of H₂ plasma
Step 4: Second N₂ purge. Repeat.

Answer: It increased until it reached a plateau at 0.2 Å/cycle after a 4 s pulse. Shorter pulses (1–2 s) gave no measurable thickness.

Answer: The surface became fully covered with precursor after 4 s; longer pulses couldn’t add more copper because all reaction sites were occupied a sign of self-limiting ALD behavior.

Answer: Mostly yes—EDS showed it was mainly copper metal with <5% carbon impurity. The growth rate (0.2 Å/cycle) is within the typical range for copper ALD, making it potentially useful for chip interconnects or barrier layers.


Figure 4. (Color online) The growth per cycle for remote plasma and thermal ALD of Pt and remote plasma ALD of  $\mathrm{PtO_2}$  as a function of the substrate temperature. At  $100^{\circ}\mathrm{C}$  the growth rate of the remote plasma process including a  $\mathrm{H}_{2}$  gas exposure step in the ALD cycle is shown. For thermal ALD of  $\mathrm{Pt}$  deposition took place on  $10 \mathrm{nm}$  thick  $\mathrm{Pt}$  starting surfaces prepared by remote plasma ALD at  $300^{\circ}\mathrm{C}$  The lines serve as guides to the eye.

The chart shows the growth per cycle of different ALD  processes (Thermal ALD Pt , Remote plasma ALD Pt , Remote plasma ALD PtO2)  at varying deposition temperatures. Remote plasma Pt ALD yields a relatively weak temperature dependence, whereas thermal ALD Pt shows little growth at lower temperatures and increases sharply only above ~200 °C. Growth per cycle decreases with temperature for remote plasma PtO2 ALD.

| Deposition temperature (°C) | Process | Growth per cycle (nm/cycle) |
|---|---|---|
| 150 |  Thermal ALD Pt  |  0.001 |
| 200 |  Thermal ALD Pt  | 0.01 |
| 225 |  Thermal ALD Pt  | 0.035 |
| 250 |  Thermal ALD Pt  | 0.037 |
| 300 |  Thermal ALD Pt  | 0.044 |
| 150 |  Thermal ALD Pt  |  0.001 |
| 100 |  Remote plasma ALD Pt  with H2 step | 0.038 |
| 200 |  Remote plasma ALD Pt  | 0.044 |
| 300 |  Remote plasma ALD Pt  | 0.046 |
| 100 |  Remote plasma ALD PtO2 | 0.06 |
| 200 |  Remote plasma ALD PtO2  | 0.057 |
| 300 |  Remote plasma ALD PtO2  | 0.047 |

Answer: Thermal ALD Pt.

Answer: Temperatures around ~225–300 °C are closest to an ideal ALD window for thermal Pt ALD. In this range, the measured growth per cycle changes only slightly (within the error bars), indicating relatively stable, self-limited behavior. At lower temperatures, the growth rate is  changing rapidly.

Answer: Remote plasma ALD Pt is the least temperature-sensitive between 200 and 300 °C.

Answer:
At 200 °C, the  values rank as:
1. Remote plasma ALD PtO₂ (~0.058–0.060 nm/cycle)
2. Remote plasma ALD Pt (~0.045 nm/cycle)
3. Thermal ALD Pt (~0.01–0.02 nm/cycle)


Figure 1. a) The film thickness of the  $\mathrm{MoS_2}$  film deposited at different temperatures ranging from 175 to  $300^{\circ}C$  The thickness of 50 ALD cycles  $\mathrm{MoS_2}$  film as a function of the b)  $\mathsf{H}_2\mathsf{S}$  exposure time, c) dose time, and d) exposure time of  $\mathsf{C}_7\mathsf{H}_8\mathsf{Mo}(\mathsf{CO})_3$  e) Spectroscopic ellipsometry curves for  $\mathrm{MoS_2}$  films deposited with varying ALD cycles (25, 50, 100, 200, and 300). f) There is a linear dependence between the number of ALD cycles and the deposited film thickness. The ALD reaction temperature was  $250^{\circ}C$  for all parameter variations except (a).

This multi-panel figure characterizes the Atomic Layer Deposition (ALD) of MoS₂ films, showing how thickness depends on various parameters such as  (a) temperature, (b) H₂S exposure time, (c) precursor dose time, (d) Mo-precursor exposure time, (e) optical properties versus cycles, and (f) linear thickness growth with cycle number.  The scatter plot shows the relationship between reaction temperature and layer thickness after 100 ALD cycles. The film thickness after 100 cycles peaks at approximately 250 °C (~9 nm), defining the optimal ALD window. Below 225 °C, growth is slow due to kinetic limitations, while above 275 °C, the thickness drops sharply, likely due to desorption or precursor decomposition.

The scatter plot shows the relationship between H₂S exposure time and layer thickness after 50 ALD cycles. The thickness saturates at approximately 30 s exposure time.

The scatter plot illustrates the effect of C₇H₈Mo(CO)₃ dose time on layer thickness after 50 ALD cycles. The growth saturates at approximately 0.8 s dose time.

The scatter plot illustrates the effect of C₇H₈Mo(CO)₃ exposure time on layer thickness after 50 ALD cycles. The thickness shows a peak at 20 s, followed by a decrease, suggesting possible etching or desorption at very long exposure times.

The line chart depicts the change in ellipsometric delta (Δ) with respect to wavelength. The delta parameter shifts monotonically with increasing ALD cycles.

The scatter plot shows the linear relationship between ALD cycle number and layer thickness. The graph confirms a highly linear growth per cycle (GPC) of 0.11 nm/cycle with R² = 0.994, demonstrating that the process is stable and self-limiting.

| Reaction Temperature (°C) | Layer Thickness After 100 ALD Cycles (nm) |
|---|---|
| 175      | 0.7       |
| 200      | 3         |
| 225      | 8         |
| 250      | 9         |
| 275      | 7.8       |
| 285      | 9.1       |
| 300      | 4         |

| H2S Exposure Time (s) | Layer Thickness After 50 ALD Cycles (nm) |
|---|---|
| 0.1 | 0.2 |
| 1   | 2   |
| 5   | 3.1 |
| 10  | 3.3 |
| 30  | 4.7 |
| 40  | 4   |
| 60  | 4.7 |

| C7H8Mo(CO)3 Dose Time (s) | Layer Thickness After 50 ALD Cycles (nm) |
|---|---|
| 0        | 0         |
| 0.25     | 3         |
| 0.5      | 4.2       |
| 0.75     | 4.8       |
| 1        | 4.7       |
| 1.5      | 5.1       |

| C7H8Mo(CO)3 Exposure Time (s) | Layer Thickness After 50 ALD Cycles (nm) |
|---|---|
| 5   | 2.7 |
| 10  | 4.9 |
| 20  | 6.5 |
| 30  | 4.7 |

| Wavelength (nm) | Delta (degree) | Number of cycles |
|---|---|---|
| 370            | 164       | 0 cycle |
| 370            | 158       | 25 cycle |
| 370            | 145       | 50 cycle |
| 370            | 135       | 100 cycle |
| 370            | 105       | 200 cycle |
| 370            | 72        | 300 cycle |
| 400            | 167       | 0 cycle |
| 400            | 163       | 25 cycle |
| 400            | 150       | 50 cycle |
| 400            | 140       | 100 cycle |
| 400            | 110       | 200 cycle |
| 400            | 83        | 300 cycle |
| 500            | 170       | 0 cycle |
| 500            | 166       | 25 cycle |
| 500            | 154       | 50 cycle |
| 500            | 143       | 100 cycle |
| 500            | 115       | 200 cycle |
| 500            | 93        | 300 cycle |
| 600            | 171       | 0 cycle |
| 600            | 169       | 25 cycle |
| 600            | 157       | 50 cycle |
| 600            | 147       | 100 cycle |
| 600            | 120       | 200 cycle |
| 600            | 98        | 300 cycle |
| 700            | 173       | 0 cycle |
| 700            | 171       | 25 cycle |
| 700            | 160       | 50 cycle |
| 700            | 149       | 100 cycle |
| 700            | 124       | 200 cycle |
| 700            | 104       | 300 cycle |
| 800            | --       | 0 cycle |
| 800            | --       | 25 cycle |
| 800            | --       | 50 cycle |
| 800            | --       | 100 cycle |
| 800            | --       | 200 cycle |
| 800            | 109      | 300 cycle |
| 900            | --       | 0 cycle |
| 900            | --       | 25 cycle |
| 900            | --       | 50 cycle |
| 900            | --       | 100 cycle |
| 900            | --       | 200 cycle |
| 900            | 114      | 300 cycle |

| ALD Cycle Number | Layer Thickness (nm) |
|---|---|
| 0   | 0  |
| 25  | 1  |
| 50  | 4  |
| 101 | 8  |
| 200 | 19 |
| 301 | 33 |

Answer: It confirms precise, atomic-level thickness control and excellent film uniformity. These characteristics are essential for reliably fabricating thin MoS₂ channels or barriers in scalable transistors and memory devices.

Answer: The optimal temperature is 250°C (highest thickness, stable growth). The film thickness drops significantly to <4 nm (compared to ~9 nm at 250°C). This indicates that 300°C is outside the stable ALD window, likely causing precursor desorption or parasitic etching, resulting in a much thinner film than intended.

Answer:
Increasing dose saturates the surface coverage (good). However, extending the residence time (exposure) beyond 20s causes a loss in thickness (bad).
This suggests a competing desorption or etching mechanism at long exposures. The process engineer cannot simply set an arbitrarily long exposure time "just to be safe." They must choose a value (e.g., 20s) that ensures saturation without crossing into the regime where the film begins to degrade or desorb.

Answer: It implies a Nucleation Delay. In an ideal scenario, the line would pass through zero. A negative intercept signifies that during the first ~10 cycles, virtually no film was deposited (incubation period). The precursor struggled to nucleate on the initial substrate surface, requiring several cycles to establish a seed layer before the steady-state growth rate of 0.11 nm/cycle was achieved.


