Fig. 5. Normalized integrated absorbances of the W-F stretching vibration at  $\sim 680~\mathrm{cm^{-1}}$  and the  $\mathrm{Si - H}$  stretching vibrations at 2115 and  $2275~\mathrm{cm^{-1}}$  versus  $\mathrm{WF}_6$  exposure during the  $\mathrm{WF}_6$  half-reaction at  $425\mathrm{K}$ .

This mulitple line plot represents the normalized, integrated absorbance of key IR vibrations (W–F stretch and Si–H stretches) against the total WF₆ exposure (Pressure * Time) during the WF₆ half-reaction at 425 K. It shows the Si–H signal decaying and the W–F signal growing as exposure increases, both saturating at high exposure.

| WF6 Exposure (Torr·min) | Normalized Integrated Absorbance | Stretch       |
|-----------------------------------|----------------------------------|---------------|
| 0.0 | 0.0  | W–F Stretch |
| 0.0 | 0.0  | Si–H Stretch |
| 0.1 | 0.9  | W–F Stretch |
| 0.1 | 0.1  | Si–H Stretch |
| 0.2 | 0.95 | W–F Stretch |
| 0.2 | 0.08 | Si–H Stretch |
| 0.4 | 1.0  | W–F Stretch |
| 0.4 | 0.03 | Si–H Stretch |
| 0.6 | 1.0  | W–F Stretch |
| 0.6 | 0.03 | Si–H Stretch |

Answer: Normalized integrated absorbance is a measure of the total area under an FTIR absorption peak after scaling it relative to a reference value. It is obtained by integrating the absorbance intensity across the specific wavenumber range associated with a vibrational mode. The resulting value is then divided by a chosen baseline or maximum signal so that different spectra can be compared on the same scale.

Answer: The W–F curve rises exactly as the Si–H curve falls, proving each new tungsten-fluoride bond directly replaces a silicon-hydride bond. Both curves saturate at the same exposure, confirming the reaction is self-limiting and consumes a fixed number of surface sites. This perfect mirroring shows the half-reaction is complete, reproducible, and ideal for controlled atomic-layer deposition.

Answer: The surface structure transitions completely from Si–H termination to W–F termination as WF₆ exposure increases to the saturation point. The concurrent and complementary nature of the Si–H decay and W–F growth indicates a direct, one-to-one replacement reaction. The saturation of both signals at the same exposure value suggests the reaction consumes a fixed number of surface Si–H sites to produce a corresponding number of W–F sites, defining the stoichiometry of the surface-limited process.

Answer: This provides exceptional conformality on high-aspect-ratio 3D structures, a critical advantage. Because the reaction saturates once all surface sites are consumed, it proceeds equally on all exposed surfaces, regardless of geometry. The film property controlled with atomic-scale precision is thickness, as each ALD cycle adds a reproducible, sub-nanometer layer, enabling exact deposition in nanoscale device features.

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


Fig. 7. Normalized integrated absorbances of the W-F stretching vibration at  $\sim 680 \mathrm{cm}^{-1}$  and the  $\mathrm{Si - H}$  stretching vibrations at 2115 and  $2275 \mathrm{cm}^{-1}$  versus  $\mathrm{Si}_2\mathrm{H}_6$  exposure during the  $\mathrm{Si}_2\mathrm{H}_6$  half-reaction at  $425 \mathrm{K}$ .

This mulitple line plot represents the normalized, integrated absorbance of key IR vibrations (W–F stretch and Si–H stretches) against the total Si₂H₆ exposure during the WF₆ half-reaction at 425 K. It shows the W–F signal decaying and the Si–H signal growing as exposure increases, both saturating at high exposure.

| Si₂H₆ Exposure (Torr min) | Normalized Integrated Absorbance | Stretch |
|---|---|-----|
| 0.0 | 0.0 | W-F Stretch |
| 0.0 | 0.0 | Si-H Stretch |
| 0.1 | 0.04 | W-F Stretch |
| 0.1 | 0.8 | Si-H Stretch |
| 0.2 | 0.007 | W-F Stretch |
| 0.2 | 0.9 | Si-H Stretch |
| 0.3 | -0.01 | W-F Stretch |
| 0.3 | 1 | Si-H Stretch |
| 0.4 | -0.01 | W-F Stretch |
| 0.4 | 1 | Si-H Stretch |
| 0.5 | -0.02 | W-F Stretch |
| 0.5 | 1 | Si-H Stretch |

Answer: The plateau indicates a self-limiting control mechanism, a hallmark of ALD. Once the reactive Si-H surface sites are fully consumed (absorbance ~ 0) and replaced by W-F species, the reaction stops automatically, meaning extending the exposure time further yields no additional material growth.

Answer:
0.1 Torr·min (Speed): High throughput, but the Si-H signal is still ~0.3 (30% unreacted), and W-F coverage is only ~80%.

0.6 Torr·min (Quality): Slower throughput, but Si-H is fully removed (~0.0) and W-F is saturated (1.0).

Answer: At the crossover point, the surface is a heterogeneous mixture of approximately 50% unreacted Si-H bonds and 50% newly formed W-F species.

Answer: The saturation value greater than 1.0 indicates a high density of reactive Si–H sites, possibly including higher-order silane species (SiHₓ). Such a hydrogen-rich surface is advantageous because Si–H bonds serve as the reducing agent for WF₆. A larger population of these active sites promotes fast and uniform nucleation of tungsten in the following deposition step.


FIG. 3.  $1\mathrm{kHz}C - V$  measurements for MOS capacitors,  $\mathrm{Cu(100nm) / 10nm}$ $\mathrm{Ti - Si - N}$  barrier layer (or without the barrier layer)  $\mathrm{SiO_2}$ $100\mathrm{nm}) / N$  -type Si. a and b are the  $C - V$  profiles for the MOS capacitor without the barrier layer before and after thermal treatment at  $600^{\circ}\mathrm{C}$  for  $60~\mathrm{min}$  in  $\mathrm{H}_{2}$ $(10\%)/\mathrm{Ar}(90\%)$  respectively.c is the  $C - V$  profiles for the MOS capacitor with a  $10\mathrm{nm}$  Ti-Si-N barrier layer after thermal treatment at  $800^{\circ}\mathrm{C}$  for  $60~\mathrm{min}$  in  $\mathrm{H}_{2}$ $(10\%)/\mathrm{Ar}(90\%)$

The line chart illustrates the normalized capacitance (C/Cox) against voltage for three different conditions: before thermal treatment, no barrier capacitor at 600°C, and Ti-Si-N (10 nm) capacitor at 800°C.

| Voltage [V] | Before thermal treatment | No barrier capacitor | Ti-Si-N capacitor |
| --- | --- | --- | --- |
| -15 | 0.21 | 1.00 | 0.19 |
| -10 | 0.22 | 1.00 | 0.20 |
| -5 | 0.35 | 0.60 | 0.25 |
| 0 | 1.00 | 0.90 | 1.00 |
| 5 | 1.00 | 1.00 | 1.00 |
| 10 | 1.00 | 1.00 | 1.00 |

Answer: For both curves, the MOS capacitor does not have the barrier layer.

Answer: For all the curves, the normalized capacitance exhibits the same behavior at voltage values above 1V: it remains constant as the voltage increases.

Answer: Approximately at -3V.

Answer: The Cu atoms can enter the Si and form deep donor levels. These levels can act as the generation and recombination centers of electron-hole pairs.

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/13/Jae-Sik Min et al.pdf


Figure 3. MPC for 400 ALD cycles of either  $\mathrm{ZnO}$  (red diamonds) or  $\mathrm{GeO}_y$  (blue squares). The deposition of  $\mathrm{ZnO}$  was interrupted after 200 cycles by performing a single  $\mathrm{GeO}_y$  cycle before depositing another 200 cycles of  $\mathrm{ZnO}$ . Similarly, the deposition of  $\mathrm{GeO}_y$  was interrupted after 200 cycles by performing a single  $\mathrm{ZnO}$  cycle before depositing another 200 cycles of  $\mathrm{GeO}_y$ .

The figure plots the mass per cycle (MPC) during 400 ALD cycles for ZnO and GeOₓ films. Each deposition was interrupted after 200 cycles by inserting a single cycle of the opposite material, creating ZnO/GeOₓ/ZnO and GeOₓ/ZnO/GeOₓ sequences

| Cycle Number | ZnO / 1 cycle GeOₓ / ZnO (ng/cm²) | GeOₓ / 1 cycle ZnO / GeOₓ (ng/cm²) |
|--------------|------------------------------------|--------------------------------------|
| 0            | 140                                | 20                                   |
| 50           | 145                                | 22                                   |
| 100          | 147                                | 23                                   |
| 150          | 148                                | 24                                   |
| 200 (Interruption) | 150            | 50                                   |
| 250          | 152                                | 24                                   |
| 300          | 153                                | 25                                   |
| 350          | 155                                | 26                                   |
| 400          | 158                                | 27                                   |

Answer: The deposition of ZnO was interrupted after 200 cycles by performing a single GeOy cycle before depositing another 200 cycles of ZnO. Similarly, the deposition of GeOy was interrupted after 200 cycles by performing a single ZnO cycle before depositing another 200 cycles of GeOy. As one continuous process is interrupted, this is called an interruption experiment

Answer: An interruption experiment was performed to further understand the dynamics of the inhibition seen when mixing ZnO and GeOy subcycles into ZGO supercycles

Answer:
1. Only a minor transient in MPC was seen after the ZnO process was interrupted with a single GeOy cycle.
 2. In contrast, when the GeOy process was interrupted by a single ZnO cycle, the MPC was lowered for more than 100 consecutive GeOy cycles.

Answer: The implication of this for the ZGO supercycle processes would be that the more the GeOy cycles used in a row, the more the Ge−OH on the surface and the more the reaction sites end up being poisoned during the DEZ exposure. As a result, the GPC would decrease as the amount of GeOy cycles in the ZGO supercycle increases.

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/25/Adam Hultqvist et al.pdf


Figure 6. Optical absorption as a function of the cation ratio,  $x_{i}$  of a TGO and  $(\hat{1})$  ZGO films deposited on fused silica.

The figure shows tauc plot for TGO at various GeOx concentrations.

The figure shows tauc plot for ZGO at various GeOx concentrations.

| E (eV) | x = 0% | x = 6.5% | x = 7.7% | x = 10% | x = 16% | x = 30% |
|--------|--------|----------|----------|---------|---------|---------|
| 3.0    | 1000   | 800      | 700      | 600     | 500     | 200     |
| 3.5    | 2500   | 2200     | 2100     | 1900    | 1700    | 800     |
| 4.0    | 4000   | 3700     | 3500     | 3300    | 3000    | 1500    |
| 4.5    | 5500   | 5200     | 5000     | 4700    | 4300    | 2200    |
| 5.0    | 6000   | 5800     | 5600     | 5300    | 4900    | 2800    |

| E (eV) | x = 0% | x = 3.2% | x = 12% | x = 19% | x = 32% | x = 37% |
|--------|--------|----------|---------|---------|---------|---------|
| 3.0    | 800    | 600      | 400     | 300     | 200     | 100     |
| 3.5    | 2200   | 1900     | 1600    | 1400    | 1000    | 700     |
| 4.0    | 3700   | 3400     | 3000    | 2700    | 2200    | 1800    |
| 4.5    | 5200   | 4900     | 4500    | 4100    | 3500    | 3000    |
| 5.0    | 6000   | 5800     | 5400    | 5000    | 4400    | 3800    |

Answer:
Eg increased as the ZGO cation ratio increased. The ZnO was found to be able to incorporate small amounts of Ge into the wurtzite lattice and thereby
increase both conductivity and Eg, while larger amounts led to a high resistivity and worse crystal quality

Answer:
1. For maximum doping of TGO 0.30, Eg = 3.5 eV
2. For ZGO, ZGO 0.32 gives 4.11 eV and
3. ZGO 0.32, Eg = 4.49 eV

Answer: Yes

Answer: The bandgap Eg slowly increased as the cation ratio increased


Figure 2. Growth rate for ALD ITO versus percentage of  $\mathrm{SnO_2}$  cycles determined using VASE  $(\bullet)$  and XRF  $(\nabla)$ . Solid line guides the eye, and dashed line shows expected growth rates calculated using a rule-of-mixtures formula.

The line chart shows the variation in growth rate (in Å/cycle) as a function of SnO₂ cycle percentage. Measurements from ellipsometry and XRF are plotted, along with a dashed line representing the rule of mixtures. Both techniques show a decreasing trend in growth rate with increasing SnO₂ cycles.

| % SnO₂ Cycles | Ellipsometry (Å/cycle) | XRF (Å/cycle) |
|---------------|-------------------------|----------------|
| 0             | 1.75                    | 1.60           |
| 1             | 1.45                    | 1.40           |
| 2             | 1.35                    | 1.30           |
| 3             | 1.25                    | 1.20           |
| 4             | 1.15                    | 1.10           |
| 5             | 1.05                    | 1.00           |
| 10            | 0.95                    | 0.90           |
| 15            | 0.85                    | 0.80           |
| 20            | 0.75                    | 0.70           |
| 25            | 0.65                    | 0.60           |
| 30            | 0.55                    | 0.50           |

Answer: The growth rate decreases steadily as the % SnO₂ cycles increases, for both ellipsometry and XRF measurements, with ellipsometry consistently reading higher.

Answer: No, the trend is nonlinear, especially in the low % SnO₂ region.

Answer: Ellipsometry, X-ray fluorescence (XRF),  Rule of Mixtures model

Answer: It represents a theoretical growth rate expected from a weighted average of individual components.

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


Figure 4. Growth rate versus ALD cycles measured using in situ QCM during ITO growth using  $10\%$ $\mathrm{SnO_2}$  cycles.

