Fig. 2 XRR measurements of the two selected films with fitted simulations giving thicknesses of 32 and  $23~\mathrm{nm}$  and surface roughnesses of 0.7 and  $0.6 \mathrm{nm}$  for lanthanum titanate films with  $33\%$  and  $25\%$  of  $\mathrm{TiO_2}$  subcycles, respectively.

The chart displays X-ray Reflectivity (XRR) measurements plotted as the logarithm of intensity (in arbitrary units) versus the incident angle (in degrees). It compares the experimental reflectivity profiles against theoretical simulations for two lanthanum titanate films deposited with 33% and 25% TiO2 sub-cycles.

| Angle (°) | Log(intensity) (a.u.): 33% TiO2 sub-cycles | Log(intensity) (a.u.): Simulation for 33% TiO2 sub-cycles | Log(intensity) (a.u.):25 % TiO2 sub-cycles |Log(intensity) (a.u.): Simulation for 25% TiO2 sub-cycles |
|---|---|---|---|---|
| 0.0 | 16096 | 100000 | 1517 | 8284 |
| 0.5 | 36248 | 69142 | 3233 | 5419 |
| 1.0 | 974 | 974 | 110 | 110 |
| 1.5 | 154 | 154 | 41 | 41 |
| 2.0 | 34 | 34 | 3 | 3 |
| 2.5 | 42 | 42 | 1 | 1 |

Answer: The films are rather smooth (the presence of Kiessig fringes reveals small roughness).

Answer: The film deposited with 33% TiO2 sub-cycles is thicker (as indicated by more frequent Kiessig fringes).

Answer: The simulation deviates most when the beam is oriented closest to 90 degrees relative to the surface normal. This corresponds to 0.0 - 0.5 degrees on the X-axis. In this region, the simulations overestimate the results.  For angles higher than 0.5, the predicted values nearly perfectly align with the experimental ones.

Answer: Less than 1.0 (approx. 0.5).


Fig. 6 XPS (a) C 1s, (b) Li 1s and (c) O 1s spectra for  $\mathrm{Li}_{2}\mathrm{CO}_{3}$  grown by thermal ALD at  $150^{\circ}\mathrm{C}$ . The measured spectra (black line) and fitted peaks (blue and red) are plotted together. The obtained  $\mathrm{Li}_{2}\mathrm{CO}_{3}$  stoichiometry is  $33.0\mathrm{at\%}$  Li,  $17.7\mathrm{at\%}$  C and  $49.3\mathrm{at\%}$  O.

The figure shows the intensity of C 1s binding energy peaks at various energies

The figure displays the intensity of Li 1s binding energy peaks at various energies

The figure illustrates the intensity of O 1s binding energy peaks at various energies

| Component | Binding Energy (eV) |
|-----------|----------------------|
| Li₂CO₃    | ~290                |
| C=O       | ~288                |
| C–O       | ~286                |
| C–C       | ~284.5              |

| Component | Binding Energy (eV) |
|-----------|----------------------|
| Li₂CO₃    | ~55.5               |

| Component | Binding Energy (eV) |
|-----------|----------------------|
| Li₂CO₃    | ~532                |

Answer: No

Answer:
The binding energy scale was calibrated by using the hydrocarbon contamination C 1s peak at 285.0 eV. As expected, the C 1s spectrum shows a main peak at 290.1 eV assigned to the carbonate environment in Li2CO3. The other peaks fitted with a red line are associated with
adventitious carbon on the sample surface

Answer:
The O 1s spectrum consists of a peak with a maximum at 531.8 eV. The shape of the peak is slightly asymmetric. To visualize the asymmetry a second peak is fitted to the data. The asymmetry can be explained by the crystallographic structure of Li2CO3 in which two oxygen atoms have an identical environment,
but the third oxygen has a different environment of surrounding atoms

Answer:
The obtained stoichiometry for this flm was:
1. 33.0 at% lithium
2.  17.7 at% carbon
3. 49.3 at% oxygen
corresponding to stoichiometric Li2CO3


Figure 4. (a) In situ FTIR spectra acquired after 5, 10, 15, 20, 25, and 30 complete TMGa-O₃ ALD cycles at  $350^{\circ}\mathrm{C}$  referenced to the initial substrate spectrum. (b) Integrated absorbance of spectra in Figure 4a over the range  $500 - 800 \mathrm{cm}^{-1}$  versus the number of TMGa-O₃ ALD cycles.