Fig. 11 Optical band gap  $(E_{\mathrm{g,opt}})$  as a function of DF for ZnO:X  $(X = \mathsf{Al},\mathsf{B})$  TIB was used as a B source while DMAI and TMA were used as Al sources. The films were deposited on  $\mathrm{SiO_2}$  substrates at  $150^{\circ}C$

The figure shows the linear relationship between doping fraction (DF) and the optical band gap (Eg_opt) for three different materials: TIB, DMAI, and TMA.

| Doping fraction, DF | TIB | DMAI | TMA |
|---|---|---|---|
| 0.00 | 3.25 | 3.25 | 3.25 |
| 0.02 | 3.30 | 3.30 | 3.30 |
| 0.04 | 3.35 | 3.35 | 3.35 |
| 0.06 | 3.40 | 3.40 | 3.40 |
| 0.08 | 3.45 | 3.45 | 3.45 |
| 0.10 | 3.50 | 3.50 | 3.50 |
| 0.12 | 3.55 | 3.55 | 3.55 |

Answer: The increase in bandgap can be attributed to the Burstein–Moss shift, but only for the range of doping values for which the carrier concentration n increases

Answer:
The optical band gap (Eg,opt) of the ZnO:X films was extracted from so-called Tauc plots (i.e., (e2E^2)^2 as a function
of the photon energy E, where e2 is the imaginary part of the dielectric function extracted from the SE data

Answer: Yes

Answer: For ZnO:B, as well as for ZnO:Al, the optical band gap increases with increasing doping fraction. This increase can be attributed to the Burstein–Moss shift, for the range of DF values for which the carrier concentration n increases.  For higher DF values (DF > 0.034), in the case of ZnO:B and ZnO:Al (DMAI), the increase in the optical bandgap can be attributed to effects related to the grain size, strain and other types of imperfections.


Fig. 2 Saturation curves of the  $\mathrm{ZnO:}$  B process  $(m = 4)$  at  $150^{\circ}C$  (a) TIB precursor dose, (b) TIB precursor purge, (c)  $\mathsf{DI - H}_2\mathsf{O}$  dose, and (d)  $\mathsf{DI - H}_2\mathsf{O}$  purge. The growth per supercycle (GPSC) for each condition was averaged over 10 supercycles. The  $\mathrm{ZnO}$  standard conditions are specified elsewhere (50 ms DEZ dose, 5 s purge, 20 ms  $\mathsf{H}_2\mathsf{O}$  dose, 6 s purge) and the process saturated at a GPC of  $0.2\mathrm{nm}$  per cycle for an intrinsic  $\mathrm{ZnO}$  film deposited at  $150^{\circ}C$

The image plots GPSC as a function of TIB dose

The image plots GPSC as a function of TIB purge time

The image plots GPSC as a function of DI-H₂O dose

The image plots GPSC as a function of  DI-H₂O purge time

| TIB dose (ms) | GPSC (nm/supercycle) |
|---|---|
| 0 | 0.7 |
| 10 | 0.6 |
| 20 | 0.6 |
| 30 | 0.6 |
| 40 | 0.6 |
| 50 | 0.6 |
| 60 | 0.6 |
| 70 | 0.6 |
| 80 | 0.6 |

| TIB purge (s) | GPSC (nm/supercycle) |
|---|---|
| 0 | 0.6 |
| 1 | 0.6 |
| 2 | 0.6 |
| 3 | 0.6 |
| 4 | 0.6 |
| 5 | 0.6 |
| 6 | 0.6 |
| 7 | 0.6 |
| 8 | 0.6 |

| DI-H₂O dose (ms) | GPSC (nm/supercycle) |
|---|---|
| 0 | 0.5 |
| 10 | 0.6 |
| 20 | 0.6 |
| 30 | 0.6 |
| 40 | 0.6 |
| 50 | 0.6 |
| 60 | 0.6 |
| 70 | 0.6 |
| 80 | 0.6 |
| 90 | 0.6 |
| 100 | 0.6 |

| DI-H₂O purge (s) | GPSC (nm/supercycle) |
|---|---|
| 0 | 0.6 |
| 1 | 0.6 |
| 2 | 0.6 |
| 3 | 0.6 |
| 4 | 0.6 |
| 5 | 0.6 |
| 6 | 0.6 |
| 7 | 0.6 |
| 8 | 0.6 |

Answer: Yes

Answer:
The reduction in GSPC with increasing TIB dose observed in a could be the result of a slight etching of the ZnO by the TIB  but it could also be due to the inhibition of ZnO growth after a TIB pulse, as observed for DMAI. However, the  experiment carried out in which the film growth after every cycle (either DEZ or TIB cycle), monitored by spectroscopic ellipsometry, showed the change in thickness as a function of the number of cycles deduced from the measurements. From that it is clear that the ZnO was not etched by TIB (i.e., the film thickness did not decrease after one B cycle) but that the TIB
pulse led to an inhibition in the subsequent ZnO film growth. This growth inhibition took place during several cycles following the TIB pulse, and could also be seen from a second experiment
in which a supercycle with m = 19 was used (i.e., a total of 20 cycles comprising 19 ZnO + 1 TIB), it was evident that one TIB pulse affected the ZnO during many cycles.

Answer:
Growth per super cycle as this ALD process involves doping ZnO with boron. The saturation curves for the gas exposures and purges of the B cycle of an ALD supercycle corresponding to four DEZ
cycles and one TIB cycle for the ZnO:B process. These data were obtained by varying the duration of one of the ALD cycle steps, while keeping the duration of other steps sufficiently long to ensure  either saturation of surface reactions or sufficient purging.

Answer:
1. Temperature of deposition = 150 °C
2. Standard recipe = 50 ms DEZ dose, 5 s purge, 20 ms H2O dose, 6 s purge
3. Saturated GPC = 0.2 nm/cycle


Fig 3 Doping fraction (DF) as a function of the doping cycle ratio  $R_{x}$  for depositions at  $150^{\circ}C$ , as measured by X-ray photoelectron spectroscopy (XPS). The doping cycle ratio  $R_{x}$  (i.e. the ratio of the number of doping ALD cycles  $(X = \mathsf{Al}, \mathsf{B})$  over the total ALD cycles in one supercycle) is calculated as  $1 / (m + 1)$ . The estimated relative error for the doping fraction is  $\sim 10\%$ . The lines serve as guides to the eye.

The plot shows the relationship between dopant cycle ratio and doping fraction (DF) for TIB, DMAI, and TMA.

| Dopant Cycle Ratio (R) | TIB (DF) | DMAI (DF) | TMA (DF) |
|-------------------------|----------|-----------|----------|
| 0.02                   | 0.015    | 0.020     | 0.025    |
| 0.04                   | 0.025    | 0.045     | 0.060    |
| 0.06                   | 0.035    | 0.065     | 0.095    |
| 0.08                   | 0.045    | 0.085     | 0.135    |
| 0.10                   | 0.055    | 0.105     | 0.175    |
| 0.15                   | 0.075    | 0.115     | 0.215    |
| 0.20                   | 0.095    | —         | —        |
| 0.25                   | 0.115    | —         | —        |

Answer:
1. Trimethylaluminium (TMA)
2. Dimethylaluminium isopropoxide (DMAI)
3. Triisopropyl borate (TIB)

Answer: From the figure, comparing all three precursors, TIB results in the lowest incorporation of doping elements while TMA shows the greatest doping incorporation for same dopant cycle ratio.

Answer: This is in agreement with the data obtained by RBS/PIGE analysis, where the areal densities of B or Al per cycle were, on average, ~3.2 at per nm2 per supercycle (TIB), ~4.4 at per nm2 per supercycle (DMAI) and ~9.0 at per nm2 per supercycle (TMA ) for the cycle ratios (m) investigated.  A  combination of precursor reactivity and molecule size is most likely the cause of this trend. The bulkier isopropyl ligands in the TIB and DMAI precursors are likely to cause steric hindrance on the film surface, resulting in a more sparse distribution of the dopants on the surface and therefore a lower doping fraction.36 This is expected from the decreasing size of the monomers (TIB > DMAI > TMA).

Answer:
It is worth highlighting that the doping concentrations do not relate directly to the doping efficiency,
as some of the doping material might have formed metal oxide or alloy clusters (e.g. Al2O3) rather than merely doping the film. In this case, the dopant atoms do not contribute donating any electrons to the ZnO film.


Fig. 5 Resistivity,  $\rho$  (a), carrier concentration,  $n$ , and mobility,  $\mu$  (b) and doping fraction, DF, and doping efficiency,  $\eta$  (c) of the ZnO:B films as a function of the deposition temperature. The films with thicknesses of  $45 \pm 5 \mathrm{nm}$  were deposited on glass substrates. A cycle ratio of  $m = 24$  was employed as it resulted in optimised resistivity in the doping series at  $150^{\circ}\mathrm{C}$ . The lines serve as guides to the eye. The estimated relative statistical uncertainties for  $n$ ,  $\mu$ , DF and  $\eta$  are  $3\%$ ,  $5\%$ ,  $10\%$  and  $20\%$  respectively.

The resistivity  as a funtion of temperature is plotted and it decreases as temperature increases.

Both carrier concentration and mobility plotted against temperature increase with temperature, but the mobility decreases slightly at higher temperatures.

Doping efficiency versus temperature shows it decreases while doping fraction increases with temperature.

| Temperature (°C) | Resistivity, ρ (mΩ cm) |
|---|---|
| 150 | 3.5 |
| 200 | 2.5 |
| 250 | 2.2 |

| Temperature (°C) | Carrier concentration, n (10^20 cm^-3) | Mobility, μ (cm²V^-1s^-1) |
|---|---|---|
| 150 | 2.3 | 8 |
| 200 | 2.6 | 11 |
| 250 | 2.8 | 10 |

| Temperature (°C) | Doping fraction, DF | Doping Efficiency, η (%) |
|---|---|---|
| 150 | 0.02 | 30 |
| 200 | 0.025 | 25 |
| 250 | 0.03 | 20 |

Answer: Compared to ZnO:Al films deposited at 250 °C, it appeared that processing at 150 °C led to lower absolute values of conductivity (i.e. a higher resistivity)

Answer: The doping fraction increased with increasing deposition temperature, whereas the doping efficiency decreased slightly, despite the slight increase in carrier concentration with temperature.