The line chart shows the growth rate (Å/cycle) of SnO₂ and In₂O₃ as a function of ALD cycles. The SnO₂ growth rate exhibits periodic dips, while the In₂O₃ growth remains relatively steady with minor fluctuations.

| ALD Cycles | SnO₂ | In₂O₃ |
|---|---|---|
| 0 | 1.15 | 1.15 |
| 5 | 1.20 | 1.20 |
| 10 | 1.10 | 1.10 |
| 15 | 1.25 | 1.25 |
| 20 | 1.30 | 1.30 |
| 25 | 1.20 | 1.20 |
| 30 | 1.10 | 1.10 |
| 35 | 1.25 | 1.25 |
| 40 | 1.30 | 1.30 |

Answer: SnO₂ shows sharp dips at regular intervals, suggesting a periodic change, while In₂O₃ growth rate remains relatively stable.

Answer: SnO₂

Answer: SnO₂ growth may be affected by precursor pulsing or surface saturation ,In₂O₃ growth is more consistent, Useful for tuning multilayer structures.

Answer: Yes


Fig. 2. AES depth profile (a) and impurity contents (b) of TiN films deposited by remote PEALD method using TDMAT precursor and nitrogen plasma.

The atomic concentration of various elements throughout a film, with carbon and oxygen decreasing deeper in the film.

Atomic concentrations of carbon and oxygen as function of deposition temperature.

| Sputter Time (min) | C | O | O of SiO₂ | Ti | N | Si |
|---|---|---|---|---|---|---|
| 0 | 4 | 6 | 0 | 39 | 53 | 0 |
| 5 | 4 | 5 | 0 | 37 | 53 | 0 |
| 10 | 4 | 5 | 0 | 36 | 50 | 5 |
| 15 | 4 | 3 | 0 | 35 | 45 | 10 |
| 20 | 4 | 0 | 10 | 30 | 40 | 20 |
| 25 | 3 | 0 | 25 | 25 | 30 | 25 |
| 30 | 3 | 0 | 35 | 20 | 20 | 30 |
| 35 | 0 | 0 | 45 | 15 | 15 | 30 |
| 40 | 0 | 0 | 50 | 10 | 10 | 30 |
| 45 | 0 | 0 | 55 | 5 | 5 | 30 |
| 50 | 0 | 0 | 60 | 0 | 0 | 35 |

| Deposition Temperature (°C) | Carbon | Oxygen |
|---|---|---|
| 150 | 11 | 10 |
| 200 | 7 | 6 |
| 250 | 3 | 3 |
| 300 | 4 | 3 |
| 350 | 5 | 3 |

Answer: The lowest impurities are achieved at 250 degrees C.

Answer: A common source of carbon impurities is the precursor ligands. Oxygen impurities can arise due to background water in the reactor which is incorporated by the plasma

Answer: This is due to the penetration depth of the measurement method which is likely to be around 5-10 nm.

Answer: The TiN was deposited on silicon oxide, this is shown by the Si and O from SiO2 signal.

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/27/Ju Youn KIM et al.pdf


Figure 2. Growth rates of thermal and PE-ALD  $\mathrm{Ta_2O_5}$  as a function of water and oxygen plasma exposure time  $(t_{\mathrm{r}})$  on  $\mathrm{Si(001)}$  substrate at  $T_{\mathrm{s}} = 250^{\circ}\mathrm{C}$ .

The figure compares growth rates of thermal ALD (using H₂O) and PE-ALD (using O₂ plasma) for Ta₂O₅ as a function of reactant exposure time at 250°C. Both methods exhibit saturation behavior for t_r ≥ 1 s, with PE-ALD achieving a higher saturated growth rate (~1.2 Å/cycle) compared to thermal ALD (~0.85 Å/cycle).

| t_r, s | Growth rate thermal ALD (Å/cycle) | Growth rate PE-ALD (Å/cycle) |
|---|---|---|
| 0 | 0.05 | 0.08 |
| 0.25 | 0.30 | 0.40 |
| 0.5 | 0.75 | 0.75 |
| 1 | 0.82 | 1.10 |
| 2 | 0.83 | 1.12 |
| 3 | 0.84 | 1.14 |
| 5 | 0.85 | 1.14 |

Answer: PE-ALD achieves approximately 1.2 Å/cycle while thermal ALD reaches approximately 0.85 Å/cycle, making PE-ALD about 40% faster.

Answer: Thermal ALD uses water vapor, while PE-ALD uses oxygen plasma.

Answer: The higher growth rate in PE-ALD is attributed to the greater reactivity of the oxygen plasma species, which include atomic oxygen and activated oxygen molecules. These reactive species can more efficiently oxidize the adsorbed PDMAT precursor and potentially create more reactive surface sites for subsequent adsorption cycles compared to water vapor in thermal ALD.

Answer: Yes. Both methods show saturation of growth rate for reactant exposure times greater than approximately 1 second.

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


Figure 3. Growth rates of thermal and PE-ALD  $\mathrm{Ta_2O_5}$  as a function of growth temperature  $T_{\mathrm{s}}$ .

The figure shows the temperature dependence of Ta₂O₅ growth rate for thermal ALD and PE-ALD. Both methods exhibit three regimes: elevated growth rates at low temperatures, a stable ALD window in the middle, and increasing growth rates at high temperatures due to precursor decomposition. The ALD window spans 200 to 250°C for thermal ALD and 150 to 250°C for PE-ALD, demonstrating that PE-ALD enables ALD growth at approximately 50°C lower temperature.

| T_s, °C | Growth rate thermal ALD (Å/cycle) | Growth rate PE-ALD (Å/cycle) |
|---|---|---|
| 100 | - | 1.40 |
| 125 | 1.32 | - |
| 150 | 1.20 | 1.20 |
| 175 | - | 1.18 |
| 200 | 0.90 | 1.17 |
| 250 | 0.85 | 1.15 |
| 275 | - | 1.25 |
| 300 | 1.00 | - |
| 500 | 1.58 | 1.70 |

Answer: The ALD window is 200 to 250°C for thermal ALD and 150 to 250°C for PE-ALD.

Answer: At high temperatures, the PDMAT precursor undergoes thermal decomposition before the self-limiting surface reaction can complete. This leads to continuous CVD-like deposition rather than true ALD, resulting in higher apparent growth rates. The loss of self-limitation compromises the precise thickness control that is characteristic of ALD.

Answer: PE-ALD uses oxygen plasma containing highly reactive species such as atomic oxygen and activated oxygen molecules. These radicals have sufficient reactivity to oxidize the adsorbed precursor even at lower temperatures where water vapor in thermal ALD would be insufficiently reactive. In fact, the authors note that Ta₂O₅ could not be deposited without plasma at temperatures below 250°C.

Answer: Approximately 1.4 Å/cycle.


Figure 4. Composition of GST films as a function of (a)  $\mathrm{GeCl}_2\cdot \mathrm{C}_4\mathrm{H}_8\mathrm{O}_2$  pulse length and (b)  $\mathrm{GeTe / (GeTe + Sb_2Te_3)}$  cycling ratio.  $\mathrm{SbCl}_3$  and  $(\mathrm{Et}_3\mathrm{Si})_2\mathrm{Te}$  pulse lengths were always  $1.0~\mathrm{s}$  and purges were  $2.0~\mathrm{s}$ .

The scatter plot shows the composition of a Ge, Sb, and Te film at different pulse lengths of GeCl₄-dioxane.

The scatter plot displays the composition of a Ge, Sb, and Te film at various cycles of GeTe/(GeTe+Sb₂Te₃).

| GeCl₄-dioxane pulse length (s) | Composition (at.%)  Ge|Composition (at.%)  Sb|Composition (at.%)  Te|
|---|---|---|---|
| 1 | 15 |35|50|
| 2 | 25 |25|50|
| 3 | 30 |20|50|
| 4 | 30 |20|50|
| 6 | 30 |20|50|

| GeTe/(GeTe+Sb₂Te₃) cycling | Composition (at.%)  Ge|Composition (at.%)  Sb|Composition (at.%)  Te|
|---|---|---|---|
| 0.25 | 20 |30|50|
| 0.33 | 22 |28|50|
|0.36|28|22|50|
| 0.5 | 30 |20|50|

Answer: 4 s

Answer: Sb is replaced with Ge, as for increasing Ge exposure, the Ge percentage increases and the Sb percentage decreases. The Te percentage remains constant.

Answer: three

Answer: The method to show the cycle ratio can mean 1 to 3 but also 50 to 150, in both cases the composition will be different due to the probing depth of the measurement technique with which the composition is measured.

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


Fig.9  $I_{DS} - V_{DS}$  characteristics of the conventional HEMT and the  $\mathrm{Ga_2O_3}$  MOS-HEMT upon varying the value of  $V_{G}$  from  $-6$  to  $+2\mathrm{V}$  at a step of  $+1\mathrm{V}$

The chart shows the drain current (IDSS) versus drain-source voltage (VDS) for Ni/Au-HEMT and Ga2O3 MOS-HEMT devices.

| VDS (V) | Ni/Au-HEMT | Ga2O3 MOS-HEMT |
| --- | --- | --- |
| 0 | 0 | 0 |
| 5 | 800 | 1000 |
| 10 | 810 | 1010 |
| 15 | 805 | 1000 |
| 20 | 800 | 900 |

Answer: The Vg varies from -6 V to +2 V in steps of 1 V.

Answer: In both cases, the current increases to 5 V and then remains almost constant.

Answer: As can be seen in the figure, Ga2O3 MOS-HEMT sample reaches higher current values.

Answer: I_DSS of 608 mA/mm for Ni/Au-HEMT and I_DSS of 720 mA/mm for Ga2O3 MOS-HEMT.

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/36/Huan-Yu Shih et al.pdf


Fig. 11 a Gate leakage current and b three-terminal off-state breakdown characteristics of the conventional HEMT and the  $\mathrm{Ga}_{2}\mathrm{O}_{3}$  MOS-HEMT

The graph shows the gate-drain current (IGD) versus gate-source voltage (VGD) for Ni/Au-HEMT and Ga2O3 MOS-HEMT.

The graph shows the drain-source current (IDS) versus drain-source voltage (VDS) for Ni/Au-HEMT and Ga2O3 MOS-HEMT. Voltage values of 126 V and 170 V are highlighted.

| VGD (V) | Ni/Au-HEMT | Ga2O3 MOS-HEMT |
| --- | --- | --- |
| -10 | 10^-3 | 10^-5 |
| -8 | 10^-3 | 10^-5 |
| -6 |  10^-3  | 10^-5 |
| -4 |  10^-3  | 10^-5 |
| -2 |  10^-4  | 10^-6 |
| 0 |  10^-6  | 10^-9 |
| 2 |  10^0 | 10^0 |

| VGD (V) | Ni/Au-HEMT | Ga2O3 MOS-HEMT |
| --- | --- | --- |
| 0 | 0 | 0 |
| 30 | 0 | 0 |
| 60 | 0 | 0 |
| 90 | 0 | 0 |
| 120 | 0.15 | 0.01 |
| 150 | - | 0.05 |

Answer: Subfigure a shows the gate-drain current versus voltage gate-drain for both samples.

Answer: For the Ni/Au-HEMT, the current remains constant but begins to increase after 90 V, with a significant increase at 126 V. Meanwhile, the Ga2O3 MOS-HEMT sample remains constant until approximately 150 V and then increases significantly at 170 V.

Answer: 170 V.

Answer: The ALD Ga2O3 film can suppressed the gate leakage current density and increased the drain-state voltage.


Fig. 8 The capacitance-voltage (C-V) characteristics of the conventional HEMT and the  $\mathrm{Ga}_{2}\mathrm{O}_{3}$  MOS-HEMT

The figure shows the capacitance-voltage characteristics of the conventional HEMT and the Ga2O3 MOS-HEMT.

| Gate Voltage (V) | Ga2O3 MOS-HEMT | conventional HEMT |
|-----------------|-------|-------|
| -8             | 0   | 0   |
| -7             | 0   | 0   |
| -6             | 0   | 0   |
| -5             | 0   | 0   |
| -4             | 15  | 0   |
| -3             | 15  | 27   |
| -2             | 15  | 27   |
| -1             | 15  | 27   |
|  0             | 15  | 27   |

Answer: The capacitance-voltage characteristics were measured at 1 MHz.

Answer: For both the Ga2O3 MOS-HEMT and the conventional HEMT, the capacitance increases until it reaches plateaus of 15 and 7, respectively.

Answer: The capacitance value is o when the gate voltage varies from -8 to -4 V.

Answer: The Ga2O3 HEMT allows for the lowest possible capacitance values.


FIG. 7. Change of sheet resistance on  $\mathrm{Cu / PEALD}$  TiN  $10 \mathrm{nm} / \mathrm{Si}$  and  $\mathrm{Cu / PEALD}$  Ti-Si-N  $10 \mathrm{nm} / \mathrm{Si}$  as a function of annealing temperature.

Multiple line chart showing sheet resistance evolution of Cu/PEALD TiN and Cu/PEALD Ti–Si–N (10 nm) films on Si as a function of annealing temperature. TiN remains conductive up to ~550 °C but exhibits a sharp resistance increase at 600 °C, indicating thermal degradation. In contrast, Ti–Si–N maintains near-zero resistance up to 600 °C and shows a delayed, gradual increase at higher temperatures, demonstrating enhanced thermal stability due to silicon incorporation.

| Annealing temperature (°C) | Sheet resistance: TiN  | Sheet resistance: Ti–Si–N @ Ar  |
|----------------------------|-----------------------------|--------------------------------------|
| 450                        | ~0                          | ~0                                   |
| 500                        | ~0                          | ~0                                   |
| 550                        | ~5                          | ~0                                   |
| 600                        | ~62                         | ~0                                   |
| 650                        | –                           | ~7                                   |
| 700                        | –                           | ~30                               |

Answer:
-Nitrogen out-diffusion from TiN
, -Grain growth and grain boundary formation
, -Copper diffusion into the barrier layer
, -Loss of film continuity during annealing

Answer: TiN shows a sudden and dramatic rise in sheet resistance at 600 °C, indicating rapid loss of electrical continuity. In contrast, Ti–Si–N maintains low resistance through 600 °C and degrades only gradually at higher temperatures, reflecting superior thermal robustness.