In situ FTIR spectra acquired after 5, 10, 15, 20, 25, and 30 complete TMGa-O3 ALD cycles at 350 °C referenced to the initial substrate spectrum.

Integrated absorbance of spectra in Figure 4a over the range 500−800 cm−1 versus the number of TMGa-O3 ALD cycles.

| Wavenumber (cm⁻¹) | Absorbance 5 Cycles | Absorbance 10 Cycles | Absorbance 15 Cycles | Absorbance 20 Cycles | Absorbance 25 Cycles | Absorbance 30 Cycles |
|-------------------|------------------------|-------------------------|--------------------------|--------------------------|--------------------------|--------------------------|
| 1000              | 0.02                   | 0.03                    | 0.03                     | 0.04                     | 0.04                     | 0.05                     |
| 900               | 0.03                   | 0.05                    | 0.07                     | 0.08                     | 0.10                     | 0.12                     |
| 800               | 0.06                   | 0.10                    | 0.15                     | 0.20                     | 0.25                     | 0.30                     |
| 700               | 0.10                   | 0.18                    | 0.25                     | 0.32                     | 0.38                     | 0.45                     |
| 600               | 0.09                   | 0.20                    | 0.27                     | 0.35                     | 0.42                     | 0.48                     |
| 500               | 0.05                   | 0.12                    | 0.20                     | 0.28                     | 0.34                     | 0.40                     |

| ALD cycles | Integrated absorbance |
|---|---|
| 5 | 25 |
| 10 | 50 |
| 15 | 75 |
| 20 | 90 |
| 25 | 115 |
| 30 | 130 |

Answer: The 800–500 cm⁻¹ region was used, where the bulk Ga₂O₃ vibrational modes are expected to appear.

Answer: The absorbance increases with an increasing number of Ga₂O₃ ALD cycles, indicating progressive film growth.

Answer: SiO₂ nanopowder.

Answer: It indicates a layer-by-layer growth behavior of Ga₂O₃.

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-deposition/experimental-usecase/23/David J. Comstock et al.pdf


Figure 9, the as-deposited films were amorphous and exhibited no observable diffraction peaks, which is similar to ALD  $\mathrm{Ga}_2\mathrm{O}_3$

The chart displays XRD measurements from two 800 Å Ga2O3 films, with (a) as-deposited at 350 °C and (b) annealed at 900 °C for 20 minutes under Ar.

| Sample | 2θ (degrees) |
|---|---|
| As-deposited |  |
| Annealed at 900 °C | Peaks at 31, 32, 38, 39, 50, 60 |

Answer: 900 °C.

Answer: 800 Å

Answer: 20 minutes under argon atmosphere.

Answer: The as-deposited film (a) shows no signals in the XRD measurements, whilst the annealed film (b) does show clear peaks/signals. This means that the annealing caused the amorphous as-deposited film to crystallize. The authors have determined the crystallinity of the film to be β-Ga2O3.


Figure 4. XPS core energy spectra for (a) titanium  $2\mathrm{p}$  orbital and (b) oxygen 1s orbital.

The spectral chart shows high-resolution XPS spectra of a titanium oxide film.displays the Ti 2p spin-orbit doublet with Ti 2p₃/₂ at ~459.0 eV and Ti 2p₁/₂ at ~464.7 eV (Δ ≈ 5.7 eV), confirming titanium in the fully oxidized Ti⁴⁺ state (TiO₂).