Answer: It can be concluded that ~200 °C is the optimum deposition temperature for ZnO:B. However, it should be noted that the deposition temperature that is feasible for certain applications can be limited to lower temperatures than 200 °C.

Answer: The resistivity of the ZnO:B films decreased from 3.5 mOhm cm at 150 °C to 2.2 mOhm cm when deposited at temperatures of 200–240 °C. This was due to an increase in carrier concentration from 2.2* 10^20 /cm3 to 2.8* 10^20 /cm3 and an increase in mobility from 8 to 10.5 cm2 /Vs.


Fig. 7 (a) Intensity ratio  $I_{002} / I_{100}$  of the (002) and (100) peaks measured by XRD on the ZnO:X  $(X = \mathsf{Al},\mathsf{B})$  films reflecting the change in texture from  $\langle 002\rangle$  to  $\langle 001\rangle$  and (b)  $c$  -lattice parameter of the ZnO wurtzite unit cell and the corresponding  $2\theta$  position of the (002) peak as a function of the doping fraction in the ZnO:X  $(X = \mathsf{Al},\mathsf{B})$  . The films were deposited at  $150^{\circ}C$  on glass substrates. The  $c$  -lattice parameter of the wurtzite ZnO crystal is  $5.207\mathrm{\AA}$  6

The figure shows the variation of I_002/I_100 ratio  with doping fraction

The figure shows the variation of  c-lattice parameter with doping fraction, along with the 2θ_002 angle.

| Doping fraction, DF | I_002/I_100 TIB |I_002/I_100 DMAI |
|---|---|---|
| 0.00 | 2.20 | 2.20 |
| 0.02 | 1.80 | 1.30 |
| 0.04 | 1.60 | 0.60 |
| 0.06 | 1.30 | 0.50 |
| 0.08 | 0.80 | -        |
| 0.10 | 0.40 | -        |

| Doping fraction, DF | c-lattice parameter, Å | 2θ_002 |
|---|---|---|
| 0.00 | 5.22 | 34 |
| 0.02 |  5.20 | 34.2 |
| 0.04 |  5.18 | 34.4 |
| 0.06 |  5.16 | 34.6 |
| 0.08 |  5.14 | - |
| 0.10 | 5.12 | - |

Answer: It is a guide to the eye, the ratio I002/I100 for a powder pattern, i.e., the pattern characteristic for a film with randomly oriented crystals, has been included to illustrate the change in texture from (002) to (100).

Answer: The ratio I002/I100 for a powder pattern, i.e., the pattern characteristic for a film with randomly oriented crystals, has been included to illustrate the change in texture from (002) to (100). Secondly,

Answer:
The shift of the (002) peak as a function of the doping fraction, as a consequence of the
compression of the unit cell (i.e. a decrease of the c-lattice parameter) with increasing doping fractions. It should be noticed that the c-lattice parameter for the pure ZnO films (i.e., DF = 0) was slightly larger (5.219 Å) than the value reported for the wurtzite ZnO crystal lattice (5.207 Å).

Answer:
A significant shift of the peaks to  higher 2theta values was observed for increasing B fractions, which
was likely due to compressive stress in the ZnO unit cell caused by the substitution of Zn2+ (ionic radius of 0.60 Å, assuming a four-coordinate environment as expected for wurtzite structures)
132 with smaller B3+ ions (four-coordinate ionic radius of 0.11 Å).132 This effect was significantly smaller in the case of ZnO:Al films doped by DMAI (Al3+, four-coordinate ionic radius of 0.39 Å).


Figure 11. (Color online) Galvanostatic cycling for TiN prepared by sputtering and remote plasma ALD at a constant current of  $3\mu \mathrm{A} / \mathrm{cm}^2$ . The remote plasma ALD TiN film shows a lower capacity for Li, indicating better barrier properties.

The line chart shows the Li-capacity (µAh/cm²) of two different TiN samples over galvanostatic cycles. The blue circles represent 'Sputtered TiN', while the red circles represent 'TiN (H₂-N₂ 30:4 plasma)'. Both samples exhibit a slight increase in capacity over time.

| Galvanostatic cycles | Li-capacity (µAh/cm²) Sputtered TiN |  Li-capacity (µAh/cm²) TiN |
|---|---|---|
| 0 | 0.3 | 0.2 |
| 5 | 0.3 | 0.2 |
| 10 | 0.3 | 0.2 |
| 15 | 0.3 | 0.2 |
| 20 | 0.3 | 0.2 |
| 25 | 0.3 | 0.2 |
| 30 | 0.3 | 0.2 |
| 35 | 0.3 | 0.2 |
| 40 | 0.3 | 0.2 |
| 45 | 0.3 | 0.2 |
| 50 | 0.3 | 0.2 |

Answer: Sputtered TiN and ALD-grown TiN.

Answer: 50.

Answer: 0.3  µAh/cm².

Answer: 0.2  µAh/cm².


FIG. 4. (Color online) Growth rate per cycle of  $\mathrm{TaN}_{x,x\leqslant 1}$  films as a function of the ALD process parameters: (a) PDMAT dosing time, (b)  $\mathrm{H}_{2}$  plasma exposure time, and (c) deposition temperature. The growth rates are determined by in situ spectroscopic ellipsometry by varying the process parameters during one deposition run (closed symbols) and by the deposition of a thick film under constant process conditions (open symbols). The lines in (a) and (b) are exponential fits to the data.

The figure shows the growth rate (nm/cycle) versus the PDMAT dosing (s). The growth rate increases with increasing PDMAT dosing time until it plateaus.

The figure shows the growth rate (nm/cycle) versus the plasma exposure time (s). The growth rate increases with increasing plasma exposure time.

The figure shows the growth rate (nm/cycle) versus the deposition temperature (°C). The growth rate remains constant across different deposition temperatures.

| PDMAT dosing (s) | Growth rate (nm/cycle) |
|---|---|
| 0 | 0.00 |
| 1 | 0.035 |
| 2 | 0.035 |
| 3 | 0.040 |
| 4 | 0.040 |
| 5 | 0.040 |

| Plasma exposure time (s) | Growth rate (nm/cycle) |
|---|---|
| 0 | 0.00 |
| 5 | 0.04 |
| 10 | 0.042 |
| 15 | - |
| 20 | - |
| 25 | - |
| 30 | 0.05 |

| Deposition temperature (°C) | Growth rate (nm/cycle) |
|---|---|
| 150 | 0.05 |
| 175 | 0.05 |
| 200 | 0.05 |
| 225 | 0.05 |
| 250 | 0.05 |

Answer: The saturation point can be observed after approximately three seconds of PDMAT.

Answer: To analyze the growth rate for the ALD process, the deposition temperature was changed from 150 °C to 250 °C.

Answer: The growth rate remains constant across deposition temperatures.

Answer: Yes.


FIG. 6. (Color online) Resistivity of  $\mathrm{TaN}_{x,x\leqslant 1}$  films with an  $\sim 30 \mathrm{nm}$  thickness deposited by remote plasma ALD using different  $\mathrm{H}_{2}$  plasma exposure times within the cycle. The resistivity is determined from in situ SE (closed symbols) and ex situ FPP measurements (open symbols). The line serves as a guide to the eyes. The low-resistivity  $\mathrm{TaN}_{x,x\leqslant 1}$  film deposited using  $3\mathrm{~s~H}_{2}$  plasma in the ALD cycle has been indicated separately (open triangle).

The scatter plot shows the relationship between resistivity and plasma exposure time (s). The fitted curve indicates that resistivity decreases as plasma exposure time increases.

| Plasma exposure time (s) | In-situ SE | Ex-situ SE |
| --- | --- | --- |
| 0 | 10^4 | 10^5 |
| 5 | - | - |
| 10 | 10^3 | 10^3 |
| 15 | - | - |
| 20 | - | - |
| 25 | - | - |
| 30 | - | 6*10^2 |

Answer: This process corresponds to a remote plasma ALD.

Answer: The resistivity decreases as the plasma exposure time increases for both measurements (in-situ and ex-situ SE).

Answer: The lowest resistivity is observed after 30 s of plasma exposure.

Answer: There is a slight difference between the two SE measurements. The ex-situ SE shows higher resistivity values, which could be related to environmental contamination.


Figure 2. Saturation plots of ALD  $\mathrm{Y}_2\mathrm{O}_3$  films at a substrate temperature  $200^{\circ}\mathrm{C}$  with  $\mathrm{Y}(\mathrm{EtCp})_2(\mathrm{iPr - amd})$  and (a)  $\mathrm{H}_2\mathrm{O}$ , (b)  $\mathrm{O}_2$  plasma, and (c)  $\mathrm{H}_2\mathrm{O}$  plasma as a reactant. (d) Film thickness determined by in situ SE versus the ALD cycle number under saturated conditions.