Answer: Silicon incorporation disrupts long-range crystallinity and suppresses grain boundary formation, which are common diffusion pathways. This structural modification stabilizes the film against high-temperature degradation, delaying resistance increase compared to pure TiN.

Answer: Because Ti–Si–N maintains low sheet resistance at higher annealing temperatures, indicating improved thermal and diffusion-barrier stability.


FIG. 1. Effective lifetime as a function of the excess carrier density for low resistivity  $p$ -type  $(300\mu \mathrm{m}$ ,  $(111)$ ,  $2.0\Omega \mathrm{cm}$  float zone  $c$ -Si substrate passivated with 30 and  $15\mathrm{nm}$  thick  $\mathrm{Al}_2\mathrm{O}_3$  films.

The scatter plot shows the relationship between injection level and effective lifetime for two different thickness passivation layers (30 nm and 15 nm). The data points are clustered around a curve, indicating a non-linear relationship.

| Injection level Δn (cm⁻³) | Effective lifetime (s), 30 nm|Effective lifetime (s), 15 nm|
|---|---|---|
| 10¹² | 2*10⁻⁴ |-|
| 10¹³ | 4*10⁻⁴ |10⁻³|
| 10¹⁴ | 6*10⁻⁴ |10⁻³ |
| 10¹⁵ | 9*10⁻⁴ |10⁻³ |
| 10¹⁶ | 10⁻³ |10⁻³ |
| 10¹⁷ | 10⁻⁴ |10⁻⁴ |

Answer: The 15 nm thick layer, this thickness seems to have the best effect over a broader range of injection level.

Answer: 0.001 s.

Answer: Scattered data does not show a straight line. In addition, both axes are logarithmic.

Answer: 0.0001 s


FIG. 2. Effective lifetime as a function of the excess carrier density for low resistivity  $n$ -type  $(275\mu \mathrm{m}$ ,  $(100)$ ,  $1.9\Omega \mathrm{cm}$  float zone  $c$ -Si substrate passivated with 30, 15, and  $7\mathrm{nm}$  thick  $\mathrm{Al}_2\mathrm{O}_3$  films.

The chart shows the effective lifetime of a system as a function of injection level Δn, with data points represented by different symbols corresponding to different thickness passivation layers (26, 13, and 7 nm).

| Injection level Δn (cm⁻³) | Effective lifetime (s), 26 nm|Effective lifetime (s), 13 nm|Effective lifetime (s), 7 nm|
|---|---|---|---|
| 10¹² | 10⁻³ |-|-|
| 10¹³ | 2*10⁻³ |10⁻³|10⁻³|
| 10¹⁴ | 5*10⁻³ |2*10⁻³ |2*10⁻³ |
| 10¹⁵ | 7*10⁻³ |3*10⁻³ |3*10⁻³ |
| 10¹⁶ | 10⁻³ |8*10⁻⁴ |8*10⁻⁴|
| 10¹⁷ | - |-|10⁻⁴ |

Answer: The difference between the 7 and 13 nm thick passivating layers is negligable, whereas the 26 nm layer does show an increase in passivation.

Answer: The overal trends look similar, important is that the maximum effective lifetime seems to shift to higher injection levels with thicker passivation layers.

Answer: 0.008 s with a passivation layer of 26 nm.

Answer: 10^15 per cubic centimeter.


Fig.4 Resistivity.  $\rho$  a),carrier concentration,  $n$  b),mobility,  $\mu$  c and doping efficiency  $\eta$  (d) of the ZnO:X  $\mathbb{X} = \mathbb{A}\mathbb{I}$  B) films as a function of the doping fraction (DF) measured by XPS. TIB was used as a B source while DMAI and TMA were used as A sources. All films had a thickness of  $45\pm$ $5\mathrm{nm}$  and were deposited on glass substrates at  $150^{\circ}C$  The lines serve as guides to the eye. The error bars for  $\rho$  are plotted in the graph (some of them lying within the data points) and the estimated relative statistical uncertainties for n,  $\mu$  and  $\eta$  are  $3\%$ $5\%$  and  $20\%$  respectively.

The resistivity of TIB, DMAI, and TMA decreases as the doping fraction increases and then slightly increases

The carrier concentration of TIB, DMAI, and TMA initially increases and then decreases as the doping fraction increases.

The Mobility also increases initially and then decreases

Doping efficiency increases at the beginning and then decreases, but for TMA it remains constant.

| Doping fraction, DF | TIB (mΩ·cm) | DMAI (mΩ·cm) | TMA (mΩ·cm) |
|---|---|---|---|
| 0.00 |  0          |   0           | 70          |
| 0.020   | 6           | 10           | 20          |
| 0.040   | 8           |  8           | 15          |
| 0.060   | 10         | 10          | 12          |
| 0.080   | 28          | 18           | -         |
| 0.100   | -             | 25           | 22          |

| Doping fraction, DF | TIB (10^20 cm^-3) | DMAI (10^20 cm^-3) | TMA (10^20 cm^-3) |
|---|---|---|---|
| 0.00 | 0.0 | 0.0 | 0.0 |
| 0.01 | 1 | 1 | - |
| 0.02 | 1.5 | 1.5 | - |
| 0.03 |3.0 | 2.5 | 0.5 |
| 0.04 | -    | 2.5 | 1.0 |
| 0.05 | 2.75 | - | -   |
| 0.06 | 2.0 | 2.2 | 1.5 |
| 0.08 | 1.5 | - | - |
| 0.09 | 1.0 | 2.2 | - |
| 0.10 |- 000 | 2.2 | 1.5 |

| Doping fraction, DF | TIB (cm²/V·s^-1) | DMAI (cm²/V·s^-1) | TMA (cm²/V·s^-1) |
|---|---|---|---|
| 0.00 | 7.0 | 7.0 | 7.0 |
| 0.01 | 8.0 | 8.0 | 8.0 |
| 0.02 | 9.0 | 9.0 | 9.0 |
| 0.03 | 10.0 | 10.0 | 10.0 |
| 0.04 | 11.0 | 11.0 | 11.0 |
| 0.05 | 12.0 | 12.0 | 12.0 |
| 0.06 | 10.0 | 10.0 | 10.0 |
| 0.07 | 8.0 | 8.0 | 8.0 |
| 0.08 | 6.0 | 6.0 | 6.0 |
| 0.09 | 4.0 | 4.0 | 4.0 |
| 0.10 | 2.0 | 2.0 | 2.0 |

Answer: The addition of a small amount of B sharply reduced the resistivity of the films to a minimum of ~3.5 mOhm cm for a doping fraction (DF) of 0.016. The addition of Al also reduced the resistivity of the films to a minimum in both cases. Doping with DMAI resulted in ZnO:Al films with the same minimum resistivity than ZnO:B films at the same DF of 0.016, while doping with TMA resulted in ZnO:Al films with a higher minimum resistivity of 8 mO cm for a higher DF of 0.040. The resistivity of ZnO:Al films increased in both cases after achieving the minimum resistivity value, but this increase was more gradual than observed for the ZnO:B films.

Answer:
The overall lower mobility values obtained for the three doping materials and the trend of mobility decreasing with increasing doping fraction over the full range studied can most likely be attributed to grain boundary scattering. Furthermore, it is rather striking that m increases when going
from undoped ZnO to low B-doping concentrations, as one would expect more ionized impurity scattering. Yet a similar  trend in mobility was observed for ZnO:B films prepared by the
sol–gel technique.

Answer: TIB and DMAI, showed the highest doping efficiency at low doping levels, i.e., 30–40% for a range of DF of 0.016–0.018 that resulted in the lowest resistivities for the ZnO:B and ZnO:Al (doped with DMAI) films. Both alternative precursors outperformed TMA in terms of doping efficiency, as a maximum doping efficiency of 6% was achieved using this conventional precursor.

Answer: The increase of the carrier concentration for low doping fractions in the three cases can be assigned to the effective doping of B and Al, respectively (i.e., substitution of Zn2+ by B3+ or Al3+). The sharp decrease of the carrier concentration for TIB and the local saturation for DMAI and TMA might occur as a result of dopant occupying interstitial sites, dopant clustering, formation of oxides, or formation of metastable phases, making dopant inactive, which is possibly related to reaching the solubility limit of the B and Al into the ZnO lattice.


FIG. 5. Growth rate of the ruthenium films grown from  $\mathrm{RuCp}_2$  on iridium as a function of the deposition temperature, the film thicknesses being measured by EDX and XRR. The  $\mathrm{RuCp}_2$  and oxygen pulse times were 0.5 and  $0.2\mathrm{s}$ , respectively, and the purge period between the pulses was  $0.5\mathrm{s}$ .

The figure shows the growth rate of ruthenium films deposited from RuCp2 on an iridium substrate as a function of deposition temperature. Film thicknesses were measured by EDX and XRR, and the growth rate increases with temperature, ranging from about 0.12 Å/cycle at 225 °C to 0.35 Å/cycle at 275 °C.

| Deposition temperature (°C) | Growth rate (Å cycle⁻¹) |
|---|---|
| 225 | 0.12 |
| 230 | 0.15 |
| 250 | 0.25 |
| 275 | 0.35 |
| 280 | 0.33 |

Answer: Increasing the deposition temperature generally improves the growth rate and can enhance film uniformity by promoting consistent precursor adsorption and reaction across the surface. However, excessively high temperatures might risk precursor decomposition or unwanted side reactions, so optimization is required to balance growth rate and film quality.

Answer: Yes, the growth rate on iridium is higher than on Al2O3 at similar deposition temperatures. For example, at 275 °C, the growth rate on iridium is 0.35 Å/cycle, while on Al2O3 it is 0.23 Å/cycle.

Answer: As the deposition temperature increases from 225 °C to 275 °C, the growth rate of ruthenium films increases almost linearly. At lower temperatures, the growth rate is slower (around 0.12 Å/cycle) and reaches approximately 0.35 Å/cycle at higher temperatures. This indicates that higher temperatures enhance the reactivity of the RuCp2 precursor and improve film deposition efficiency.

Answer: Iridium provides a higher nucleation density, promoting faster film growth, Al₂O₃ shows a longer incubation period at the beginning, reducing the overall growth rate, Substrate type influences the minimum temperature required for film growth due to precursor reactivity differences


Figure 8.  $P - V$  hysteresis loops for (a) Fe-; (b) Co-; and (c) Ni-doped  $\mathrm{ZnO}$  films.

The figure shows the polarization (P) as a function of applied voltage (V) for ZnO:Fe

The figure shows the polarization (P) as a function of applied voltage (V) for ZnO:Co

The figure shows the polarization (P) as a function of applied voltage (V) for ZnO:Ni

| Applied Voltage (V) | P (μC/cm²) at 1.5 kHz | P (μC/cm²) at 3 kHz | P (μC/cm²) at 5 kHz |
|---|---|---|---|
| -3.0 | -40 | -38 | -36 |
| -2.0 | -30 | -28 | -26 |
| -1.0 | -15 | -14 | -13 |
| 0.0  | 0   | 0   | 0   |
| 1.0  | 15  | 14  | 13  |
| 2.0  | 30  | 28  | 26  |

| Applied Voltage (V) | P (μC/cm²) |
|---|---|
| -3.0 | -40 |
| -2.0 | -30|
| -2.0 | -30 |
| -1.0 | -15 |
| 0.0  | 0   |
| 1.0  | 15  |
| 2.0  | 30  |

| Applied Voltage (V) | P (μC/cm²) |
|---|---|
| -3.0 | -40 |
| -2.0 | -30 |
| -1.0 | -15 |
| 0.0  | 0   |
| 1.0  | 15  |
| 2.0  | 30  |

Answer: The ferroelectric P−V hysteresis loops for TM doped ZnO films are measured using a Sawyer−Tower circuit

Answer: The Fe-doped layers (Figure 8a) reveal a ferroelectric like behavior with a well-resolved P−V loop and the polarization increasing with the decreasing frequency

Answer: No

Answer: The results for Ni- and Co-doped layers, though showing some P− V hysteresis, are not that convincing for the existence of ferroelectricity


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


Δm₁ (open markers) is consistently higher than Δm₀ (filled markers) across 100–400 °C for all three cycle-time sequences. Δm₁ peaks around ~250–300 °C (depending on marker set) and then trends downward toward 400 °C, while Δm₀ stays comparatively flat through ~350 °C. The 5–2–2–5 s condition shows a notable Δm₀ increase at ~400 °C relative to the other sequences. Overall, varying the first-step pulse time mainly impacts Δm₁ magnitude and its temperature dependence, more than Δm₀.

Two cycle-time sequences are compared, and the separation between Δm₁ (open) and Δm₀ (filled) is maintained across the full temperature range. Δm₁ rises toward a maximum near ~300 °C and then decreases at higher temperature, whereas Δm₀ remains near ~35–40 with only modest changes. Differences between the two purge-time conditions are clearer in Δm₁ than in Δm₀. The data suggest temperature sensitivity is concentrated in the Δm₁ response rather than the baseline Δm₀ increment.

| Growth temperature (°C) | Δm1 (0.5-2-2-5 s, open ○) | Δm1 (2-2-2-5 s, open □) | Δm1 (5-2-2-5 s, open △) | Δm0 (0.5-2-2-5 s, filled ●) | Δm0 (2-2-2-5 s, filled ■) | Δm0 (5-2-2-5 s, filled ▲) |
|---|---:|---:|---:|---:|---:|---:|
| 100 | ~86 | ~92 | ~88 | ~44 | ~45 | ~47 |
| 150 | ~75 | ~84 | ~85 | ~35 | ~39 | ~40 |
| 200 | ~88 | ~90 | ~95 | ~33 | ~37 | ~37 |
| 250 | ~88 | ~105 | ~102 | ~36 | ~37 | ~37 |
| 300 | ~101 | ~100 | ~112 | ~37 | ~38 | ~44 |
| 350 | ~96 | ~101 | ~100 | ~38 | ~39 | ~39 |
| 400 | ~90 | ~85 | ~98 | ~45 | ~45 | ~64 |

| Growth temperature (°C) | Δm1 (2-2-0.5-5 s, open ○) | Δm1 (2-2-5-5 s, open □) | Δm0 (2-2-0.5-5 s, filled ●) | Δm0 (2-2-5-5 s, filled ■) |
|---|---:|---:|---:|---:|
| 100 | ~80 | ~99 | ~41 | ~52 |
| 150 | ~75 | ~90 | ~36 | ~39 |
| 200 | ~87 | ~98 | ~34 | ~38 |
| 250 | ~89 | ~101 | ~35 | ~37 |
| 300 | ~104 | ~110 | ~36 | ~37 |
| 350 | ~98 | ~99 | ~38 | ~35 |
| 400 | ~83 | ~87 | ~40 | ~40 |

Answer: The third step (purge time) was varied between 0.5 s and 5 s.