The spectral chart  shows an O 1s peak at ~530.5 eV from lattice oxygen, with a higher-binding-energy shoulder (~532 eV) attributed to surface hydroxyl groups or adsorbed species.

| Binding Energy (eV) | Intensity (10³ counts/s) | Condition         | Remark          |
|-------------------:|--------------------:|-------------------|-----------------|
| 454                | 0.49                | Ti 2p measured    |                 |
| 454                | 0.49                | Background        |                 |
| 455                | 0.55                | Ti 2p measured    |                 |
| 455                | 0.55                | Background        |                 |
| 456                | 0.60                | Ti 2p measured    |                 |
| 456                | 0.60                | Background        |                 |
| 457                | 0.71                | Ti 2p measured    |                 |
| 457                | 0.49                | Background        |                 |
| 458                | 1.61                | Ti 2p measured    |                 |
| 458                | 0.49                | Background        |                 |
| 459                | 17.23               | Ti 2p measured    | Primary peak    |
| 459                | 0.91                | Background        |                 |
| 460                | 8.48                | Ti 2p measured    |                 |
| 460                | 1.34                | Background        |                 |
| 461                | 2.08                | Ti 2p measured    |                 |
| 461                | 1.50                | Background        |                 |
| 462                | 1.76                | Ti 2p measured    |                 |
| 462                | 1.50                | Background        |                 |
| 463                | 2.13                | Ti 2p measured    |                 |
| 463                | 1.50                | Background        |                 |
| 464                | 3.77                | Ti 2p measured    |                 |
| 464                | 1.55                | Background        |                 |
| 465                | 6.20                | Ti 2p measured    | Secondary peak  |
| 465                | 1.76                | Background        |                 |
| 466                | 4.04                | Ti 2p measured    |                 |
| 466                | 1.87                | Background        |                 |
| 467                | 2.45                | Ti 2p measured    |                 |
| 467                | 2.03                | Background        |                 |
| 468                | 2.13                | Ti 2p measured    |                 |
| 468                | 2.03                | Background        |                 |
| 469                | 2.03                | Ti 2p measured    |                 |
| 469                |                     | Background        |                 |
| 470                | 2.24                | Ti 2p measured    |                 |
| 470                |                     | Background        |                 |

| Binding Energy (eV) | Intensity (10³ counts/s) | Condition        | Remark        |
|-------------------:|--------------------:|------------------|---------------|
| 525                | 2.26                | O 1s measured   |               |
| 525                | 2.26                | O 1s TiOx       |               |
| 525                | 2.26                | O 1s            |               |
| 525                |                     | Background      |               |
| 526                | 2.26                | O 1s measured   |               |
| 526                | 2.26                | O 1s TiOx       |               |
| 526                | 2.26                | O 1s            |               |
| 526                |                     | Background      |               |
| 527                | 2.26                | O 1s measured   |               |
| 527                | 2.26                | O 1s TiOx       |               |
| 527                | 2.26                | O 1s            |               |
| 527                |                     | Background      |               |
| 528                | 2.39                | O 1s measured   |               |
| 528                | 2.39                | O 1s TiOx       |               |
| 528                | 2.39                | O 1s            |               |
| 528                |                     | Background      |               |
| 529                | 2.78                | O 1s measured   |               |
| 529                | 2.71                | O 1s TiOx       |               |
| 529                | 2.45                | O 1s            |               |
| 529                | 2.39                | Background      |               |
| 530                | 22.20               | O 1s measured   | Primary peak  |
| 530                | 21.70               | O 1s TiOx       |               |
| 530                | 2.71                | O 1s            |               |
| 530                | 2.45                | Background      |               |
| 531                | 16.40               | O 1s measured   |               |
| 531                | 15.11               | O 1s TiOx       |               |
| 531                | 3.88                | O 1s            |               |
| 531                | 2.65                | Background      |               |
| 532                | 5.03                | O 1s measured   |               |
| 532                | 3.22                | O 1s TiOx       |               |
| 532                | 4.71                | O 1s            |               |
| 532                | 2.84                | Background      |               |
| 533                | 3.48                | O 1s measured   |               |
| 533                | 2.84                | O 1s TiOx       |               |
| 533                | 3.55                | O 1s            |               |
| 533                | 2.78                | Background      |               |
| 534                | 2.78                | O 1s measured   |               |
| 534                | 2.78                | O 1s TiOx       |               |
| 534                | 2.84                | O 1s            |               |
| 534                | 2.71                | Background      |               |
| 535                | 2.90                | O 1s measured   |               |
| 535                | 2.90                | O 1s TiOx       |               |
| 535                |                     | O 1s            |               |
| 535                |                     | Background      |               |
| 536                | 3.16                | O 1s measured   |               |
| 536                | 3.16                | O 1s TiOx       |               |
| 536                |                     | O 1s            |               |
| 536                |                     | Background      |               |