Scatter plot showing the growth per cycle  (Å/cycle) of Y_2O_3 films as a function of pulse time for precursors Y(EtCp)_2(iPr-amd) and H_2O. The data confirms self-limiting surface reactions

Scatter plot showing the growth per cycle  (Å/cycle) of Y_2O_3 films as a function of pulse time for precursors Y(EtCp)_2(iPr-amd) and O_2 plasma. The data confirms self-limiting surface reactions

Scatter plot showing the growth per cycle  (Å/cycle) of Y_2O_3 films as a function of pulse time for precursors Y(EtCp)_2(iPr-amd) and H_2O plasma. The data confirms self-limiting surface reactions

The chart showing the thickness of the Y_2O_3 films as a function of ALD cycle number for H_2O plasma, O_2 plasma, and H_2O processes.

| Pulse time (s) | GPC (Å/cycle) | Precursor|
|---|---|---|
| 0,00 | 0,00 | Water |
| 1,02 | 0,35 | Water |
| 1,93 | 0,52 | Water |
| 3,86 | 0,62 | Water |
| 6,10 | 0,70 | Water |
| 7,83 | 0,74 | Water |
| 9,97 | 0,73 | Water |
| 15,05 | 0,73 | Water |
| 18,00 | 0,72 | Water |
| 20,03 | 0,72 | Water |
| 0,00 | 0,00 | Y(EtCp)2(iPr-amd) |
| 1,93 | 0,32 | Y(EtCp)2(iPr-amd) |
| 5,19 | 0,43 | Y(EtCp)2(iPr-amd) |
| 8,03 | 0,53 | Y(EtCp)2(iPr-amd) |
| 9,86 | 0,62 | Y(EtCp)2(iPr-amd) |
| 12,10 | 0,70 | Y(EtCp)2(iPr-amd) |
| 14,85 | 0,74 | Y(EtCp)2(iPr-amd) |
| 18,20 | 0,71 | Y(EtCp)2(iPr-amd) |
| 20,14 | 0,73 | Y(EtCp)2(iPr-amd) |
| 24,81 | 0,71 | Y(EtCp)2(iPr-amd) |
| 29,69 | 0,73 | Y(EtCp)2(iPr-amd) |

| Pulse time (s) | GPC (Å/cycle) | Precursor|
|---|---|---|
| 0,00 | 0,00 | O2 Plasma |
| 0,94 | 0,37 | O2 Plasma |
| 1,89 | 0,54 | O2 Plasma |
| 2,94 | 0,66 | O2 Plasma |
| 3,99 | 0,73 | O2 Plasma |
| 5,03 | 0,81 | O2 Plasma |
| 5,77 | 0,84 | O2 Plasma |
| 8,29 | 0,86 | O2 Plasma |
| 10,17 | 0,85 | O2 Plasma |
| 11,96 | 0,84 | O2 Plasma |
| 0,00 | 0,00 | Y(EtCp)2(iPr-amd) |
| 1,99 | 0,46 | Y(EtCp)2(iPr-amd) |
| 4,83 | 0,66 | Y(EtCp)2(iPr-amd) |
| 8,18 | 0,71 | Y(EtCp)2(iPr-amd) |
| 9,86 | 0,80 | Y(EtCp)2(iPr-amd) |
| 11,96 | 0,84 | Y(EtCp)2(iPr-amd) |
| 15,10 | 0,87 | Y(EtCp)2(iPr-amd) |
| 17,94 | 0,89 | Y(EtCp)2(iPr-amd) |
| 19,72 | 0,87 | Y(EtCp)2(iPr-amd) |
| 25,17 | 0,87 | Y(EtCp)2(iPr-amd) |
| 30,00 | 0,86 | Y(EtCp)2(iPr-amd) |

| Pulse time (s) | GPC (Å/cycle) | Precursor|
|---|---|---|
| 0,00 | 0,00 | H2O Plasma |
| 0,73 | 0,53 | H2O Plasma |
| 1,99 | 0,76 | H2O Plasma |
| 3,67 | 0,91 | H2O Plasma |
| 5,98 | 0,99 | H2O Plasma |
| 7,66 | 1,08 | H2O Plasma |
| 9,86 | 1,11 | H2O Plasma |
| 11,64 | 1,06 | H2O Plasma |
| 14,58 | 1,07 | H2O Plasma |
| 0,00 | 0,06 | Y(EtCp)2(iPr-amd) |
| 0,84 | 0,44 | Y(EtCp)2(iPr-amd) |
| 2,94 | 0,69 | Y(EtCp)2(iPr-amd) |
| 5,03 | 0,79 | Y(EtCp)2(iPr-amd) |
| 7,87 | 0,88 | Y(EtCp)2(iPr-amd) |
| 9,86 | 0,95 | Y(EtCp)2(iPr-amd) |
| 11,64 | 0,99 | Y(EtCp)2(iPr-amd) |
| 14,69 | 1,10 | Y(EtCp)2(iPr-amd) |
| 19,93 | 1,04 | Y(EtCp)2(iPr-amd) |
| 24,65 | 1,00 | Y(EtCp)2(iPr-amd) |
| 29,69 | 1,06 | Y(EtCp)2(iPr-amd) |

| ALD cycle number | Thickness (nm) | Precursor|
|---|---|---|
| 0.00 | 0.0 | H2O |
| 40 | 2.65 | H2O |
| 68 | 5.05 | H2O |
| 100 | 7.68 | H2O |
| 0 | 0 | H2O Plasma |
| 42 | 4.41 | H2O Plasma |
| 100 | 10.39 | H2O Plasma |
| 0 | 0 | O2 Plasma |
| 50 | 4.88 | O2 Plasma |
| 100 | 8.67 | O2 Plasma |

Answer: Water achieves saturation faster than the yttrium precursor. The graph shows that the growth per cycle (GPC) for water stabilizes at its saturation point with a pulse time of approximately 8 seconds. In contrast, the yttrium precursor requires a longer pulse time of about 12 seconds to reach  saturation level.

Answer: After ~5 seconds.

Answer: H2O plasma.

Answer: H2O: ~0.74 nm/cycle, O2 palsma: ~0.83 nm/cycle, H2O palsma: ~0.103 nm/cycle


Figure 8. Water contact angles of as-deposited and  $\mathrm{Y}_2\mathrm{O}_3$  films with a thickness of 5, 10, 20, and  $30~\mathrm{nm}$  with (a)  $\mathrm{H}_2\mathrm{O}$ , (b)  $\mathrm{O}_2$  plasma, (c)  $\mathrm{H}_2\mathrm{O}$  plasma, and (d) the surface free energy.


Figure 9. Water contact angles of as-deposited  $30~\mathrm{nm}$  thick  $\mathrm{Y}_2\mathrm{O}_3$  surfaces (a) before and after annealing at  $500^{\circ}\mathrm{C}$  for  $2\mathrm{~h}$  in static air and (b) after treatment with hexane, toluene, ethanol, and isopropanol for  $24\mathrm{~h}$ .


FIG. 1. Growth rate of  $\mathrm{Ga}_2\mathrm{O}_3$  thin films as a function of (a)  $\mathrm{O}_2$  plasma flow duration at  $250^{\circ}\mathrm{C}$  and (b) deposition temperature. TMG dose and  $\mathrm{O}_2$  plasma flow rate were constant at  $0.015\mathrm{s}$  and  $25\mathrm{scm}$  respectively. (c)  $\mathrm{Ga}_2\mathrm{O}_3$  film thickness as a function of the number of PEALD cycles.

The deposition rate increases rapidly with increasing O₂ plasma duration up to 10 seconds, then plateaus.

The deposition rate remains relatively constant across a wide range of temperatures, with a slight decrease at higher temperatures.

Film thickness increases linearly with the number of PEALD cycles.

| O2 plasma duration (s) | Deposition rate (nm/cycle) |
|---|---|
| 2 | 0.020 |
| 5 | 0.043 |
| 10 | 0.051 |
| 20 | 0.053 |
| 40 | 0.051 |
| 60 | 0.052 |

| Temperature (°C) | Deposition rate (nm/cycle) |
|---|---|
| 30 | 0.061 |
| 100 | 0.054 |
| 150 | 0.053 |
| 200 | 0.053 |
| 250 | 0.053 |
| 300 | 0.053 |
| 350 | 0.052 |
| 400 | 0.053 |

| Number of PEALD cycles | Film thickness (nm) |
|---|---|
| 50 | 3.0 |
| 150 | 8.0 |
| 300 | 16.0 |
| 500 | 26.5 |

Answer: The deposition rate rises rapidly from about 0.02 nm per cycle at 2 s to about 0.05 nm per cycle by about 10 s, then stays near that level up to 60 s. Saturation begins at roughly 10 s.

Answer:
The growth per cycle is approximately constant over the tested cycle counts.

There is no strong incubation delay in thickness accumulation over this range.

The process behaves in a self limiting manner consistent with ALD type growth.

Answer: The squares are measured deposition rate values at different substrate temperatures. The dashed line indicates the approximate constant growth per cycle within the ALD temperature window, about 0.53 Å per cycle.

Answer: A broad temperature window with stable growth per cycle makes the process easier to transfer across tools and substrates because small temperature variations have limited impact on thickness control. It also enables deposition on temperature sensitive substrates by selecting a lower temperature while keeping similar thickness per cycle. In practice, this supports more predictable film thickness targeting across devices and wafer areas.


FIG. 2. Growth rate of the platinum films grown from  $\mathrm{MeCpPtMe}_3$  as a function of the deposition temperature, the film thicknesses being measured by EDX and XRR. The  $\mathrm{MeCpPtMe}_3$  and oxygen pulse times were  $0.7$  and  $1.0\mathrm{s}$ , respectively, and the purge period between the pulses was  $0.7\mathrm{s}$ .

The figure shows the growth rate of platinum films deposited from MeCpPtMe₃ as a function of deposition temperature (200–300 °C). The film thicknesses were measured using EDX and XRR. The plot illustrates that the growth rate increases with temperature, from about 0.30 Å/cycle at 200 °C to 0.51 Å/cycle at 300 °C. Pulse and purge times for the precursor and oxygen were 0.7–1.0 s.

| Deposition temperature (°C) | Growth rate (Å cycle⁻¹) |
|---|---|
| 200 | 0.30 |
| 220 | 0.36 |
| 240 | 0.41 |
| 260 | 0.45 |
| 280 | 0.48 |
| 300 | 0.51 |

Answer: Using pure oxygen instead of air allows deposition of platinum films at significantly lower temperatures. In previous work using air, no film was obtained below 300 °C, whereas with pure oxygen, films could be grown starting at 200 °C. The higher oxygen partial pressure is key to enabling film growth at these lower temperatures without affecting the maximum growth rate at 300 °C.