Answer:
1. 0.5 - 2 - 2 - 5 s
, 2. 2 - 2 - 2 - 5 s
, 3. 5 - 2 - 2 - 5 s

Answer: It varies only weakly, staying clustered near ~35–45 arbitrary units across most of 100–350 °C.

Answer: Δm₁ is systematically larger than Δm₀ across the entire temperature range, typically ~80–110 versus ~30–45 in arbitrary units. Δm₁ also shows a clearer temperature response, with a broad maximum around ~250–300 °C before decreasing at higher temperature. By contrast, Δm₀ is comparatively flat through ~350 °C, with only small offsets between marker sets. The main temperature sensitivity therefore sits in Δm₁ rather than Δm₀.


Fig.2.  $\Delta m_0$  and  $\Delta m_1$  as functions of growth temperature. Buffer layers were deposited at 100 and  $300^{\circ}\mathrm{C}$ . The  $\mathrm{TiCl_4}$  pulse time, first purge time,  $\mathrm{H}_2\mathrm{O}$  pulse time, and second purge time were 2, 2, 2, and  $5\mathrm{s}$ , respectively.

Scatter plot comparing mass increments Δm₀ and Δm₁ vs. growth temperature for films grown on buffer layers deposited at 100 °C (circles) and 300 °C (squares). It shows that the 300 °C buffer layer generally results in higher or increasing Δm₁ values, particularly above 200 °C.

| Growth Temp (°C) | Buffer 100°C: Δm0 (●) | Buffer 100°C: Δm1 (○) | Buffer 300°C: Δm0 (■) | Buffer 300°C: Δm1 (□) |
|---|---|---|---|---|
| 100 | ~50 | ~95 | ~45 | ~92 |
| 150 | ~35 | ~75 | ~40 | ~85 |
| 200 | ~30 | ~68 | ~38 | ~92 |
| 250 | ~25 | ~60 | ~38 | ~105 |
| 350 | ~28 | ~62 | ~40 | ~100 |

Answer:
1.  2 s (TiCl₄)
, 2.  2 s (First purge)
, 3.  2 s (H₂O pulse)
, 4.  5 s (Second purge)

Answer: Yes, the open symbols are consistently plotted higher on the y-axis than the corresponding filled symbols.

Answer: The buffer layer deposited at 300 °C  (open squares) generally results in significantly higher Δm₁ values compared to the buffer deposited at 100 °C (open circles). This difference is most notable at higher growth temperatures (above 200 °C), where the 300 °C buffer sample shows an increasing trend, reaching values over 100 units, while the 100 °C buffer sample decreases to around 60 units.

Answer: The temperature at which the buffer layer was grown (300 °C for squares vs 100 °C for circles).


Fig.6.  $\Delta m_0$ ,  $\Delta m_1$  and  $\Delta m_1 - \Delta m_2^{\prime}$  recorded at  $350^{\circ}\mathrm{C}$  as functions of  $\mathrm{TiCl_4}$  pulse time. The first purge time,  $\mathrm{H}_2\mathrm{O}$  pulse time, and second purge time were 10, 2 and  $5\mathrm{s}$ , respectively.

This figure shows Δm₀, Δm₁, and Δm₁ − Δm₂′ as functions of TiCl₄ pulse time at 350 °C. Δm₁ and Δm₁ − Δm₂′ increase rapidly at short pulse times and saturate beyond ~2 s, consistent with self-limiting surface adsorption. In contrast, Δm₀ continues to increase with pulse time, indicating an additional non-saturating mass-gain contribution. The divergence between Δm₁ saturation and Δm₀ growth suggests the onset of parasitic or CVD-like processes at longer TiCl₄ exposures.

| TiCl4 Pulse Time (s) | Δm1 (Triangles) | Δm1 - Δm2' (Squares) | Δm0 (Circles) |
|---|---|---|---|
| 0.5 | ~82 | ~69 | ~37 |
| 1.0 | ~84 | ~73 | ~40 |
| 2.0 | ~88 | ~74 | ~41 |
| 5.0 | ~88 | ~75 | ~43 |
| 10.0 | ~88 | ~80 | ~50 |

Answer: 350 °C.

Answer: Yes—closer to Δm₁.

Answer: Δm₁ rises rapidly at short pulse times and then plateaus, indicating saturation of surface-limited reactions. Δm₀, however, continues to increase with pulse time, suggesting an additional mass-gain mechanism that does not self-limit. This contrast implies that extended precursor exposure contributes to non-ideal growth behavior.

Answer: Since Δm₁ saturates by ~2 s, longer TiCl₄ pulses do not improve self-limiting growth but instead promote parasitic mass gain. Optimizing pulse time near the saturation threshold minimizes cycle time while avoiding unwanted CVD-like contributions.


Fig.8.  $\Delta m_0 / (\Delta m_1 - \Delta m_2')$  as a function of growth temperature determined at different  $\mathrm{TiCl_4}$  pulse times. Buffer layers were grown at temperatures of 100 and  $300^{\circ}\mathrm{C}$ . Notation of cycle times is the same as in Fig. 3.

Scatter plot showing the ratio Δm₀/(Δm₁−Δm₂) as a function of growth temperature (~100–400 °C) for three different cycle sequences where the first pulse time varies (0.5 s, 2 s, 5 s). The ratio generally decreases with temperature up to ~250–300 °C for the longer pulse-time conditions before increasing again at higher temperatures.

| Growth Temp (°C) | 5s Pulse (Squares) | 0.5s Pulse (Open Circ) | 2s Pulse (Filled Circ) | 2s Pulse (Triangles, TB=100) |
|---|---|---|---|---|
| 100 | ~0.56 | ~0.52 | ~0.50 | - |
| 150 | ~0.50 | ~0.50 | ~0.50 | ~0.53 |
| 200 | ~0.41 | ~0.40 | ~0.42 | ~0.48 |
| 250 | ~0.39 | ~0.41 | ~0.39 | ~0.46 |
| 300 | ~0.44 | ~0.40 | ~0.43 | - |
| 350 | ~0.45 | ~0.44 | ~0.45 | ~0.47 |
| 400 | ~0.75 | ~0.58 | ~0.65 | - |

Answer: Δm₀/(Δm₁−Δm₂)

Answer: No, the ratio increases significantly from approximately 0.44 to 0.75 in that temperature range.

Answer: The mass ratio for the 5 s pulse time sample starts at approximately 0.56 at 100 °C and decreases steadily as the temperature rises, reaching a minimum value around 250 °C. After this point, the trend reverses. Above 300 °C, the ratio increases sharply, reaching its maximum value of ~0.75 at 400 °C.

Answer: 100 °C and 300 °C.


Fig. 3.  $\Delta m_0$  and  $\Delta m_1$  as functions of substrate temperature measured at (a) different  $\mathrm{TiCl_4}$  pulse times and (b) different  $\mathrm{H}_2\mathrm{O}$  pulse times. Buffer layer was grown at  $300^{\circ}\mathrm{C}$ . Cycle times shown in the inset denote the  $\mathrm{TiCl_4}$  pulse time, first purge time,  $\mathrm{H}_2\mathrm{O}$  pulse time, and second purge time, respectively. Fig. 5.  $\Delta m_0$  as a function of (a) the first purge time and (b) the second purge time. Notation of cycle times is the same as in Fig. 3. Buffer layer was deposited at  $300^{\circ}\mathrm{C}$ .

Δm₀ decreases sharply with increasing first purge time up to ~1–2 s and then plateaus for both growth temperatures. At all purge times, Δm₀ remains higher at 150 °C than at 350 °C.

A similar behavior is observed when varying the second purge time, with Δm₀ dropping rapidly at short purge times and stabilizing beyond ~2 s. The persistence of a temperature offset indicates that growth temperature influences the net mass increment even after sufficient purging.

| First purge time x (s) | Δm₀ at 150 °C (circles) | Δm₀ at 350 °C (squares) |
|---|---|---|
| 0.1 | ~56 | ~41 |
| 0.5 | ~44 | ~35 |
| 1.0 | ~41 | ~36 |
| 2.0 | ~41 | ~34 |
| 5.0 | ~39 | ~30 |
| 10.0 | ~40 | ~30 |

| Second purge time x (s) | Δm₀ at 150 °C (circles) | Δm₀ at 350 °C (squares) |
|---|---|---|
| 0.1 | ~54 | ~43 |
| 0.5 | ~45 | ~38 |
| 1.0 | ~45 | ~34 |
| 2.0 | ~42 | ~34 |
| 5.0 | ~40 | ~35 |
| 10.0 | ~40 | ~35 |

Answer: Yes

Answer: The similar purge-time dependence indicates that both purge steps play comparable roles in removing residual species. Once a critical purge duration is reached, surface reactions become self-limiting regardless of purge order.

Answer: The first purge step following the TiCl₄ pulse.

Answer: No


Fig. 4.  $\Delta m_2^{\prime}$  as a function of growth temperature recorded at different  $\mathrm{TiCl_4}$  pulse times. Buffer layers were deposited at  $T_{\mathrm{B}} = 100$  and  $300^{\circ}\mathrm{C}$ . Notation of cycle times is the same as in Fig. 3.

This figure shows Δm₂′ as a function of growth temperature (≈100–400 °C) for different TiCl₄ pulse-time sequences, with buffer layers grown at TB = 100 °C and TB = 300 °C. Δm₂′ increases with temperature for all conditions, with a pronounced rise at ≳300 °C. At lower growth temperatures (≈100–250 °C), samples with TB = 100 °C consistently exhibit lower Δm₂′ values than those with TB = 300 °C. At higher temperatures, Δm₂′ converges to larger values across pulse times, indicating reduced sensitivity to buffer-layer temperature.

| Growth Temp (°C) | 5 s pulse (■) | 2 s pulse (●, TB = 300 °C) | 0.5 s pulse (○) | 2 s pulse (▲, TB = 100 °C) |
|---|---|---|---|---|
| 100 | ~4.0 | ~3.0 | — | ~2.0 |
| 150 | ~3.0 | ~5.0 | — | ~4.0 |
| 200 | ~6.0 | ~7.0 | ~6.5 | ~4.5 |
| 250 | ~7.0 | ~9.0 | — | ~5.0 |
| 300 | ~13.0 | ~13.0 | ~11.0 | — |
| 350 | ~13.0 | ~13.0 | ~11.0 | ~10.0 |
| 400 | ~13.0 | ~15.0 | ~12.0 | — |

Answer: Δm₂ (arbitrary units).

Answer: No, Δm₂  generally increases with increasing growth temperature.

Answer: At lower growth temperatures (≈100–250 °C), the TB = 100 °C triangle series sits below the TB = 300 °C circle/square series, meaning Δm2′ is smaller when the buffer is grown at 100 °C. For example, near 200 °C the triangle point is around ~4–5, while TB=300 °C points cluster closer to ~6–7. At higher temperatures (≥300 °C), Δm2′ rises for all conditions and the separation becomes less consistent, with the largest values appearing near 400 °C.

Answer:
1.     0.5 - 2 - 2 - 5 s
, 2.     2 - 2 - 2 - 5 s
, 3.     5 - 2 - 2 - 5 s


Figure 4. Film thickness measured by in situ SE as a function of the  $\mathrm{In}_2\mathrm{O}_3\cdot \mathrm{H}$  ALD cycles on  $\mathrm{SiO}_2$  open triangles) and on a-Si:H (open circles). Ex situ SE measurements were taken only for 600 and 780 ALD cycles on a-Si:H. Above 600 ALD cycles the selectivity of the process appears to degrade.

The line chart shows the relationship between ALD cycles and the thickness of In_{2}O_{3}:H, with SiO_{2} and a-Si:H marked by different symbols

| ALD cycles | SiO₂ (nm) | a-Si:H (nm) |
|---|---|---|
| 0 | 0 | 0 |
| 50 | 0 | 0 |
| 100 | 2 | 0 |
| 150 | 7 | 0 |
| 200 | 12 | 0 |
| 250 | 17 | 0 |
| 300 | 22 | 0 |
| 350 | 27 | 0 |
| 400 | 32 | 0 |
| 450 | 38 | 0 |
| 500 | 43 | 0 |
| 550 | 48 | 0 |
| 600 | 53 | 0 |
| 650 | 58 | 0 |
| 700 | 63 | 0 |
| 750 | 68 | 0 |
| 800 | 75 | 10 |

Answer:
x-axis: ALD cycles

, y-axis: In₂O₃:H thickness (nm)

, Triangles: SiO₂ substrate

, Circles: a-Si:H substrate

Answer: On SiO₂, the film thickness increases steadily with cycle number after a small initial delay, indicating normal nucleation and a roughly constant growth per cycle. On a-Si:H, the thickness stays close to zero across most of the cycle range, indicating a long nucleation delay. Only at very high cycle count does measurable growth begin to appear on a-Si:H.