Answer: The binding energy at ~459 eV is characteristic of fully oxidized Ti⁴⁺ in a TiO₂ lattice. If the film were under-oxidized or metallic (Ti⁰), the Ti 2p₃/₂ peak would shift to a much lower binding energy, around 453.8–454 eV.

Answer: Annealing typically drives off loosely bound surface species (water/hydroxyle) and densifies the lattice. Therefore, the shoulder peak (~532 eV) would decrease in area, while the lattice peak (530.5 eV) would become sharper and more dominant. This would imply a more stable, stoichiometric, and dense TiO2 film with fewer surface defects.

Answer: The sharp, symmetrical peaks in panel (a) confirm the absence of Ti³⁺ (sub-oxide) states. This is important because Ti³⁺ is associated with oxygen vacancies, which act as conductive defects (n-type dopants). A film containing Ti³⁺ would show higher leakage current, whereas the purely Ti⁴⁺ film observed here ensures good electrical insulation.

Answer: The peak at ~532 eV typically corresponds to surface hydroxyl groups (Ti-OH). In ALD, these hydroxyls act as the reactive nucleation sites. Without them, the incoming precursor (like TiCl4 or TDMAT) would have no chemical handle to react with, leading to poor nucleation or no growth.


Figure 5. TOF-SIMS profiles of carbon contamination for films deposited between 235 and  $295^{\circ}\mathrm{C}$ . The deposition temperature increases along the arrow. The decrease of carbon contamination with increasing deposition temperature can be observed. The sample is divided into regions: the surface (I), the thin film region (II), the interface between the thin film and the substrate (III), and the bulk substrate (IV).

The multi line chart shows Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) depth profiles characterizing carbon contamination decreases with increasing deposition temperature (235–295 °C). Films grown at lower temperature exhibit higher carbon content, while higher temperatures promote cleaner films due to more complete ligand removal and byproduct desorption.