Answer: At 300 °C.

Answer: Yes. The growth rate increases as the deposition temperature increases from 200 °C to 300 °C.

Answer: Deposition temperature (200–300 °C), Oxygen partial pressure (higher in current study compared to previous air-based study), Pulse times of MeCpPtMe₃ (0.7 s) and oxygen (1.0 s), Purge time between pulses (0.7 s)


A scatter plot showing the linear increase in thickness (in nm) as a function of ALD cycle number.

| ALD Cycle (#) | Thickness (nm) |
|---|---|
| 0 | 0 |
| 20 | 2.5 |
| 40 | 5 |
| 60 | 7 |
| 80 | 9 |
| 100 | 11 |

Answer: 300 °C.

Answer: Roughly 9 nm.

Answer: For both O2 plasma exposure steps, roughly 0.16 nm is removed.

Answer: During the TDMAP and TMA exposure steps, material is deposited, roughly 0.20 and 0.24 nm, respectively. During O2-plasma exposure, material is removed, roughly 0.16 and 0.17 nm for the first and second exposure, respectively. This yields a net growth of 0.11 nm/cycle.

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/69/Ruben Blomme et al.pdf


FIG. 5. In situ ellipsometry data for the different combinations of precursors that were tested at  $300^{\circ}\mathrm{C}$ . Depicted are the thicknesses obtained from the SE measurements conducted at the end of each full cycle.

The chart shows the thickness of as a function of the number of ALD cycles for 5 different precursor combinations.

| ALD Cycle (#) | Thickness (nm) TDMAP - TMA | Thickness (nm) TDMAP - O₂* | Thickness (nm) TDMAP - O₂* - TMA | Thickness (nm) TDMAP - TMA - O₂* | Thickness (nm) TDMAP - O₂* - TMA - O₂* |
|---|---|---|---|---|---|
| 0 | 0 | 0 | 0 | 0 | 0 |
| 20 | 0 | 2.0 | 2.0 | 2.0 | 3.5 |
| 40 | 0 | 2.0 | 4.0 | 4.0 | 6.0 |
| 60 | 0 | 2.0 | 6.0 | 6.0 | 8.0 |
| 80 | 0 | 2.0 | 7.0 | 7.0 | 10.0 |
| 100 | 0 | 2.0 | 8.0 | 8.0 | 12.0 |

Answer: TP–O–TAl–O (TDMAP–O₂*–TMA–O₂*).

Answer: The TP–O–TAl–O process yields a phosphorus content of approximately 11%, which is very similar to that obtained for the TP–TAl–O process.

Answer: The TP–TAl process shows no sustained growth beyond an initial thickness increase of about 0.37 nm after the first cycle, indicating very low reactivity without a coreactant.

Answer: The TP–O (TDMAP–O₂*) process shows limited growth that saturates at a total film thickness of approximately 2 nm.


FIG. 7. In situ ellipsometry data of three processes with different AIO-PO ratios. As the contribution of PO increases, the overall growth of the material also increases.

The scatter plot displays the ratio of oxygen to phosphorus (O/P) against various elements (Al, Ti, Ca, Li, Fe, La, Zn, Co, Na, Mg, V, Ni). The points are color-coded, and there's a horizontal dashed line indicating a specific value.

| M (Element) | TMP | TMP* | DEPA | DEPA* | TDMAP | This work |
|---|---|---|---|---|---|---|
| Al | 4.8 | 3.4 |  |  |  | 5.6 |
| Ti | 3.9 | 2.6 |  | 1.9 |  |  |
| Ca | 3.7 | 3.3 |  |  |  |  |
| Li | 3.8 | 2.2 | 2.4 |  |  |  |
| Fe | 3.9 | 2.5 |  |  |  |  |
| La | 4.9 |  |  |  |  |  |
| Zn |  | 2.0 |  |  |  |  |
| Co | 4.5 | 2.9 |  |  |  |  |
| Na |  |  | 3.7 |  |  |  |
| Mg |  |  |  |  | 3.2 |  |
| V  |  | 3.4 |  |  |  |  |
| Ni |  | 2.8 |  |  |  |  |

Answer: The aluminum phosphate deposited in this work has a P/M ratio of 0.51 and an O/P ratio of 5.65, which deviates strongly from an ideal orthophosphate composition (P/M = 1 and O/P = 4), indicating phosphorus deficiency and oxygen excess.

Answer: The aluminum phosphate in this work shows a lower P/M ratio (0.51 vs 0.67) and a higher O/P ratio (5.65 vs 3.16) than the TDMAP-based magnesium phosphate, highlighting a substantial difference in phosphorus incorporation between the two systems.

Answer: The comparison demonstrates that both the phosphorous precursor and the metal precursor significantly influence the final film composition. In particular, the TDMAP-based aluminum phosphate deposited in this work exhibits an unusually low P/M ratio and a very high O/P ratio, placing it far from the stoichiometry of an orthophosphate. This behavior contrasts with TMP-, TMP*-, DEPA-, and DEPA*-based processes, which generally yield compositions closer to P/M = 1. The stark difference with the TDMAP-based magnesium phosphate further suggests that the metal precursor itself can dictate growth chemistry and ligand exchange efficiency in ALD, reinforcing that phosphorus incorporation is not solely controlled by the phosphorous precursor but emerges from the combined metal–phosphorus chemistry.

Answer: Processes based on TMP, TMP*, DEPA, and DEPA* generally show higher P/M ratios than TDMAP-based processes, indicating more efficient phosphorus incorporation.


The line chart illustrates the growth of thickness over ALD supercycles for different AIO-PO ratios.

| ALD Supercycle (#) | Thickness (nm) AlO-PO (1-1) | Thickness (nm) AlO-PO (1-3) | Thickness (nm) AlO-PO (1-6) |
|---|---|---|---|
| 0 | 0 | 0 | 0 |
| 20 | 3 | 5 | 7 |
| 40 | 5 | 8 | 12 |
| 60 | 8 | 12 | 16 |
| 80 | 10 | 16 | 22 |
| 100 | 13 | 20 | 28 |

Answer: Roughly 7 nm.

Answer: Roughly 13 nm.

Answer: Roughly 17 nm.

Answer: Figure 7 illustrates that splitting the original four-step process into separate TDMAP–O₂* and TMA–O₂* cycles and combining them in a supercycle provides a practical lever to control film composition and growth behavior. Increasing the number of TDMAP–O₂* cycles per supercycle (from 1 to 3 and 6, with one TMA–O₂* cycle fixed) systematically increases both the growth per supercycle and the phosphorus content of the deposited film. Unlike the standalone TP–O process, which saturates at a thickness of approximately 2 nm, the periodic insertion of a TMA–O₂* cycle effectively resets the surface chemistry, allowing continued chemisorption and further growth during subsequent TDMAP–O₂* cycles. As a result, the supercycle approach overcomes growth saturation while enabling tunable phosphorus incorporation, analogous to previously reported TMP-based supercycle strategies.


Figure 3. Process development steps of Eu-HQA thin films that show temperature scanning (left), surface saturation of precursors (middle), and thickness control over the number of ALD/MLD cycles (right). (Reproduced under CC licence from ref. [55], 2023, Royal society of chemistry).

The graph shows the relationship between deposition temperature (Tdep) and GPC (Å/cycle). As the temperature increases, GPC decreases.

The graph illustrates the impact of pulse length on GPC. Longer pulse lengths result in higher GPC values.

The line chart demonstrates the increase in thickness with the number of cycles. There's a linear relationship indicating that more cycles lead to thicker layers.

| Tdep (°C) | GPC (Å/cycle) |
|---|---|
| 210 | 6.8 |
| 220 | 6.5 |
| 230 | 6.0 |
| 240 | 5.5 |

| Pulse length (s) | GPC (Å/cycle) |
|---|---|
| 1 | 5.7 |
| 2 | 6.5 |
| 3 | 7.0 |
| 4 | 7.2 |
| 5 | 7.3 |

| Cycles | Thickness (nm) |
|---|---|
| 50 | 50 |
| 100 | 75 |
| 150 | 100 |

Answer: Yes. The linear relationship between thickness and cycle number, passing through the origin, confirms self-limiting, layer-by-layer growth characteristic of ideal ALD/MLD processes.

Answer: Both Eu-thd and HQA precursors reach saturation at approximately 3 seconds pulse length.

Answer: Blue points represent Eu-thd (europium tris-tetramethylheptanedionate) precursor saturation, and green points represent HQA (2-hydroxyquinoline-4-carboxylic acid) organic precursor saturation.

Answer: This decreasing GPC trend is typical for ALD/MLD processes involving organic precursors. At higher temperatures, organic molecules may partially desorb from the surface before reacting, or undergo thermal decomposition. Additionally, increased thermal energy can enhance desorption of physisorbed species, reducing the effective surface coverage per cycle.

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/8/Adv Materials Inter - 2024 - Ghazy - Atomic and Molecular Layer Deposition of Functional Thin Films Based on Rare Earth.pdf


Figure 6. Growth rates of different  $\Upsilon_{2}\bigcirc_{3}$  processes (left) with different Y-precursors and  $\mathsf{H}_2\mathsf{O}$  as co-reactant, and (right) with different co-reactants and  $\Upsilon (^{(\mathsf{IPr2}}\mathsf{amd})(^{\mathsf{Et}}\mathsf{Cp})_2$  as Y-precursor.

Comparison of GPC values across ten yttrium precursors with H₂O as co-reactant, showing Yᴱᵗ(Cp)₃ achieves the highest GPC (~1.7 Å) and Y(ᵗBu₂-Famd)₃ the lowest (~0.67 Å).