Answer: SiO₂ typically presents oxygen-containing / hydroxylated sites that can readily react with many ALD precursors, enabling fast nucleation. In contrast, a-Si:H is H-terminated and comparatively less reactive toward oxide ALD chemistry until it is modified (e.g., oxidized or activated). The plot is consistent with that difference: rapid nucleation on SiO₂ and strongly delayed nucleation on a-Si:H.

Answer: Area-selective ALD relies on having one surface where growth proceeds and another where growth is delayed or suppressed over the desired number of cycles. The strong inhibition on a-Si:H relative to SiO₂ provides that selectivity window. This enables pattern formation by locally converting only selected regions into the “fast nucleation” surface while keeping the rest in the “slow nucleation” state.

icdar2026-competition-data/train/atomic-layer-deposition/simulation-usecase/10/Alfredo Mameli et al.pdf


FIG. 12. (a) Average wafer coverage and (b)  $3\sigma$  wafer thickness variability for an ideal and a soft-saturating ALD process. Simulation conditions are the same as for Fig. 10(c).

The line chart shows the average coverage over time for two conditions: 'Ideal' and 'f2 = 0.1'. The 'Ideal' condition reaches a plateau at approximately 0.9, while 'f2 = 0.1' reaches a plateau slightly below.

The line chart illustrates the 3σ variability percentage over time for two conditions: 'Ideal' and 'f2 = 0.1'. Both conditions show a decreasing trend, with 'Ideal' reaching near-zero variability around 1.0 seconds and 'f2 = 0.1' stabilizing around 1.5%.

| Time, s | Average coverage f_2 = 0.1 | Average coverage Ideal |
|---|---|---|
| 0.0 | 0.0 | 0.0 |
| 0.5 | 0.7 | 0.75 |
| 1.0 | 0.9 | 1.0 |
| 1.5 | 0.9 | 1.0 |
| 2.0 | 0.9 | 1.0 |
| 2.5 | 0.9 | 1.0 |

| Time, s | 3σ variability (%) f_2 = 0.1 | 3σ variability (%) Ideal |
|---|---|---|
| 1.0 | 3.0 | 0 |
| 1.5 | 2.0 | 0 |
| 2.0 | 1.5 | 0 |
| 2.5 | 1.5 | 0 |

Answer: It is 0% for the ideal case and about 1.5% for f_2 = 0.1.

Answer: Near 0 s, the reaction is not saturated and the surface thickness is highly dependent on dose time, which also means the surface thickness varies a lot in this region. When the surface starts to become saturated, the surface thickness no longer depends on the dose time (ideal case) and only very little for the non-ideal case. In this last case, the surface thickness becomes much less variable, which is reflected in the figure as the variability plateaus.

Answer: It is 1.0 for the ideal case and about 0.95 for f_2 = 0.1.

Answer: The same as in figure 10c.

icdar2026-competition-data/train/atomic-layer-deposition/simulation-usecase/11/Angel Yanguas-Gil et al.pdf


FIG. 15. Evolution of the average coverage (a) and  $3\sigma$  variability (b) in  $300\mathrm{mm}$  wafers for two values of by-product reaction probability:  $\beta_{bp} = 10^{-4}$  and  $\beta_{bp} = 10^{-3}$ . The precursor reactivity is  $\beta_{10} = 10^{-2}$ .

The figure shows the average coverage over time for two different βbp values, where βbp = 10-4 and βbp = 10-3.

The figure shows the 3σ variability over time for two different βbp values, where βbp = 10-4 and βbp = 10-3.

| Time, s | Average coverage βbp = 10-4 | Average coverage βbp = 10-3 |
|---|---|---|
| 0.0 | 0.0 | 0.0 |
| 0.5 | 0.4 | 0.4 |
| 1.0 | 0.85 | 0.8 |
| 1.5 | 1.0 | 0.85 |
| 2.0 | 1.0 | 0.85 |
| 2.5 | 1.0 | 0.85 |
| 3.0 | 1.0 | 0.85 |

| Time, s | 3σ variability (%) βbp = 10-4 | 3σ variability (%) βbp = 10-3 |
|---|---|---|
| 1.0 | 95 | 80 |
| 1.5 | 10 | 20 |
| 2.0 | 2 | 20 |
| 2.5 | 2 | 20 |
| 3.0 | 2 | 20 |

Answer: Around 80 for βbp = 10-3 and 90 for βbp = 10-4.

Answer: Around 20 for βbp = 10-3 and 2 for βbp = 10-4.

Answer: Around 0.4.

Answer: Around 0.85 for βbp = 10-3 and 1.00 for βbp = 10-4.


Figure 2. Comparison of electrical characteristics of the PEALD-IGZO TFTs deposited using $\mathrm { O } _ { 2 }$ and $\mathrm { N } _ { 2 } \mathrm { O }$ plasma reactants. (a) Transfer curves and (b) PBTS results of the IGZO TFTs. XPS (c) O 1s and (d) N 1s peaks of the IGZO films.

The figure shows the drain current–gate voltage characteristics of IGZO TFTs fabricated under different ambient conditions. The shift in threshold voltage reflects changes in carrier concentration and device switching behavior.

The figure illustrates the positive bias temperature stress (PBTS) stability of IGZO TFTs measured at 95 °C and an electric field of 2 MV/cm. Differences in threshold voltage shift indicate variations in stress reliability under different ambients.

The figure presents the O 1s XPS spectra of IGZO films processed under different ambient conditions. The relative peak areas reveal changes in lattice oxygen and oxygen-defect concentrations.

The figure shows the N 1s XPS spectra of IGZO films grown under different ambient conditions. The presence and intensity of the N 1s peak confirm nitrogen incorporation into the IGZO matrix.

| Gate Voltage (V) | Drain Current (A) | Condition          |
|-----------------:|-----------------:|------------------|
| -6  | 10⁻¹² | O₂⁺ 1 s |
| -6  | 10⁻¹² | N₂O⁺ 1 s |
| -6  | 10⁻¹³ | N₂O⁺ 5 s |
| -5  | 10⁻¹¹ | O₂⁺ 1 s |
| -5  | 10⁻¹¹ | N₂O⁺ 1 s |
| -5  | 10⁻¹² | N₂O⁺ 5 s |
| -4  | 10⁻¹⁰ | O₂⁺ 1 s |
| -4  | 10⁻¹⁰ | N₂O⁺ 1 s |
| -4  | 10⁻¹¹ | N₂O⁺ 5 s |
| -3  | 10⁻⁹  | O₂⁺ 1 s |
| -3  | 10⁻⁹  | N₂O⁺ 1 s |
| -3  | 10⁻¹⁰ | N₂O⁺ 5 s |
| -2  | 10⁻⁷  | O₂⁺ 1 s |
| -2  | 10⁻⁷  | N₂O⁺ 1 s |
| -2  | 10⁻⁸  | N₂O⁺ 5 s |
| -1  | 10⁻⁵  | O₂⁺ 1 s |
| -1  | 10⁻⁵  | N₂O⁺ 1 s |
| -1  | 10⁻⁶  | N₂O⁺ 5 s |
| 0   | 10⁻⁴  | O₂⁺ 1 s |
| 0   | 10⁻⁴  | N₂O⁺ 1 s |
| 0   | 10⁻⁵  | N₂O⁺ 5 s |
| 1   | 10⁻³ | O₂⁺ 1 s |
| 1   | 10⁻³ | N₂O⁺ 1 s |
| 1   | 10⁻⁴| N₂O⁺ 5 s |
| 2   | 10⁻³| O₂⁺ 1 s |
| 2   | 10⁻³ | N₂O⁺ 1 s |
| 2   | 10⁻³| N₂O⁺ 5 s |
| 3   | 10⁻³ | O₂⁺ 1 s |
| 3   | 10⁻³ | N₂O⁺ 1 s |
| 3   | 10⁻³ | N₂O⁺ 5 s |
| 4   | 10⁻³ | O₂⁺ 1 s |
| 4   | 10⁻³ | N₂O⁺ 1 s |
| 4   | 10⁻³ | N₂O⁺ 5 s |

| Gate Voltage (V) | Drain Current (A) | Condition      |
|-----------------:|------------------:|----------------|
| -6 | 10⁻¹² | O₂⁺ 1 s |
| -6 | 10⁻¹² | N₂O⁺ 1 s |
| -6 | 10⁻¹² | N₂O⁺ 5 s |
| -5 | 10⁻¹² | O₂⁺ 1 s |
| -5 | 10⁻¹² | N₂O⁺ 1 s |
| -5 | 10⁻¹² | N₂O⁺ 5 s |
| -4 | 10⁻¹¹ | O₂⁺ 1 s |
| -4 | 10⁻¹¹ | N₂O⁺ 1 s |
| -4 | 10⁻¹¹ | N₂O⁺ 5 s |
| -3 | 10⁻¹⁰ | O₂⁺ 1 s |
| -3 | 10⁻¹⁰ | N₂O⁺ 1 s |
| -3 | 10⁻¹⁰ | N₂O⁺ 5 s |
| -2 | 10⁻⁸  | O₂⁺ 1 s |
| -2 | 10⁻⁸  | N₂O⁺ 1 s |
| -2 | 10⁻⁸  | N₂O⁺ 5 s |
| -1 | 10⁻⁶  | O₂⁺ 1 s |
| -1 | 10⁻⁶  | N₂O⁺ 1 s |
| -1 | 10⁻⁶  | N₂O⁺ 5 s |
| 0  | 10⁻⁵  | O₂⁺ 1 s |
| 0  | 10⁻⁵  | N₂O⁺ 1 s |
| 0  | 10⁻⁵  | N₂O⁺ 5 s |
| 1  | 10⁻⁴  | O₂⁺ 1 s |
| 1  | 10⁻⁴  | N₂O⁺ 1 s |
| 1  | 10⁻⁴  | N₂O⁺ 5 s |
| 2  | 10⁻⁴  | O₂⁺ 1 s |
| 2  | 10⁻⁴  | N₂O⁺ 1 s |
| 2  | 10⁻⁴  | N₂O⁺ 5 s |
| 3  | 10⁻⁴  | O₂⁺ 1 s |
| 3  | 10⁻⁴  | N₂O⁺ 1 s |
| 3  | 10⁻⁴  | N₂O⁺ 5 s |
| 4  | 10⁻⁴  | O₂⁺ 1 s |
| 4  | 10⁻⁴  | N₂O⁺ 1 s |
| 4  | 10⁻³  | N₂O⁺ 5 s |

| Binding energy (eV) | Intensity (a.u.) |
|---|---|
|534 | 70.5% |
|532 | 22.5% |
|530 | 7.0% |

| Binding Energy (eV) | Normalized Intensity | Condition        | Remark |
|-------------------:|---------------------:|------------------|--------|
| 408 | 0.0 | All O₂⁺ 1 s | — |
| 408 | 0.0 | All N₂O⁺ 1 s | — |
| 408 | 0.1 | All N₂O⁺ 5 s | — |
| 404 | 0.0 | All O₂⁺ 1 s | — |
| 404 | 0.1 | All N₂O⁺ 1 s | — |
| 404 | 0.1 | All N₂O⁺ 5 s | — |
| 400 | 0.2 | All O₂⁺ 1 s | — |
| 400 | 0.2 | All N₂O⁺ 1 s | — |
| 400 | 0.2 | All N₂O⁺ 5 s | — |
| 396 | 1.0 | All O₂⁺ 1 s | Peak |
| 396 | 1.0 | All N₂O⁺ 1 s | Peak |
| 396 | 1.0 | All N₂O⁺ 5 s | Peak |
| 392 | 0.2 | All O₂⁺ 1 s | — |
| 392 | 0.2 | All N₂O⁺ 1 s | — |
| 392 | 0.2 | All N₂O⁺ 5 s | — |

Answer: Metal–nitrogen (Ga–N or M–N) bonds. This indicates successful incorporation of nitrogen into the oxide lattice via anion substitution, which helps passivate oxygen vacancies and improve device stability.

Answer: Decrease. The relative area of the O𝑑𝑒𝑓 peak decreases from 22.5% in the O₂ sample to 19.9% in the N₂O (5 s) sample, indicating a reduction in oxygen vacancy concentration.

Answer: The curves shift to the right, indicating that N2O plasma treatment increases the turn-on voltage compared to the O2 plasma reference, likely due to a reduction in carrier concentration or modification of interface traps.

Answer: Lower ΔV𝑇𝐻. The N₂O-treated devices (Red/Blue) exhibit significantly smaller threshold voltage shifts under stress compared to the O₂ reference (Black), which is critical for maintaining stable current driving in OLED pixels.

icdar2026-competition-data/train/atomic-layer-deposition/simulation-usecase/19/Dong-Gyu Kim et al.pdf


Figure 7. PBTS stability of the selective $\mathrm { N } _ { 2 } \mathrm { O }$ applied IGZO TFTs. (a) Transfer curves as a function of PBTS time of the reference and selectivel $\mathrm { N } _ { 2 } \mathrm { O }$ plasma applied IGZO TFTs. (b) Degree of $\mathrm { V } _ { \mathrm { T H } }$ shift after 10000 s of PBTS time for IGZO TFTs.

Transfer characteristics (drain current versus gate voltage) of IGZO TFTs under positive bias temperature stress (PBTS) for devices where individual cation layers (In, Ga, or Zn) are selectively treated with N₂O plasma, showing different degrees of threshold voltage shift.