| Sputtering time (s) | Carbon content (counts/s) | Condition |
|-------------------:|--------------------------:|-----------|
| 0                  | 213.8                     | 235 °C    |
| 0                  | 171.8                     | 250 °C    |
| 0                  | 172.0                     | 260 °C    |
| 0                  | 172.0                     | 270 °C    |
| 0                  | 172.0                     | 285 °C    |
| 0                  | 172.0                     | 295 °C    |
| 50                 | 306.0                     | 235 °C    |
| 50                 | 259.7                     | 250 °C    |
| 50                 | 129.8                     | 260 °C    |
| 50                 | 79.2                      | 270 °C    |
| 50                 | 41.6                      | 285 °C    |
| 50                 | 20.8                      | 295 °C    |
| 100                | 440.2                     | 235 °C    |
| 100                | 369.2                     | 250 °C    |
| 100                | 222.11                    | 260 °C    |
| 100                | 117.33                    | 270 °C    |
| 100                | 79.27                     | 285 °C    |
| 100                | 29.0                      | 295 °C    |
| 150                | 1301.25                   | 235 °C    |
| 150                | 923.36                    | 250 °C    |
| 150                | 574.89                    | 260 °C    |
| 150                | 189.0                     | 270 °C    |
| 150                | 113.02                    | 285 °C    |
| 150                | 54.16                     | 295 °C    |
| 200                | 612.56                    | 235 °C    |
| 200                | 507.79                    | 250 °C    |
| 200                | 453.20                    | 260 °C    |
| 200                | 516.03                    | 270 °C    |
| 200                | 465.80                    | 285 °C    |
| 200                | 318.64                    | 295 °C    |
| 250                | 511.71                    | 235 °C    |
| 250                | 381.82                    | 250 °C    |
| 250                | 343.76                    | 260 °C    |
| 250                | 306.09                    | 270 °C    |
| 250                | 238.98                    | 285 °C    |
| 250                | 217.79                    | 295 °C    |
| 300                | 427.74                    | 235 °C    |
| 300                | 343.76                    | 250 °C    |
| 300                | 301.77                    | 260 °C    |
| 300                | 255.86                    | 270 °C    |
| 300                | 222.11                    | 285 °C    |
| 300                | 176.20                    | 295 °C    |
| 350                | 348.00                    | 235 °C    |
| 350                | 276.66                    | 250 °C    |
| 350                | 243.00                    | 260 °C    |
| 350                | 217.79                    | 270 °C    |
| 350                | 192.68                    | 285 °C    |
| 350                | 138.13                    | 295 °C    |

Answer: The engineer should increase the temperature to 295°C. The peak carbon count in Region III drops from ~1350 counts/s at 235°C to ~350 counts/s at 295°C. This roughly 4x reduction confirms that operating at the upper limit of the thermal window is essential for film purity.

Answer: If the substrate is a temperature-sensitive polymer (e.g., PET or PEN) with a glass transition temperature below 250°C, operating at 295°C would melt or warp the device. In this case, the engineer must accept the higher carbon contamination of the 235°C process as the necessary trade-off to maintain mechanical integrity.

Answer: The spike in Region III suggests that during the initial cycles (nucleation), the reaction chemistry is different from the steady-state growth. The precursors likely reacted incompletely with the native substrate surface or were trapped by initial surface contaminants, creating a specific carbon-rich interfacial layer before the film quality stabilized in Region II.

Answer: The TOF-SIMS data shows significantly lower carbon content in Region II for the 285°C sample compared to the 250°C sample. Lower carbon means fewer defect sites to trap charge or facilitate conduction paths (leakage), thereby improving the dielectric's reliability and resistance to breakdown over time.


Figure 9. Portion of the RBS spectra for hafnium oxide deposited from tetrakis(ethylmethylamido)hafnium at 400 and  $450^{\circ}\mathrm{C}$ .

The spectrum plots detected counts versus energy for  400 °C and  450 °C, showing separate signals attributed to carbon from the substrate and film and nitrogen in the film.

| Energy (MeV) | 400 °C: Counts | 450 °C: Counts |
|---|---|---|
| 0.475 | 90.9 | 125.1 |
| 0.488 | 33.1 | 76.7 |
| 0.515 | 24.9 | 61.3 |
| 0.594 | 18.9 | 29.1 |
| 0.619 | 15.1 | 25.5 |
| 0.645 | 16.2 | 25.7 |
| 0.675 | 75.3 | 124.2 |

Answer: No. The visible peaks for carbon and nitrogen at 450 °C  indicate a significant contamination. A suitable ALD process window would be at lower temperatures, where impurity signals are lower.

Answer: Higher intensity of the carbon and nitrogen in film.

Answer: The counts most likely come from the oxygen signal.