Effect of five different co-reactants on GPC when using Y(ⁱPr₂amd)(ᴱᵗCp)₂ precursor, with O₃ giving the highest (~1.1 Å) and O₂ plasma the lowest (~0.83 Å).

| GPC (Å) | Compound Name |
| --- | --- |
| 0.75 | Y(iPr2-amd)3 |
| 0.85 | Y(Me)(Cp)3 |
| 1.00 | Y(Cp)3 |
| 1.10 | Y(iPr2-amd)(EtCp)2 |
| 1.20 | Y(Bu)(Cp)3 |
| 1.25 | Y(DPDMG)3 |
| 1.35 | Y(iPr2-amd)(iPrCp)2 |
| 1.45 | Y(iPr2-Famd)3 |

| GPC (Å) | Gas Type |
| --- | --- |
| 0.75 | O2 plasma |
| 0.85 | H2O plasma |
| 0.95 | O3 |
| 1.05 | O2 |
| 1.15 | H2O |

Answer: Ozone produces the highest GPC (~1.1 Å), followed by H₂O and H₂O plasma (~1.03–1.05 Å), then O₂ (~0.9 Å), with O₂ plasma yielding the lowest (~0.83 Å). This suggests that chemical reactivity of the oxidizer toward the precursor ligands, rather than plasma activation alone, primarily determines growth rate.

Answer: The y-axis represents growth-per-cycle (GPC) measured in angstroms (Å), indicating the film thickness deposited per ALD cycle.

Answer: Yᴱᵗ(Cp)₃ achieves the highest GPC of approximately 1.7 Å.

Answer: Key factors include: (1) steric bulk of ligand substituents affecting surface packing; (2) ligand lability influencing reaction kinetics with H₂O; (3) molecular footprint controlling maximum surface coverage per cycle.


Fig. B2 - Comparison between pressure readings by capacitance manometer and Pirani gauge.

The scatter plot compares the capacitance and Pirani guage readings with Argon flow

| Pirani Gauge (Torr) | Capacitance Manometer (Torr) |
|----------------------|------------------------------|
| 0.00                | 0.00                        |
| 0.02                | 0.03                        |
| 0.04                | 0.06                        |
| 0.06                | 0.09                        |
| 0.08                | 0.11                        |
| 0.10                | 0.14                        |
| 0.12                | 0.17                        |
| 0.14                | 0.20                        |

Answer: Yes

Answer: The capacitance manometer readings measure pressure consistently with the Pirani gauge with respect to the argon flow

Answer: The model predictions for the pressure to a value(Pconv) to be compared with the Pirani gauge measurements.Although the above assumption is not validated for H2O orTMA, experimental measurements show that it can be used for the Ar flow. However, only by using  the same assumption for the reactants, as it is the only way to compare the outlet measurements with the model predictions

Answer: A capacitance manometer is a highly accurate electronic gauge that measures pressure (especially vacuum) by detecting changes in electrical capacitance caused by the deflection of a thin diaphragm, converting this physical movement into a precise electrical signal, making it gas-independent and ideal for lab use

icdar2026-competition-data/train/atomic-layer-deposition/simulation-usecase/32/reactorGP Gakis et al.pdf


Fig. 4 - Outlet pressure vs inlet Ar flow rate: model predictions (line) and experimental measurements (dots).

The chart compares the experimental data and model prediction on the relationship between the inlet argon flow rate (in sccm) and the outlet pressure (in Torr). There is a linear increase in outlet pressure as the inlet argon flow rate increases.

| Inlet Argon Flow Rate (sccm) | Outlet Pressure - Experiments (Torr) | Outlet Pressure - Model (Torr) |
|------------------------------|--------------------------------------|--------------------------------|
| 0                            | 0.000                               | 0.000                         |
| 50                           | 0.015                               | 0.012                         |
| 75                           | 0.022                               | 0.020                         |
| 100                          | 0.030                               | 0.028                         |
| 150                          | 0.045                               | 0.043                         |
| 200                          | 0.060                               | 0.058                         |
| 250                          | 0.075                               | 0.073                         |
| 300                          | 0.085                                | 0.08                         |

Answer: Yes

Answer: The outlet pressure varied linearly with respect to inlet argon flow rate. As the argon flow rate increases, outlet pressure increases.

Answer: in order to compare the predicted values, Pcalc,with the Pirani measurements, Pexp, the former is converted using the formula , Pconv = Pcalc ( kmixture/kNitrogen),  which accounts for the dependence, assumed linear, of the pressure reading on the ratio of the thermal conductivities of the gas mixture and nitrogen

Answer: kmixture is the thermal conductivity of the gas mixture,kNitrogen is the thermal conductivity of nitrogen, Pcalc is the calculated pressure. Using the kinetic gas theory, the thermal conductivity of pure nitrogen at the outlet temperature, i.e270◦C, is estimated 0.041106 W/mK.


Fig. 1. Effect of  $\mathrm{AlMe}_3$  reaction temperature on the amount of aluminum adsorbed,  $\Delta c_{\mathrm{Al}}$ , in the  $\mathrm{AlMe}_3$  reaction with alumina heat-treated at  $560^{\circ}\mathrm{C}$  (adapted from reference [21]). Results up to reaction at  $300^{\circ}\mathrm{C}$  are shown; above  $300^{\circ}\mathrm{C}$ ,  $\mathrm{AlMe}_3$  decomposes [21,29]. A line has been fitted to the experimental data; the confidence limits represent 1 standard deviation.

The scatter plot shows the amount of aluminum adsorbed (Δc_Al) as a function of AlMe₃ reaction temperature on alumina pretreated at 560°C. The fitted line (y = a + bx) yields a = 2.9 ± 0.1 nm⁻² and b = −0.0003 ± 0.0005, indicating that Δc_Al remains essentially constant (~2.9 nm⁻²) across the 80–300°C range, demonstrating temperature independence of aluminum adsorption in this regime.

| AlMe₃ reaction temperature [°C] | Δcₐ [nm²] |
|---|---|
| 100 | 2.9 ± 0.1 |
| 150 | 2.9 ± 0.1 |
| 200 | 2.9 ± 0.1 |
| 250 | 2.9 ± 0.1 |
| 300 | 2.9 ± 0.1 |

Answer: No. The fitted slope b = −0.0003 ± 0.0005 is statistically indistinguishable from zero, meaning Δc_Al remains constant at approximately 2.9 nm⁻² regardless of reaction temperature in this range.

Answer: Above 300°C, AlMe₃ undergoes thermal decomposition, which would introduce non-ALD growth mechanisms and invalidate the self-limiting surface reaction assumption.

Answer: The temperature independence indicates that the AlMe₃ chemisorption reaction is not kinetically limited within the 80–300°C window; rather, it proceeds to completion regardless of thermal energy input. This behavior is characteristic of self-terminating ALD reactions where surface site availability (OH groups) and steric hindrance by adsorbed methyl groups, not reaction kinetics, determine the saturation coverage. The constant Δc_Al value of ~2.9 nm⁻² therefore reflects a thermodynamically controlled endpoint defined by the fixed OH concentration on the 560°C pretreated alumina surface.

Answer: The y-axis shows Δc_Al, the surface concentration of aluminum atoms adsorbed per ALD cycle, expressed in units of nm⁻² (atoms per square nanometer).


Figure 8. Hacac pressure contours across the wafer in (a) R1 at  $2\mathrm{s}$  and (b) R4 at  $3\mathrm{s}$ . The red region in (a,b) indicates the area that is covered with the reagent, Hacac. Distribution of exposure time for all nodes in the wafer for (c) R1 and (d) R4.  $\mu$  and  $\sigma$  represent the average and standard deviation, respectively. There are 10,410 nodes in R1 and 6737 nodes in R4.

Hacac partial pressure contour on wafers in reactor R1 at 2 s, showing coverage regions in red and illustrating spatial distribution of the reagent.

Hacac partial pressure contour on wafers in reactor R4 at 3 s, showing coverage regions in red and illustrating spatial distribution of the reagent.

Bar chart of Hacac exposure times for all wafer nodes in reactor R1, showing a broader distribution with average 2.717 s and standard deviation 0.1925 s.

Bar chart of Hacac exposure times for all wafer nodes in reactor R4, showing a tightly centered distribution with average 2.701 s and standard deviation 0.0079 s.

| x-coordinate|y-coordinate|
|-------------|------------|
|0.1|-0.05|
|0.15|-0.1|
|0.2|-0.15|
|0.25|-0.2|
|0.3|-0.25|

| x-coordinate|y-coordinate|
|-------------|------------|
|0.05|-0.1|
|0.1|-0.15|
|0.15|-0.2|
|0.2|-0.25|
|0.25|-0.3|

| Exposure time (s)|Number of nodes|
|------------------|---------------|
|2.0|0|
|2.1|0|
|2.2|0|
|2.3|0|
|2.4|0|
|2.5|0|
|2.6|0|
|2.7|0|
|2.8|0|
|2.9|0|
|3.0|0|
|3.1|0|
|3.2|0|
|3.3|0|
|3.4|0|
|3.5|0|
|3.6|0|
|3.7|0|
|3.8|0|
|3.9|0|
|4.0|0|

Answer: Reactor geometry (shape of reaction zones), Wafer rotation speed (angular velocity), Radial position of nodes on the wafer, Design of inlet and outlet configurations, Arc length of reaction zones relative to radial distance

Answer: Yes. R1 exhibits a wider exposure time distribution with higher standard deviation, whereas R4 has a tightly centered distribution with low variability, despite similar average exposure times.

Answer: Exposure time is determined by recording the Hacac partial pressure at every node of the wafer as it passes through the reaction zone. Each node is considered exposed as long as the pressure is above a threshold, and the total time in this state defines the exposure time. The wafer rotation and geometry of the reaction zones influence how long each node remains in contact with the reagent, which is then visualized as a distribution across all nodes.