Summary of the corresponding threshold voltage shifts (ΔV_TH), demonstrating that N₂O treatment during the gallium oxide sub-cycle significantly improves stability (~50% reduction), while treatment during the indium oxide sub-cycle degrades stability (≈68% increase in ΔV_TH).

| Gate voltage (V) | Pristine (A) | 100 s (A) | 500 s (A) | 1500 s (A) | 2500 s (A) | 3500 s (A) | 3600 s (A) | 7200 s (A) | 10000 s (A) |
|------------------|--------------|-----------|-----------|------------|------------|------------|------------|------------|-------------|
| -6               | 1e-12        | 1e-12     | 1e-12     | 1e-12      | 1e-12      | 1e-12      | 1e-12      | 1e-12      | 1e-12       |
| -4               | 1e-11        | 1e-11     | 1e-11     | 1e-11      | 1e-11      | 1e-11      | 1e-11      | 1e-11      | 1e-11       |
| -2               | 1e-10        | 1e-10     | 1e-10     | 1e-10      | 1e-10      | 1e-10      | 1e-10      | 1e-10      | 1e-10       |
| 0                | 1e-9         | 1e-9      | 1e-9      | 1e-9       | 1e-9       | 1e-9       | 1e-9       | 1e-9       | 1e-9        |
| 2                | 1e-7         | 1e-7      | 1e-7      | 1e-7       | 1e-7       | 1e-7       | 1e-7       | 1e-7       | 1e-7        |
| 4                | 1e-5         | 1e-5      | 1e-5      | 1e-5       | 1e-5       | 1e-5       | 1e-5       | 1e-5       | 1e-5        |

| Controlled cation elements | O₂ 1s (Ref) ΔV_TH (V) | N₂O 1s ΔV_TH (V) | N₂O 5s ΔV_TH (V) |
|----------------------------|-----------------------|------------------|------------------|
| Indium oxide               | ~2.4                  | ~1.6 (33% decrease) | ~1.2 (50% decrease) |
| Gallium oxide              | ~2.0                  | ~1.0 (50% decrease) | ~0.8 (60% decrease) |
| Zinc oxide                      | ~1.8                  | ~1.7 (8% decrease)  | ~1.6 (11% decrease) |

Answer: Gallium oxide. The Gallium oxide modification results in a ~50% decrease in ΔV𝑇𝐻 (improved stability), whereas the Indium oxide modification causes a ~68% increase (worsened stability) relative to the reference.

Answer: Suppression of oxygen vacancies. Gallium is a strong oxygen binder. Selective N₂O treatment during the Gallium cycle effectively reduces oxygen vacancies and defect states (which act as electron traps) without severely disrupting channel conduction, leading to the most stable device operation.

Answer: No. For the Zinc Oxide–controlled cation, increasing the N₂O exposure to 5 s significantly increases the instability, resulting in a ΔV𝑇𝐻 of +0.83 V compared to the more stable Gallium condition (+0.45 V).

Answer: Selective N₂O on Gallium Oxide. This condition yields the lowest ΔV𝑇𝐻 (+0.45 V) compared to Indium (+1.51 V) or Zinc (+0.83 V), ensuring the most stable switching performance under thermal and bias stress.


Figure 5. Growth properties as a function of surface hydroxyl density. (a) Al atoms added vs OH density. (b) Ligand/Al ratio vs surface OH concentration. Present results compared to data from Puurunen.

The scatter plot shows Al atoms added per unit area (Al/nm²) against OH surface density (OH/nm²) for the present study (blue) and Puurunen (black). Both datasets show that generally higher OH surface density corresponds to greater Al uptake.

The scatter plot displays the ligand-to-aluminum ratio versus OH surface density  for the present study (blue) and Puurunen (black). Generally, the ligand:Al ratio decreases as OH density increases.

|Study| Al atoms added, Al/nm² | OH Surface Density, OH/nm² |
|---|---|---|
|Puurunen|2.23| 1.48|
|Puurunen|2.94| 3.51|
|Puurunen|3.71| 5.49|
|Puurunen|4.43| 7.48|
|Present study|2.78| 2.17|
|Present study|3.32| 4.11|
|Present study|3.44| 4.08|
|Present study|3.62| 4.22|
|Present study|3.86| 4.33|
|Present study|3.69| 4.49|
|Present study|3.12| 4.61|
|Present study|4.06| 4.59|
|Present study|3.85| 4.72|
|Present study|3.86| 5.16|

|Study| OH Surface Density, OH/nm² |  Ligand : Aluminum Ratio |
|---|---|---|
|Puurunen|1.18| 2.39|
|Puurunen|3.40| 1.84|
|Puurunen|6.01| 1.49|
|Puurunen|8.78| 1.2|
|Present study|2.24| 1.88|
|Present study|4.06| 1.68|
|Present study|4.13| 1.58|
|Present study|4.29| 1.65|
|Present study|4.26| 1.59|
|Present study|4.47| 1.37|
|Present study|4.54| 1.55|
|Present study|4.64| 1.48|
|Present study|4.69| 1.42|
|Present study|5.14| 1.52|

Answer: Puurunen's results show a positive correlation. This conclusion is supported by the upward trend of the data points, which rises from left to right. This indicates that as the OH surface density increases (on the x-axis), the number of Al atoms added also increases (on the y-axis).

Answer: No

Answer: Puurunen's results  show a negative correlation. This is supported by the downward trend  of the data points, which descends from left to right. This indicates that as the OH surface density increases, the Ligand : Aluminum Ratio also decreases.

Answer: Pruununen’s  study covers a wider range of OH surface densities.

icdar2026-competition-data/train/atomic-layer-deposition/simulation-usecase/25/Kristopher S. Brown et al.pdf


Figure 15. Growth rate of  $\mathsf{HfO_2}$  in different circumstances versus time for the 16th-20th cycles. The thickness of a monolayer of  $\mathsf{HfO_2}$  is  $2.8\dot{A}$ . Cross shows growth rate considering all observed ALD reactions. Circle shows growth rate when direct ligand exchange during oxygen pulse is considered rather than cooperative effect. Triangle shows growth rate when migration process is switched off. [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

The scatter plot shows the relationship between simulation time and growth rate, with three different conditions represented by different markers: considering all ALD reactions (red +), cooperative effect is excluded (green circles), and when the migration process is switched off (blue triangle). Excl. cooperation gives the highest growth (~1.4–1.6 Å/cycle), incl. all is intermediate (~0.5–0.75 Å/cycle), and excl. migration is lowest (~0.12–0.22 Å/cycle).

| Simulation time (s) | Growth rate – incl. all (Å/cycle) | Growth rate – excl. cooperation (Å/cycle) | Growth rate – excl. migration (Å/cycle) |
|---|---|---|---|
| 0.0064 | 0.75 | 1.58 | 0.19 |
| 0.0068 | 0.59 | 1.45 | 0.12 |
| 0.0072 | 0.50 | 1.42 | 0.21 |
| 0.0076 | 0.50 | 1.42 | 0.22 |
| 0.0080 | 0.65 | 1.59 | 0.16 |

Answer: Excl. cooperation, Incl. all, Excl. migration

Answer: Disabling migration reduces the growth rate compared to the full model.

Answer: Migration is more important to sustain growth. The evidence is that when migration is disabled (“excl. migration”), the growth rate collapses to very low values (~0.12–0.22 Å/cycle) at every time point, far below the full model (~0.5–0.75 Å/cycle). In contrast, disabling cooperation (“excl. cooperation”) does not reduce growth.

Answer: Cooperation hinders film growth in this model. The evidence is that when cooperation is removed (“excl. cooperation”), the growth rate jumps to the highest values in the plot (~1.4–1.6 Å/cycle) across all times, well above the full model (~0.5–0.75 Å/cycle). By contrast, removing migration lowers growth (~0.12–0.22 Å/cycle), so migration is not what limits growth.

icdar2026-competition-data/train/atomic-layer-deposition/simulation-usecase/26/Mahdi Shirazi et al.pdf


Fig. 10. Surface state of the adsorbed complex  $-\mathrm{MCl}_x$  of the precursor vs. process temperature. Circles and squares correspond to experiments with  $\mathrm{ZrO_2}$  from [10] and [11], respectively; triangles correspond to  $\mathrm{HfO_2}$  experiment [6]; dashed and dashed-dotted lines correspond to the present study modeling for  $\mathrm{ZrO_2}$  and  $\mathrm{HfO_2}$ , respectively.

The scatter plot shows the relationship between temperature (T, °C) and the ratio x = Cl / Me. Data points represent experimental measurements, whereas calculations for Zr and Hf are shown with lines..

| T,°C | x = Cl / Me |
|---|---|
| 100 | 2.00 |
| 200 | 2.25 |
| 300 | 2.30 |
| 400 | 2.60 |
| 500 | 2.80 |
| 600 | 3.00 |

Answer: No the experimental value does not nicely overlap. Only the Hf experiments of J. Aarik come close, however they are still of by .25 on average.

Answer: The calculated values are in the error margins of the data points, so it could be that they overlap.

Answer: They both show an s shape, where initially there is an increase with temperature, but this saturates.

Answer: No it is not, the upper limit of the error bars is at 3.50, this would mean that out of four chlorine atoms, still more than three are present. This means that non of them reactive with the surface leading to adsorption.

icdar2026-competition-data/train/atomic-layer-deposition/simulation-usecase/28/Maxim Deminsky et al.pdf


Fig. 11. Temperature dependence of the residual chlorine concentration in the growing film; triangles are experimental points [10], and diamonds are simulation results.

The line chart shows the relationship between temperature and chlorine concentration, indicating a negative correlation where chlorine concentration decreases as temperature increases.

| Temperature, °C | Chlorine concentration, % |
|---|---|
| 200 | 2.3 |
| 250 | 1.5 |
| 300 | 1.0 |
| 350 | 0.5 |
| 400 | 0.1 |

Answer: The temperature has a huge influence on the reaction rates that occur during the ALD cycle. This can be the reason for the higher chlorine content.

Answer: XPS is a technique that can be used to determine the chlorine concentration In this technique, electrons are removed from the material by photons that give insight into the materials composition.

Answer: 1.5%

Answer: No


Fig. 6.  $\mathrm{ZrO_2}$  film mass increment as a function of the precursor source temperature. Circles and solid line are experimental [10] and modeling results at the reaction chamber temperature 290  $^\circ \mathrm{C}$ ; squares and dashed line are experimental [10] and modeling results at the reaction chamber temperature  $180^{\circ}\mathrm{C}$ .

The line chart illustrates the relationship between the mass increment and the ZrCl₄ source temperature for two different reactor temperatures. As the temperature increases, the mass increment also increases, showing a positive correlation, till there is soft-saturation for both reactor temperatures.

| ZrCl₄ source temperature, °C | Mass increment, a.u. 290|Mass increment, a.u. 180|
|---|---|---|
| 130 | 0.2 |-|
| 135 | 0.3 |-|
| 140 | 0.67 |-|
| 145 | 0.85 |0.80|
| 150 | 0.91 |1.05|
| 155 | 0.95 |1.1|
| 160 | 1.0 |1.15|
| 165 | - |1.20|

Answer: Lower temperature can lead to more ligand incorporation which in its turn leads to higher mass as Cl is heavier than oxygen.

Answer: If this difference is not high enough there can be condensation of the precursor in the reactor, whereas there is always the desire to only work with gas phase species.

Answer: For the higher source temperature ranges. This is mostly in the saturated growth regime.

Answer: 1.15 a.u.


Fig. 7.  $\mathrm{ZrO_2}$  film growth rate (average film mass and thickness increments per cycle) as a function of the process temperature: squares and circles correspond to experimental average film thicknesses and mass increments per cycle [10]. Dashed and solid lines correspond to the calculated results by the minimum and extended mechanism. The dashed area corresponds to sensitivity analysis for the extended mechanism.

The chart shows the relationship between temperature (T °C) and the thickness and mass increment per cycle, experimentally measured and calculated using minimum and extended mechanisms.

| T °C |average increment |
|---|---|
| 0 | 0.4 |
| 100 | 1.2 |
| 200 | 1.0 |
| 300 | 0.9 |
| 400 | 0.75 |
| 500 | 0.7 |
| 600 | 0.55 |

Answer: The points fall in the range of the extended model and can therefore be fitted with such a model.

Answer: There probably is a minimum temperature as the source temperature has to be lower than the processing temperature, but high enough to evaporate the precursor.

Answer: 1.2 a.u./cycle

Answer: Except for some outliers in general the model overestimates the experimental data, even when considering the error bars.


Fig. 8.  $\mathrm{HfO_2}$  film growth rate (average film mass and thickness increments per cycle) as a function of the process temperature: squares and circles correspond to experimental results [6,8]. Dashed and solid lines correspond to the calculated results by the minimum and extended mechanism. Dashed area corresponds to sensitivity analysis for the extended mechanism.

The chart shows the relationship between temperature (T, °C) and the thickness and mass increments per cycle for an experiment. The data points are compared with calculated values using minimum and extended mechanisms.

| T °C |average increment |
|---|---|
| 0 | 0.55 |
| 100 | 1.2 |
| 200 | 1.1 |
| 300 | 0.95 |
| 400 | 0.8 |
| 500 | 0.6 |
| 600 | 0.4 |

Answer: The simple model does not cover the data points, but the range that the extended model does overlap with all the data points, so the extended model is required.

Answer: 175 degrees Celcius.

Answer: The maximum temperature that the reactor can achieve, or the stability of this temperature.

Answer: Yes


Fig.6. the experimental growth rate in which deposition was carried out at  $50^{\circ}C$  substrate temperature using  $3s$  water vapor pulse (Xie et al., 2007). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of the article.)