Answer: No


Figure 3. (a) Core level XPS spectra for  $40~\mathrm{nm}$  LiPON films deposited under conditions of varying temperature and plasma power. By reducing the deposition temperature more nitrogen is incorporated in the layer. When increasing the plasma power, more nitrogen becomes incorporated in triply coordinated form. (b) Temperature dependence of conductivity for different LiPON deposition conditions. A clear increase in conductivity is detected by reducing the temperature and increasing the plasma power. However, saturation seems to appear from  $5\times 10^{-7}\mathrm{S / cm}$  on.

The figure shows the intensity of N 1s peaks for different plasma powers and temperatures.

The figure illustrates the conductivity (Cond) of LiPO and LiPON materials as a function of inverse temperature (1000/T).

| Binding Energy (eV) | 275 °C 100 W | 275 °C 200 W | 275 °C 300 W | 100 °C 100 W |
| --- | --- |--- | --- | --- |
| 408 | - | - | - | - |
| 406 | - | - | - | - |
| 404 | - | - | - | - |
| 402 | - | - | - | - |
| 400 | - | - | - | - |
| 398 | peak at 399 eV | -  | peak at 399 eV  | peak at 399 eV  |
| 396 | peak at 397 eV  | peak at 397 eV | peak at 397 eV | peak at 397 eV |
| 394 | - | - | - | - |

| Cond (S/cm) | LiPO 275C | LiPON 275C 100 W | LiPON 275C 300 W | LiPON 200C 100 W | LiPON 100C 100 W |
| --- | --- | --- | --- | --- | --- |
| 2.9 | 10^-8 | 10^-7 | 10^-5 | 10^-5 | 10^-5 |
| 3.0 | 10^-9 | 10^-7 | 10^-6 | 10^-5 | 10^-5 |
| 3.1 | 10^-9 | 10^-8 | 10^-6 | 10^-5 | 10^-6 |
| 3.2 | 10^-10 | 10^-8 | 10^-6 | 10^-6 | 10^-6 |
| 3.3 | 10^-10 | 10^-8 | 10^-7 | 10^-6 | 10^-6 |

Answer: 275 °C and 100 °C, and plasma power of 100 W, 200 W and 300 W.

Answer: The 100 °C, 100 W sample exhibits more intense peaks, as well as a shoulder related to the presence of other N species.

Answer: Conductivity decreases for all the samples, as the 1000/T value increases.

Answer: Adding N2 plasma increases the conductivity of the samples.


FiG. 3. (Color online) (a) Emission spectrum from a steady-state  $\mathrm{O}_2$  plasma and a spectrum of an  $\mathrm{O}_2$  plasma exposure during a plasma-assisted ALD cycle of  $\mathrm{Al}_2\mathrm{O}_3$ . The latter spectrum was recorded after an  $\mathrm{Al(CH}_3\mathrm{)}_3$  dosing step during the first  $200~\mathrm{ms}$  of plasma exposure, whereas the steady-state  $\mathrm{O}_2$  plasma spectrum was recorded well after the plasma half-reaction reached saturation. (b) Time-resolved intensities of emission lines related to plasma species and reaction products after an  $\mathrm{Al(CH}_3\mathrm{)}_3$  dose had preceded. The plasma was ignited at time  $t = \sim 0.5 \mathrm{s}$ .

The figure shows OES spectra of an O2 plasma in saturation and shortly after TMA dosing in an ALD cycle.

The figure displays the intensity of O, H, O2+, CO, and OH over time, where the plasma is struck after a TMA dose.

| Wavelength (nm) | Intensity (a.u.) O2 plasma |Intensity (a.u.) O2 plasma after ALD cycle |
|---|---|---|
| 260-350 | - | OH range |
| 350-720 | - | CO range |
| 560 | O2+ peak |O2+ peak |
| 610 | - | H peak |
| 780 | O peak |O peak |

| Time (s) | Intensity (a.u.)  O |Intensity (a.u.)  H |Intensity (a.u.)  O2+ |Intensity (a.u.)  CO |Intensity (a.u.)  OH |
|---|---|---|---|---|---|
| 0 | 0 |0 | 0 |0 | 0 |
| 1 | 400 |400|750|750|400|
| 2 | 500 |0|900|0|0|
| 3 | 500 |0|900|0|0|
| 4 | 500 |0|900|0|0|
| 5 | 500 |0|900|0|0|

Answer: The spectrum related to the plasma after the TMA dose shows a broad range of emissions. Such a range usually denoted emission from molecular species.