Answer:
R1: Average exposure time = 2.717 s, Standard deviation = 0.1925 s
R4: Average exposure time = 2.701 s, Standard deviation = 0.0079 s

icdar2026-competition-data/train/atomic-layer-deposition/simulation-usecase/38/Sungil Yun et al.pdf


Figure 2.  $\mathrm{ZnO}$  thickness evolution as a function of the number of cycles for (a) sequence 1: Hacac and  $\mathrm{O}_2$  gas (circles); (b) sequence 2: Hacac and  $\mathrm{O}_2$  plasma (squares); and (c) sequence 3: only  $\mathrm{O}_2$  plasma pulses (diamonds). Significant  $\mathrm{ZnO}$  thickness decrease was observed only for sequence 2. All of the experiments were carried out at a temperature of  $250^{\circ}C$

The ZnO thickness remains constant at approximately 585 Å for Hacac + O₂ gas and O₂ plasma treatments, while it decreases linearly for Hacac + O₂ plasma treatment.

The ZnO thickness decreases linearly with increasing number of cycles for Hacac + O₂ plasma treatment.

The ZnO thickness remains constant at approximately 585 Å for O₂ plasma treatment.

| Number of cycles | Hacac + O₂ gas |
|------------------|----------------|
| 0               | 584            |
| 10              | 585            |
| 20              | 585            |
| 30              | 585            |
| 40              | 585            |

| Number of cycles | Hacac + O₂ plasma |
|------------------|--------------------|
| 0                 | 585                |
| 10              | 572                |
| 20              | 560                |
| 30              | 550                |
| 40              | 530                |

| Number of cycles | O₂ plasma |
|------------------|-----------|
| 0               | 585       |
| 10              | 585       |
| 20              | 585       |
| 30              | 585       |
| 40              | 585       |

Answer: From the figure, image b when Hacac and O2 plasma are exposed sequentially, we observe actual etching taking place as the thickness decreases.

Answer:
1. Hacac
, 2. O2 gas
, 3. O2 plasma.

Answer: No

Answer: Upon exposure to Hacac an apparent thickness increase of ∼2 Å was detected after the first 10 cycles, whereas the thickness decreases slightly afterward. This apparent thickness increase can be attributed to the adsorption of Hacac molecules onto the ZnO surface, similarly to what has been observed on Al2O3 substrates for the ABC-type area-selective ALD of SiO2. The subsequent thickness decrease might be due to partial decomposition of acac species on the ZnO surface . Note that the measured thickness does not decrease below the starting ZnO thickness during sequence 1.

icdar2026-competition-data/train/atomic-layer-etching/experimental-usecase/11/Isotropic Atomic Layer Etching of ZnO Using Acetylacetone and O2 Plasma.pdf


Figure 3. (a) EPC as a function of the Hacac exposure time for a fixed  $\mathrm{O}_2$  plasma step of  $5\mathrm{s}$ . Saturation (self-limiting behavior) was reached for a total Hacac exposure of  $27\mathrm{s}$ , resulting in an EPC of  $1.31\mathrm{\AA / cycle}$ . (b) EPC as a function of the  $\mathrm{O}_2$  plasma exposure time for a fixed Hacac dose of  $27\mathrm{s}$ . A saturated EPC value was measured for all the investigated  $\mathrm{O}_2$  plasma exposure times  $(\geq 2\mathrm{s})$ . The processing temperature was  $250^{\circ}\mathrm{C}$ . The dashed lines serve as a guide to the eye.

The line chart shows the relationship between Hacac exposure time and EPC (Å/cycle). Saturation achieved after 20 s

The line chart illustrates the impact of O₂ plasma exposure time on EPC (Å/cycle). Saturation achieved after 3s.

| Hacac Exposure (s) | EPC (Å/cycle) |
|---------------------|---------------|
| 0                  | 0.0           |
| 5                  | 0.4           |
| 10                 | 0.8           |
| 15                 | 1.0           |
| 20                 | 1.2           |
| 30                 | 1.3           |
| 40                 | 1.4           |

| O₂ Plasma Exposure (s) | EPC (Å/cycle) |
|-------------------------|---------------|
| 0                      | 0.0           |
| 1                      | 1.2           |
| 2                      | 1.3           |
| 4                      | 1.3           |
| 6                      | 1.3           |
| 8                      | 1.3           |
| 10                     | 1.3           |

Answer:
1. Hacac exposure was observed to saturate at a value of 1.31 ± 0.08 Å for a total Hacac exposure time of 27 s
2. O2 plasma exposure time shows saturation already after 2 s  at EPC of 1.31 Å/cycle

Answer: By observing the saturation curves, as the process saturates with respect to the Hacac and O2 plasma exposure, the ALE rate will remain the same irrespective of longer duration indicating the process has hit its reactive limit, therefore the images depict the self-limiting behaviour.

Answer: The processing temperature was 250 °C.

Answer: Yes


Figure 5. Etch depth versus number of etching cycles.

The scatter plot shows the relationship between the number of cycles and etch depth. As the number of cycles increases, the etch depth also increases.

| Number of cycles | Etch depth [nm] |
|---|---|
| 0 | 0 |
| 5 | 3 |
| 7 | 5 |
| 16 | 11 |
| 24 | 17 |

Answer: 3 nm.

Answer: 5 nm.

Answer: 11 nm.

Answer: 17 nm.

icdar2026-competition-data/train/atomic-layer-etching/experimental-usecase/13/Low-Damage and Self-Limiting (Al)GaN Etching Process.pdf


Figure 4. Mass change per cycle (MCPC) showing the self-limiting nature of the  $\mathrm{SF}_4$  and  $\mathrm{Sn(acac)}_2$  reactions during  $\mathrm{Al}_2\mathrm{O}_3$  ALE at 200  $^\circ \mathrm{C}$ . (a)  $\mathrm{SF}_4$  exposure time,  $X_{r}$  is varied as the  $\mathrm{Sn(acac)}_2$  exposure time is held constant at  $2.5\mathrm{s}$ . (b)  $\mathrm{Sn(acac)}_2$  exposure time,  $X_{r}$  is varied as the  $\mathrm{SF}_4$  exposure time is held constant at  $2.5\mathrm{s}$ . Purge times after each reactant exposure are  $55\mathrm{s}$ .

This dual-panel figure illustrates how MCPC (mass change per cycle) varies with precursor exposure time for both SF₄ and Sn(acac)₂ in the Al₂O₃ ALE process. In both cases, the MCPC decreases rapidly with increasing exposure time and asymptotically approaches a saturation point, indicating that each half-reaction becomes self-limiting beyond a certain exposure threshold. These saturation behaviors confirm that both precursors operate via self-limiting surface chemistry, a defining feature of atomic layer etching processes.

| SF₄ Exposure Time (s) | MCPC (ng/cm²) |
|------------------------|----------------|
| 0                      | 3.8            |
| 0.5                    | 2.1            |
| 1                      | 1.1            |
| 2                      | 0.7            |
| 3                      | 0.5            |

| Sn(acac)₂ Exposure Time (s) | MCPC (ng/cm²) |
|-----------------------------|----------------|
| 0                           | 3.6            |
| 0.5                         | 2.3            |
| 1                           | 1.2            |
| 2                           | 0.6            |
| 3                           | 0.4            |

Answer: SF₄.

Answer: The decreasing trends in MCPC for both SF₄ and Sn(acac)₂ exposures show that each precursor reaction is self-limiting, a hallmark of ALE chemistry. Initially, as exposure time increases, there is a sharp drop in MCPC due to rapid surface reactions. However, beyond ~2 seconds, additional exposure yields diminishing returns, indicating saturation of available reactive sites. This suggests that both the fluorination and ligand-exchange steps are well-controlled and reach completion under sufficient exposure durations, enabling precise layer-by-layer material removal.

Answer: Yes

Answer: Self-limiting reaction, efficient early-stage removal, surface saturation by ~2–3 s, stable MCPC plateau for repeatability

icdar2026-competition-data/train/atomic-layer-etching/experimental-usecase/17/SF4 as the Fluorination Reactant for Al2O3 and VO2.pdf


Panel (a) shows the mass loss (ng/cm²) of material as a function of MoF₆ dose duration, revealing rapid initial etching followed by saturation beyond ~1 second.

Panel (b) plots mass loss against H₂O dose time, similarly showing an initial sharp increase that levels off near 4 seconds. The graphs indicate self-limiting behaviour characteristic of atomic layer etching (ALE), where further dosing does not result in additional material removal beyond a certain threshold.

| MoF₆ dose (s) | Mass Loss (ng/cm²) |
|---|---|
| 0.0 | 0.0 |
| 0.5 | 16.0 |
| 1.0 | 18.0 |
| 1.5 | 18.0 |
| 2.0 | 18.0 |
| 2.5 | 18.0 |
| 3.0 | 18.0 |

| H₂O dose (s) | Mass Loss (ng/cm²) |
|---|---|
| 0.0 | 0.0 |
| 0.5 | 9.0 |
| 1.0 | 16.0 |
| 2.0 | 19.0 |
| 3.0 | 22.0 |
| 4.0 | 22.0 |

Answer: MoF₆: Mass loss quickly reaches saturation around 0.5–1.0 s, H₂O: Mass loss increases over a wider dose range, saturating near 3–4 s.

Answer: They exhibit self-limiting behaviour, indicating atomic layer etching (ALE) characteristics

Answer: The data show that MoF₆ achieves most of its etching effect within the first second, after which further increases in dose do not increase mass loss. This suggests a surface-limited reaction where all available reactive sites are quickly consumed. In contrast, H₂O dosing results in a more gradual increase in mass loss, reaching a plateau around 4 seconds. This indicates that the removal step may depend on the availability of MoF₆-reacted surface species and the diffusion/reactivity of H₂O, making it the rate-limiting factor in the overall ALE cycle.

Answer: Yes

icdar2026-competition-data/train/atomic-layer-etching/experimental-usecase/22/Thermal Atomic Layer Etching of MoS2 Using MoF6 and H2O.pdf


FiG. 2. EPC of ALE for the AlGaN film as a function of Ar plasma exposure time in the removal step with a self-bias voltage of  $45~\mathrm{V}$ .