The scatter plot illustrates the validation of a computational model for Atomic Layer Deposition (ALD) by comparing the calculated growth rates (nm/cycle) against pulse time (s)  with experimental data (measured and interpolated). The coefficient of determination is 0.85.

| Pulse Time (s) | Growth Rate (nm/cyc) | Data series |
|---|---|---|
| 0 |  0 | GR exp |
| 1 |  0.121 | GR exp |
| 2 |  0.121 | GR exp |
| 10 |  0.120 | GR exp |
| 0.0 | 0.001 | Gr exp (Interp) |
| 0.2 | 0.013 | Gr exp (Interp) |
| 0.4 | 0.033 | Gr exp (Interp) |
| 0.6 | 0.059 | Gr exp (Interp) |
| 0.8 | 0.079 | Gr exp (Interp) |
| 1.0 | 0.101 | Gr exp (Interp) |
| 1.2 | 0.108 | Gr exp (Interp) |
| 1.4 | 0.114 | Gr exp (Interp) |
| 1.6 | 0.119 | Gr exp (Interp) |
| 1.8 | 0.121 | Gr exp (Interp) |
| 2.0 | 0.120 | Gr exp (Interp) |
| 4.0 | 0.119 | Gr exp (Interp) |
| 6.0 | 0.120 | Gr exp (Interp) |
| 8.0 | 0.120 | Gr exp (Interp) |
| 10.0 | 0.120 | Gr exp (Interp) |
| 0.2 | 0.039 | Gr calc |
| 0.5 | 0.056 | Gr calc |
| 0.6 | 0.066 | Gr calc |
| 0.8 | 0.075 | Gr calc |
| 1.0 | 0.081 | Gr calc |
| 1.2 | 0.089 | Gr calc |
| 1.4 | 0.095 | Gr calc |
| 1.6 | 0.099 | Gr calc |
| 1.8 | 0.104 | Gr calc |
| 2.0 | 0.109 | Gr calc |
| 4.0 | 0.128 | Gr calc |
| 6.0 | 0.135 | Gr calc |
| 8.0 | 0.138 | Gr calc |
| 10.0 | 0.139 | Gr calc |

Answer: The transition occurs between the 2-second and 4-second pulse times. The theoretical model underestimates the growth rate at 2 s. By the 4 s mark, the model surpasses the experimental data.

Answer: The experimental data reaches saturation faster than the theoretical model .

Answer: The experimental data more closely resembles an ideal ALD process.

Answer: The theoretical model predicts that the substrate requires a pulse time of approximately 4 to 6 seconds to reach full saturation, whereas the experimental data demonstrates that saturation is actually achieved in just 1 second. Consequently, an engineer relying solely on the model would likely program the reactor to dose the precursor for longer than necessary to ensure full coverage. This discrepancy leads to waste because the excess precursor introduced after the 1-second mark cannot react with the already saturated surface and is simply purged from the system.

icdar2026-competition-data/train/atomic-layer-deposition/simulation-usecase/29/Mina Shahmohammadi et al.pdf


Fig.7. t t t references to colour in this figure legend, the reader is referred to the web version of this article.)

The scatter plot illustrates the validation of a computational model for Atomic Layer Deposition (ALD) with TDEAT by comparing the calculated growth rates (nm/cycle) against pulse time (s) with experimental data (measured and interpolated). The coefficient of determination is 0.99, which indicates a strong correlation.

| Pulse Time (s) | Growth Rate (nm/cyc) | Data series |
| --- | --- | --- |
| 0,0 | 0,000 | Gr exp |
| 1,0 | 0,023 | Gr exp |
| 2,0 | 0,040 | Gr exp |
| 4,0 | 0,040 | Gr exp |
| 0,0 | 0,000 | Gr exp (interpolated) |
| 0,4 | 0,010 | Gr exp (interpolated) |
| 0,8 | 0,020 | Gr exp (interpolated) |
| 1,0 | 0,023 | Gr exp (interpolated) |
| 1,4 | 0,027 | Gr exp (interpolated) |
| 1,8 | 0,032 | Gr exp (interpolated) |
| 2,0 | 0,033 | Gr exp (interpolated) |
| 2,4 | 0,035 | Gr exp (interpolated) |
| 2,8 | 0,038 | Gr exp (interpolated) |
| 3,0 | 0,038 | Gr exp (interpolated) |
| 3,4 | 0,039 | Gr exp (interpolated) |
| 3,8 | 0,040 | Gr exp (interpolated) |
| 4,0 | 0,040 | Gr exp (interpolated) |
| 0,4 | 0,014 | Gr calc |
| 0,8 | 0,020 | Gr calc |
| 1,0 | 0,023 | Gr calc |
| 1,4 | 0,028 | Gr calc |
| 1,8 | 0,030 | Gr calc |
| 2,0 | 0,032 | Gr calc |
| 2,4 | 0,034 | Gr calc |
| 2,8 | 0,036 | Gr calc |
| 3,0 | 0,037 | Gr calc |
| 3,4 | 0,039 | Gr calc |
| 3,8 | 0,041 | Gr calc |
| 4,0 | 0,041 | Gr calc |

Answer: The graph displays an R² value of 0.99. It implies an excellent statistical fit.  This value means that the theoretical model explains 99% of the variance in the experimental data and predicts the growth rate with very high accuracy .

Answer: The data point at 2 seconds.

Answer: No. At 0.5 seconds, the growth rate is only about ~0.01 nm/cycle. It is below the saturation level of ~0.04 nm/cyc. This indicates the surface is not fully covered, which would lead to poor film quality.

Answer: At 2s.


Fig.8. of the references to colour in this figure legend, the reader is referred to the web version of this article.)

The scatter plot illustrates the validation of a computational model for Atomic Layer Deposition (ALD) with TDEAH by comparing the calculated growth rates (nm/cycle) against pulse time (s) with experimental data. The coefficient of determination is 0.93, which indicates a strong correlation.

| Pulse Time (s) | Growth Rate (nm/cyc) | Data series |
| --- | --- | --- |
| 0,0 | 0,000 | Gr exp |
| 1,0 | 0,039 | Gr exp |
| 2,0 | 0,088 | Gr exp |
| 3,0 | 0,115 | Gr exp |
| 4,0 | 0,121 | Gr exp |
| 5,9 | 0,133 | Gr exp |
| 8,0 | 0,145 | Gr exp |
| 12,0 | 0,141 | Gr exp |
| 1,0 | 0,064 | Gr calc |
| 2,0 | 0,079 | Gr calc |
| 3,0 | 0,094 | Gr calc |
| 4,0 | 0,109 | Gr calc |
| 6,0 | 0,125 | Gr calc |
| 8,0 | 0,134 | Gr calc |
| 12,0 | 0,150 | Gr calc |

Answer: It generally underestimates the experimental values, except for the first and the last data points.

Answer: After ~ 8s.

Answer: No. While the experimental data shows the growth rate reaching a saturation between 8 and 12 seconds, the model predicts a continued increase in growth rate during that same interval. This discrepancy leads the model to overestimate the growth rate at 12 seconds, failing to replicate the self-limiting behavior of an ALD process.

Answer: Between 1 and 2 seconds and between 8 and 12 seconds.


Fig.9. t t references to colour in this figure legend, the reader is referred to the web version of this article.)

The scatter plot illustrates the validation of a computational model for Atomic Layer Deposition (ALD) with TEMAH by comparing the calculated growth rates (nm/cycle) against pulse time (s) with experimental data. The coefficient of determination is 0.93, which indicates a strong correlation.

| Pulse time (s) | Growth Rate (nm/cyc) | Data series |
|---|---|---|
| 0,0 | 0,000 | Gr exp |
| 0,2 | 0,030 | Gr exp |
| 0,5 | 0,066 | Gr exp |
| 0,8 | 0,070 | Gr exp |
| 1,2 | 0,071 | Gr exp |
| 1,6 | 0,072 | Gr exp |
| 2,0 | 0,072 | Gr exp |
| 3,0 | 0,074 | Gr exp |
| 4,0 | 0,074 | Gr exp |
| 0,2 | 0,044 | Gr calc |
| 0,5 | 0,054 | Gr calc |
| 0,8 | 0,061 | Gr calc |
| 1,2 | 0,067 | Gr calc |
| 1,6 | 0,069 | Gr calc |
| 2,0 | 0,071 | Gr calc |
| 3,0 | 0,073 | Gr calc |
| 4,0 | 0,075 | Gr calc |

Answer: The experimental process reaches saturation faster.

Answer: The beginning of the curve contributes the most.

Answer: After ~ 1s.

Answer: It would have no effect on the film thickness. The experimental data shows a saturation plateau; this confirms the process is self-limiting. Once the surface is saturated (which happens before 2 seconds), adding extra precursor due to an accidental fluctuation does not result in extra growth.


Fig. 16 - Time evolution of the maximum reactant mole fraction inside the reactor chamber.

The line chart plot the maximum reactant mole fraction as a function of time for TMA and water.

| Time (s) | Water Mole Fraction | TMA Mole Fraction |
|----------|----------------------|--------------------|
| 0.0      | 1.00                | 1.00              |
| 0.1      | 0.70                | 0.30              |
| 0.2      | 0.40                | 0.20              |
| 0.3      | 0.25                | 0.15              |
| 0.5      | 0.10                | 0.05              |
| 1.0      | 0.02                | 0.02              |
| 2.0      | 0.00                | 0.01              |
| 5.0      | 0.00                | 0.01             |

Answer: In order to study the purging efficiency of the reactor, the maximum reactant mole fraction inside the whole chamber was traced during the ALD pulses and purging steps of the ALD cycle, for both reactants.

Answer: The maximum mole fraction inside the chamber during the first stages of the exposure time is close to 1, as the computed reactant pulses have a high reactant composition. After the reactant pulses, the maximum mole fraction quickly drops, as the reactor purging step begins.

Answer: Yes

Answer: The results are obtained bysimulating only the transport of chemical species inside thereactor. In order to get a more reliable value for the purging time, chemical reaction kinetics and adsorption/desorption ofspecies on the reactor walls must be taken into account

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


Fig. 8 - Feeding system model results for the TMA and  $\mathbf{H}_2\mathbf{O}$  reactant pulses: a) flow rate, b) molar fraction averaged at the feeding system outlet.

The line chart shows the results from feeding system model of the flow rate of TMA and water over time, with both decreasing rapidly.

The line chart displays the averaged molar fraction of TMA and water over time for feeding system outlet, with both fractions decreasing.

| Time (s) | Flow Rate - Water (sccm) | Flow Rate - TMA (sccm) |
|----------|---------------------------|-------------------------|
| 0.00     | 700                       | 450                     |
| 0.02     | 500                       | 300                     |
| 0.05     | 200                       | 100                     |
| 0.10     | 50                        | 20                      |
| 0.15     | -                       | -        |

| Time (s) | Molar Fraction - Water | Molar Fraction - TMA |
|----------|-------------------------|-----------------------|
| 0.00     | 0.95                    | 0.90                  |
| 0.02     | 0.80                    | 0.60                  |
| 0.05     | 0.40                    | 0.20                  |
| 0.10     | 0.10                    | 0.05                  |
| 0.15    | 0.06                     |0.05                   |
| 0.2        | 0.03                  |0.02                   |
| 0.25     |     0                        | 0                   |
| 0.3       | 0                         |0                   |

Answer: The calculated TMA and H2O pulses as a function of time, in terms of flow rate  and averaged molar fraction at the feeding system outlet are shown in images a and b respectively

Answer: A higher flow rate for H2O than for TMA for the whole duration of the pulse, leading to an overall higher quantity of the delivered H2O. This is attributed to the higher vapor pressure of H2O inside the reactant bottles and to the longer opening time of the ALD valve above the H2O bottle(60 ms and 25 ms for H2O and TMA, respectively).

Answer: The reactant molar fraction is substantial during both pulses, whereas Ar represents only roughly10 wt% of the gas mixture. Notably, it is predicted that although the H2O valve opening time is longer and the quantity of H2O entering the feeding system is higher, the TMA molecules evacuate the feeding system slower, i.e the feeding system takes more time to purge. This is attributed to the slower diffusion rate in N2of TMA compared to H2O, since the molecules of the former are bigger and heavier than the latter

Answer:
1. The feeding system is purged from both reactants in 0.3 s.
2. The total calculated amounts entering the reactor are 0.63 mg for TMA and 0.408 mg for H2O.
3. The flow rate of the feeding system after the reactant pulses are 30 sccm


Fig. 9 - Outlet pressure variation vs time: model predictions vs Pirani gauge measurements.

The chart compares the outlet pressure over time for experimental data and a model.

| Time (s) | Outlet Pressure - Experiments (Torr) | Outlet Pressure - Model (Torr) |
|----------|---------------------------------------|---------------------------------|
| 0        | 0.049                                | 0.049                          |
| 5        | 0.075 (H₂O peak)                     | 0.074                          |
| 10       | 0.058 (TMA peak)                     | 0.057                          |
| 15       | 0.075 (H₂O peak)                     | 0.074                          |
| 20       | 0.049                                | 0.049                          |
| 25       | 0.075 (H₂O peak)                     | 0.074                          |
| 30       | 0.058 (TMA peak)                     | 0.057                          |
| 35       | 0.075 (H₂O peak)                     | 0.074                          |
| 40       | 0.049                                             |  0.049                        |

Answer: The predicted outlet pressure with the Pirani conversion(Pconv) variation during three ALD cycles shown in the figure is compared with the experimental measurements.

Answer: Yes

Answer: In particular, the outlet peak heights are captured and thus the dynamic response to the reactant pulses. This validates the coupling of the two CFD models

Answer: As the pressure reading given by the Pirani gauge is gas dependent, it will vary with the gas composition. The pressure reading is performed via the measurement of the gas thermal conductivity, which is inversely proportional to the molecular mass of the gas. As the gauge is calibrated for nitrogen, a gas with a higher molecular mass than N2(28 g/mol) will lead to a lower pressure reading, while a gas with a lower molecular mass will have the opposite effect


Fig. 2. Effect of substrate heat-treatment temperature on the amount of aluminum adsorbed  $\Delta c_{\mathrm{Al}}$  in the  $\mathrm{AlMe}_3$  reaction (a) with alumina (reaction at  $150^{\circ}\mathrm{C}$ :  $(\Delta \Omega)$  [21]) and (b) with silica (reaction at  $150^{\circ}\mathrm{C}$ :  $(\bigcirc)$  [20], reaction at  $250^{\circ}\mathrm{C}$ :  $(\square)$  [19]). Lines have been fitted to the experimental data; the confidence limits represent one standard deviation. Surface OH group concentrations  $c_{(\mathrm{O})\mathrm{H}}(\times , + )$  are shown for reference [20-22].