The scatter plot shows the relationship between Ar plasma exposure time and etch depth per cycle. As the exposure time increases, the etch depth also increases, till it soft-saturates.

| Ar Plasma Exposure Time (s) | Etch Depth per Cycle (nm) |
|---|---|
| 0 | 0 |
|10|0.3|
| 25 | 0.43 |
|30|0.55|
| 50 | 0.5 |
| 100 | 0.6 |

Answer: The etching is probably induced by the ion influence from the plasma. If there is no plasma, there is also no etching.

Answer: With ALE only the modified layer is selectively etched. It seems that the modification depth is roughly 0.5 nm, so there is soft-saturation at this level.

Answer: No there is no such benefit, saturation means that there is no more significant increase.

Answer: Plasma pressure, with high pressures, there are usually less energetic ions bombarding the substrate, whereas low-pressure plasmas do show this.

icdar2026-competition-data/train/atomic-layer-etching/experimental-usecase/29/Atomic layer etching of AlGaN using Cl2 and Ar gas.pdf


Fig. 1. EPC of GaN as a function of bias voltage for a fixed Ar step time of  $5\mathrm{s}$ .

The line chart shows GaN etch per cycle (EPC) versus bias voltage for an Ar removal step time of 5 s. EPC increases at low bias, is nearly constant around 0.4 nm from about 50 to 100 V (self limited ALE window), and rises strongly above about 100 V.

| Bias Voltage [V] | EPC [nm] |
|----------------|---------|
| 0              | 0.0     |
| 50             | 0.3     |
| 100            | 0.4     |
| 150            | 1.1     |

Answer: The x axis is bias voltage in V, and the y axis is EPC in nm.

Answer: The ALE window is about 50 to 100 V. In this region EPC is almost constant at about 0.4 nm, consistent with a self limited removal per cycle rather than steadily increasing sputter yield.

Answer: It suggests a transition toward physical sputtering, where ion energy exceeds the sputtering threshold for GaN. In that regime, EPC rises with increasing bias because removal is no longer limited mainly by the prior chlorination step.

Answer:
Ion energy is insufficient to fully remove the chlorinated, modified surface layer each cycle.

Some modified species remain, so net removal per cycle stays low until bias is increased into the self limited regime.

icdar2026-competition-data/train/atomic-layer-etching/experimental-usecase/30/Atomic layer etching of GaN and AlGaN.pdf


Figure 3. InGaAs etch depth measured as a function of (a) first grid voltage (acceleration grid voltage) of the ICP ion gun for chlorine species (ions/radicals) exposure time of  $15\mathrm{min}$  and (b) the chlorine adsorption time for the first grid voltages of  $+10$  and  $+15\mathrm{V}$  during the chlorine adsorption step. The other conditions are the same as those in figure 2.

Line chart showing InGaAs etch depth as a function of acceleration grid voltage for a fixed Cl species exposure time of 15 min. Etching is negligible below 10 V and increases sharply between 15 and 30 V, indicating a threshold-like voltage dependence.

Multiple line chart showing InGaAs etch depth as a function of Cl species exposure time at acceleration voltages of 15 V and 10 V. Etching proceeds more rapidly at 15 V, while the 10 V condition shows a delayed onset and substantially lower etch depth over the same time range.

| Acceleration Voltage (V) | Etch Depth (Å) |
|---|---|
| 0 | 0 |
| 5 | 0 |
| 10 | 0 |
| 15 | ~45 |
| 20 | ~75 |
| 30 | ~150 |

| Exposure Time (min) | 15V Etch Depth (Å) | 10V Etch Depth (Å) |
|---|---|---|
| 0 | 0 | 0 |
| 5 | 0 | 0 |
| 10 | 0 | 0 |
| 15 | ~5 | 0 |
| 25 | ~20 | ~5 |
| 35 | ~65 | ~15 |

Answer: No

Answer: After ~10–15 min, 15 V increases much faster, reaching ~60–70 Å by ~35 min, while 10 V rises slowly to only ~10–20 Å by ~35 min. This indicates a strong voltage/ion-energy dependence of the etch step.

Answer: 15 V.

Answer: 15 min.

icdar2026-competition-data/train/atomic-layer-etching/experimental-usecase/32/Atomic layer etching of InGaAs.pdf


Figure 4. Sputter etch depth of InGaAs itself during the  $\mathrm{Ar^{+}}$  ion gun operation as a function of (a) different first grid voltages for the  $\mathrm{Ar^{+}}$  ion exposure time of 50 s/cycle and (b)  $\mathrm{Ar^{+}}$  ion exposure time for the first grid voltages of  $+10$  and  $+30\mathrm{V}$ . The sputtering was cyclic processed for 100 cycles without adsorption of chlorine during the chlorine adsorption step. The power of the ICP ion gun for the  $\mathrm{Ar^{+}}$  ion was maintained at  $200\mathrm{W}$  at the process chamber pressure of  $3.0\mathrm{mTorr}$  Ar. The second grid voltage to the ICP ion gun was maintained at  $-100\mathrm{V}$  for a directional ion beam while the third grid voltage was grounded.

Scatter plot of Ar⁺ sputter etch depth vs acceleration grid voltage (50 s/cycle × 100 cycles). Etching is negligible up to 10 V, becomes measurable by ~30 V, and increases sharply by 50 V, indicating a strong voltage/ion-energy dependence.

Multiple scatter plot showing InGaAs etch depth as a function of Ar⁺ ion exposure time at acceleration grid voltages of 10 V and 30 V. The 30 V condition produces substantially higher etch depths over the same exposure times, indicating a strong dependence of sputter yield on ion energy.

| Acceleration Grid Voltage (V) | Etch Depth (Å) |
|---|---|
| 0 | 0 |
| 10 | 0 |
| 30 | ~10 |
| 50 | ~60 |

| Ar+ Ion Exposure Time (sec) | 30V Etch Depth (Å) | 10V Etch Depth (Å) |
|---|---|---|
| 0 | 0 | 0 |
| 50 | ~20 | 0 |
| 100 | ~95 | 0 |
| 150 | ~210 | ~75 |

Answer: Yes

Answer: Etch depth increases non-linearly with exposure time for both, but 30 V increases much faster (≈20 → 95 → 210 Å) while 10 V stays ~0 up to 100 s and only rises by 150 s (~75 Å). This implies sputtering is strongly ion-energy dependent; at lower voltage there’s an effective “low-yield” regime over much of the time range.

Answer: Around 30 V.

Answer: 50 s/cycle × 100 cycles.


FIG. 4. EPC of the TiN films as a function of the radical exposure time. The dashed line is provided as a guide to the eye only.

The scatter plot shows the relationship between Radical Exposure Time (in seconds) and EPC (in nm/cycle). There is a positive correlation where EPC increases as the Radical Exposure Time increases, but form as saturation is observed.

| Radical Exposure Time (s) | EPC (nm/cycle) |
|---|---|
| 0 | 0 |
| 10 | 0.9 |
| 30 | 0.6|
| 50 | 1.2 |
| 60 | 2.8 |
| 120 | 3 |
| 240 | 3.3 |

Answer: It seems as if the EPC is soft-saturated, meaning that additional radical exposure time after 250 s will still increase the EPC.

Answer: No, there is mostly overlap for longer exposure times. The shorter exposure times shows less overlap.

Answer: Somewhere between 50 and 100 of radical exposure time.

Answer: 3.4 nm/cycle.

icdar2026-competition-data/train/atomic-layer-etching/experimental-usecase/33/Atomic layer etching of titanium nitride.pdf


FIG. 6. Etching amount of TiN films as a function of the number of ALE cycles. The radical exposure time and IR annealing time were set at 60 and  $30~\mathrm{s}$ , respectively. The dashed line on the plot was obtained from least squares fitting to the data points.

The scatter plot shows a positive linear relationship between the number of cycles and etching amount, indicating that the etching amount increases proportionally with the number of cycles.

| Number of Cycles | Etching Amount (nm) |
|-----------------|--------------------|
| 0               | 0                  |
| 2               | 3                  |
| 4               | 10                 |
| 6               | 12                 |
| 8               | 17                 |
| 10              | 19                 |

Answer: There is no delay in the beginning or enhanced etching indicating that there is nbo starting effect.

Answer: The EPC can be determined by calculating the slope of the linear fit through the data points.

Answer: The EPC is 1.9 nm/cycle.

Answer: Around 5 cycles.


FIG. 1. Etching rate of  $\mathrm{CF_4}$  dry etching for  $\mathrm{Al}_2\mathrm{O}_3$  films at various  $\mathrm{CF_4}$  plasma pressures.

The figure presents a scatter plot showing how the etching rate of Al₂O₃ during CF₄ dry etching varies with working pressure. The data reveal a steep decline in etching rate as pressure increases from a high rate at near-zero pressure to almost negligible etching above ~1 Torr indicating strong pressure-dependent suppression of etching efficiency.

| Working pressure (Torr)|Etching rate (nm/min)|
|------------------------|---------------------|
|0.0|4.5|
|0.2|2.8|
|0.3|1.1|
|0.6|0.3|
|1.0|0.5|
|1.4|0.2|
|2.0|0.2|

Answer: Understanding the pressure dependence is essential because it allows engineers to precisely control the etching process for high selectivity and accuracy. Lower pressures provide higher etching efficiency, useful for rapid material removal, while higher pressures reduce etching, enabling self-limiting or low-damage processing. This knowledge helps optimize process windows for applications such as device patterning, surface preparation, and atomic layer etching, ensuring high-quality results and consistency across wafers.

Answer: At 0 Torr, the etching rate is approximately 4.5 nm/min, while at 2 Torr, it decreases to about 0.2 nm/min.

Answer: Yes

Answer: Reduced mean free path of reactive species, Increased collision frequency in the plasma, Lower energy of reactive ions reaching the surface, Decreased dissociation efficiency of CF₄ at higher pressure

icdar2026-competition-data/train/atomic-layer-etching/experimental-usecase/34/CF4 plasma-based atomic layer etching of Al2O3.pdf