The scatter plot shows the effect of alumina heat-treatment temperature on both the aluminum adsorbed per cycle (Δc_Al, triangles) and the surface OH group concentration (c_(O)H, X markers). Both quantities decrease with increasing pretreatment temperature (200–800°C). The linear fit to Δc_Al yields a = 5.9 ± 0.2 nm⁻² and b = −0.0050 ± 0.0003, indicating that higher pretreatment temperatures reduce aluminum uptake.

The scatter plot shows analogous data for silica substrates, with Δc_Al measured at two reaction temperatures (150°C: circles; 250°C: squares) and c_(O)H shown as + markers. The fit gives a = 4.7 ± 0.3 nm⁻² and b = −0.0033 ± 0.0005. Both Δc_Al and c_(O)H decrease with heat-treatment temperature, with c_(O)H declining more steeply at higher temperatures.

| Alumina heat-treatment[°C] | ΔCAl(OH)[nm-2] |
|---|---|
| 200 | 6 |
| 400 | 5 |
| 600 | 4 |
| 800 | 2 |

| Silica heat-treatment[°C] | ΔCSi(OH)[nm-2] |
|---|---|
| 200 | 7 |
| 400 | 6 |
| 600 | 5 |
| 800 | 3 |

Answer: Both Δc_Al and c_(O)H decrease with increasing heat-treatment temperature on both alumina and silica substrates. However, c_(O)H decreases more rapidly than Δc_Al, particularly at higher temperatures. At elevated pretreatment temperatures, c_(O)H can even fall below Δc_Al, indicating that the simple model where each OH group binds one aluminum atom cannot fully explain the observed growth. This divergence suggests that AlMe₃ can also adsorb through mechanisms other than ligand exchange with OH groups, such as dissociation on oxygen bridges.

Answer: Higher heat-treatment temperatures cause dehydroxylation, where pairs of surface OH groups combine to form oxygen bridges and release water, thereby reducing the concentration of reactive OH sites available for AlMe₃ chemisorption.

Answer: Circles represent Δc_Al measured at 150°C reaction temperature, squares represent Δc_Al at 250°C reaction temperature, and + markers represent the surface OH group concentration c_(O)H.

Answer: Alumina shows higher initial aluminum uptake, with a fitted intercept of a = 5.9 ± 0.2 nm⁻² compared to a = 4.7 ± 0.3 nm⁻² for silica. This difference correlates with the higher initial OH group concentration on alumina surfaces. Additionally, alumina and silica have different surface chemistries and OH group types (isolated, bridged, hydrogen-bonded), which affect their reactivity toward AlMe₃. The steeper slope for alumina (b = −0.0050) versus silica (b = −0.0033) also indicates that alumina's aluminum uptake is more sensitive to dehydroxylation.


Fig. 3. Effect of the OH group surface concentration  $c_{(\mathrm{O})\mathrm{H}}$  on the reaction of  $\mathrm{AlMe}_3$ : (a) aluminum atoms adsorbed,  $\Delta c_{\mathrm{Al}}$ , (b) methyl groups adsorbed,  $\Delta c_{\mathrm{Me}}$ , and (c) the average  $\mathrm{Me / Al}$  ratio in the adsorbed species  $(\Delta c_{\mathrm{Me}} / \Delta c_{\mathrm{Al}})$  (data for  $\Delta c_{\mathrm{Al}}$  and  $c_{(\mathrm{O})\mathrm{H}}$  from Figs. 1 and 2; data for  $\Delta c_{\mathrm{Me}}$  from references [19-21]). In panels (a) and (b), solid lines show fits to the experimental data; the confidence limits represent 1 standard deviation. The dashed line in panels (a-c) show the results expected for the chemistry of Eq. (6) (with  $\Delta c_{\mathrm{Me}}^{\mathrm{max}} = 6.0 \mathrm{nm}^{-2}$ ).

The scatter plot shows Δc_Al (aluminum adsorbed per cycle) versus surface OH concentration c_(O)H, combining data from alumina (triangles, 80–300°C) and silica (circles 150°C, squares 250°C). The solid line is a linear fit yielding a = 1.68 ± 0.09 nm⁻² and b = 0.37 ± 0.02. The dashed line represents the theoretical prediction assuming one OH binds one Al atom (Eq. 6), which clearly fails to describe the data.

The scatter plot shows Δc_Me (methyl groups adsorbed) versus c_(O)H. The solid fit gives a = 4.9 ± 0.2 nm⁻² and b = 0.14 ± 0.06, indicating Δc_Me is nearly constant (~5 nm⁻²) regardless of OH concentration. The dashed theoretical line again fails to match observations.

The scatter plot shows the average Me/Al ratio (Δc_Me/Δc_Al) versus c_(O)H. The ratio decreases from ~3 at low c_(O)H toward ~2 at high c_(O)H. The solid curve fits the experimental trend while the dashed line shows the inadequate theoretical prediction.

| c_(O)H, nm⁻² | Δc_Al 80-300°C alumina (nm⁻²) | Δc_Al 150°C silica (nm⁻²) | Δc_Al 250°C silica (nm⁻²) |
|---|---|---|---|
| 1 | 2.1 | - | - |
| 2 | 2.4 | 2.9 | - |
| 3 | 2.8 | - | 2.7 |
| 4 | 3.2 | - | 3.0 |
| 5 | 3.5 | - | - |
| 6 | 3.9 | - | - |
| 8 | 4.6 | - | - |
| 9 | 5.0 | - | - |

| c_(O)H, nm⁻² | Δc_Me 80-300°C alumina (nm⁻²) | Δc_Me 150°C silica (nm⁻²) | Δc_Me 250°C silica (nm⁻²) |
|---|---|---|---|
| 1 | 5.0 | 5.2 | - |
| 2 | 5.2 | - | - |
| 3 | 5.5 | - | 5.7 |
| 4 | 5.6 | - | 5.5 |
| 5 | 5.8 | - | - |
| 6 | 5.9 | - | - |
| 8 | 6.0 | - | - |
| 9 | 6.1 | - | - |

| c_(O)H, nm⁻² | Δc_Me/Δc_Al 80-300°C alumina | Δc_Me/Δc_Al 150°C silica | Δc_Me/Δc_Al 250°C silica |
|---|---|---|---|
| 1 | 2.4 | 1.8 | - |
| 2 | 2.2 | - | - |
| 3 | 2.0 | - | 2.1 |
| 4 | 1.8 | - | 1.9 |
| 5 | 1.7 | - | - |
| 6 | 1.5 | - | - |
| 8 | 1.4 | - | - |
| 9 | 1.3 | - | - |

Answer: The intercept represents the amount of aluminum that would adsorb on an oxide surface with zero OH groups. Since AlMe₃ retains all three methyl ligands when no OH groups are present (Me/Al = 3), this aluminum must chemisorb through dissociation or association reactions with oxygen bridges rather than ligand exchange. Multiplying a by 3 gives ~5.0 nm⁻², which matches the observed Δc_Me at low OH concentrations, confirming internal consistency of the model.

Answer: The dashed lines represent predictions from a simplified model (Eq. 6) assuming each OH group binds exactly one aluminum atom via ligand exchange. The systematic deviation from experimental data proves this simple one-to-one correspondence is invalid for the AlMe₃/H₂O ALD process.

Answer: At low c_(O)H, AlMe₃ adsorbs primarily through dissociation or association on oxygen bridges, retaining all three methyl groups (Me/Al ≈ 3). As c_(O)H increases, more aluminum atoms attach via ligand exchange reactions that release methyl groups as methane. Each OH group that reacts removes one methyl ligand, so the average number of methyl groups per adsorbed aluminum decreases. At high OH concentrations, the Me/Al ratio approaches 2, indicating that on average one methyl is released per adsorbed aluminum.

Answer: Approximately 5 to 6 methyl groups per nm² are adsorbed at saturation. This value is nearly constant because steric hindrance by the bulky methyl groups, not OH availability, determines the saturation coverage.


Figure 2. (a) WCA values as a function of ALD  $\mathrm{Al}_2\mathrm{O}_3$  cycles with a general recipe at  $150^{\circ}\mathrm{C}$  for four different substrates: ODPA/Ti, Ti,  $\mathrm{SiO}_2$ , and HF-treated Si. The insets show WCA images captured using a three-times-magnified optical lens in a WCA analyzer. (b) Al 2p XPS spectra of  $\mathrm{Al}_2\mathrm{O}_3$  on ODPA/Ti for 50, 70, and 100 ALD cycles.

The WCA plot shows distinct initial contact angles for the four substrates, followed by progressive convergence with increasing ALD cycles. ODPA/Ti maintains a high angle through early cycles before dropping sharply between 100 and 150 cycles. HF-treated Si reaches its final angle by ~25 cycles, while SiO₂ and Ti follow nearly identical trajectories after that point. By 150 cycles, all surfaces converge near ~45°.

The Al 2p spectra display a common peak centered near ~75 eV for all cycle counts. Peak intensity increases monotonically from 50 to 100 cycles, while peak position and width remain essentially unchanged. The spectra therefore differ primarily in amplitude rather than energy shift.

| ALD cycles | ODPA/Ti (deg) | HF-treated Si (deg) | SiO₂ (deg) | Ti (deg) |
|-----------|----------------|----------------------|------------|----------|
| 0         | ~110           | ~90                  | ~70        | ~60      |
| 25        | ~110           | ~45                  | ~45        | ~45      |
| 50        | ~105           | ~45                  | ~45        | ~45      |
| 100       | ~90            | ~45                  | ~45        | ~45      |
| 150       | ~45            | ~45                  | ~45        | ~45      |

| Binding energy (eV) | Relative intensity trend |
|---------------------|--------------------------|
| ~73.0               | Very low                 |
| ~74.0               | Rising                   |
| ~75.0               | Maximum (100 > 70 > 50)  |
| ~76.0               | Decreasing               |
| ~77.0               | Very low                 |

Answer: Each substrate begins with a distinct contact-angle value, but the curves progressively collapse toward a common range as ALD cycles increase. ODPA/Ti remains hydrophobic through early cycles before declining sharply, whereas HF-treated Si reaches its final angle quickly and remains constant. SiO₂ and Ti show nearly identical behavior after the initial cycles. Overall, increasing ALD cycles reduce substrate-dependent differences.

Answer: ODPA/Ti.

Answer:
-All spectra peak near ~75 eV.
, -Peak intensity increases from 50 to 100 cycles.
, -Peak widths and positions remain nearly unchanged.
, -Differences are dominated by amplitude, not energy shift.

Answer: The stable peak position indicates that the chemical state of aluminum remains consistent as the film grows. Increasing cycle count primarily increases signal intensity rather than altering bonding environment. This suggests uniform film growth rather than a change in aluminum coordination or oxidation state.

icdar2026-competition-data/train/atomic-layer-deposition/simulation-usecase/36/Seunggi Seo et al.pdf


Figure 5. WCA values as a function of the number of ALD  $\mathrm{Al}_2\mathrm{O}_3$  cycles for up to 150 cycles (a) using an ALD process with decreased TMA pressure (from 8.9 to 1.3 Torr) and (b) using a decreased TMA pressure process with increased Ar purging (TMA injection pressure decreased from 8.9 to 1.3 Torr) and no purging pressure increased from 1.3 to 8.9 Torr) over 370 cycles at  $150^{\circ}\mathrm{C}$  for three different substrates, ODPA/Ti, Ti, and  $\mathrm{SiO}_2$  and HF-treated Si. The insets show WCA images captured using a  $3\times$  magnified optical lens in a WCA analyzer.

Under reduced TMA pressure, HF-treated Si, SiO₂, and Ti exhibit a rapid decrease in WCA to ~45° within the first 25 ALD cycles, after which their values remain constant. ODPA/Ti behaves differently, maintaining a high contact angle (~110°) through early cycles and decreasing gradually to ~90° by 150 cycles.

With reduced TMA pressure and increased Ar purge, the same three substrates again converge rapidly to ~45° and remain stable over the entire 370-cycle range. ODPA/Ti shows only a slight decrease from ~110° to ~105°, indicating strong resistance to long-term hydrophilization under these conditions.

| ALD cycles | ODPA/Ti (deg) | HF-treated Si (deg) | SiO₂ (deg) | Ti (deg) |
|-----------|----------------|----------------------|------------|----------|
| 0         | ~110           | ~90                  | ~70        | ~60      |
| 25        | ~110           | ~45                  | ~45        | ~45      |
| 50        | ~110           | ~45                  | ~45        | ~45      |
| 100       | ~105           | ~45                  | ~45        | ~45      |
| 150       | ~90            | ~45                  | ~45        | ~45      |

| ALD cycles | ODPA/Ti (deg) | HF-treated Si (deg) | SiO₂ (deg) | Ti (deg) |
|-----------|----------------|----------------------|------------|----------|
| 0         | ~110           | ~90                  | ~70        | ~60      |
| 25        | ~110           | ~45                  | ~45        | ~45      |
| 150       | ~105           | ~45                  | ~45        | ~45      |
| 370       | ~105           | ~45                  | ~45        | ~45      |

Answer:
-HF-treated Si stabilizes near ~45°.
-SiO₂ and Ti follow nearly identical trajectories to ~45°.
-ODPA/Ti remains significantly higher than the others.
-The separation between ODPA/Ti and the remaining substrates persists over subsequent cycles.

Answer: A fast, stable WCA response reduces uncertainty in downstream wet processing, adhesion, or interfacial layer formation. If most substrates quickly reach a consistent wetting state, process tuning becomes simpler. The persistent exception (ODPA/Ti) also highlights where selectivity might be achievable.

Answer: The curves indicate those substrates still transition rapidly to ~45° and then remain stable, even with the modified purge scheme. That suggests the early surface change is robust to this process adjustment once the low-WCA state is reached. The main visible effect is that the long-cycle behavior remains steady rather than drifting.

Answer: ODPA/Ti.