Answer: A hydrogen line can be found at 660 nm.

Answer: The saturated plasma exposure time is 2 s. At this time there is no more intensity measured of ligand related species.

Answer: The ligands are composed of C and H atoms.


FIG. 4. (Color online) (a) Emission spectrum from a steady-state  $\mathrm{O}_2$  plasma and a spectrum of an  $\mathrm{O}_2$  plasma exposure during a plasma-assisted ALD cycle of  $\mathrm{Ta}_2\mathrm{O}_5$ . The latter spectrum was recorded after a  $\mathrm{Ta}[\mathrm{N}(\mathrm{CH}_3)_2]_5$  dosing step during the first  $200~\mathrm{ms}$  of plasma exposure. (b) Time-resolved intensities of emission lines of plasma species and reaction products after a  $\mathrm{Ta}[\mathrm{N}(\mathrm{CH}_3)_2]_5$  dose had preceded. The plasma was ignited at time  $t = \sim 0.5\mathrm{s}$ .

The figure displays a spectral intensity profile against wavelength, of an O2 plasma in saturation and shortly after a precursor dose.

The figure shows the time-dependent intensity changes of specific molecular emissions (O, H, CO, CN) over time.

| Wavelength (nm) | Intensity (a.u.) O2 plasma |Intensity (a.u.) O2 plasma after ALD cycle |
|---|---|---|
| 360-400 | - | CN range |
| 400-750 | - | CO range |
| 660 | - | H alpha peak |
| 780 | O peak |O peak |

| Time (s) | Intensity (a.u.) O |Intensity (a.u.) H |Intensity (a.u.) CO |Intensity (a.u.) CN |
|----------|------------------|----------|----------|------------------|
| 0        | 0     |0     |0     |0     |
| 0.5      | 0     |0     |0     |0     |
| 1        | 200   | 200   |100|100|
| 1.5      | 250   |130|80|80|
| 2        | 260    |80|50|50|
| 2.5      | 260    |50|50|20|
| 3        | 260    |50|50|20|
| 3.5      | 260    |50|50|20|
| 4        | 260    |50|50|20|

Answer: The used plasma is made of oxygen, but the emission also shows H, C and N species, so it it likely that these come from the ligands.

Answer: Yes, there is overlap.

Answer: The intensity of the emission of species cannot be compared to others, if the goal is to determine the densities. With OES only the presence of species can be determined.

Answer: 2.5 s would be far enough in saturation.


FIG. 5. (Color online) (a) Emission spectrum from a steady-state  $\mathrm{H}_2$  plasma and a spectrum of a  $\mathrm{H}_2$  plasma exposure during a plasma-assisted ALD cycle of  $\mathrm{TaN}$ . The latter spectrum was recorded after a  $\mathrm{Ta}[\mathrm{N}(\mathrm{CH}_3)_2]_5$  dosing step during the first  $200~\mathrm{ms}$  of plasma exposure. The inset shows the emission spectra around  $388~\mathrm{nm}$  in more detail. (b) Time-resolved emission intensity at  $388~\mathrm{nm}$  during the plasma exposure step for an ALD cycle with and without  $\mathrm{Ta}[\mathrm{N}(\mathrm{CH}_3)_2]_5$  dosing step. The plasma was ignited at time  $t = \sim 0.0\mathrm{s}$ .

The figure shows a spectral intensity plot with two curves representing H2 plasma and an H2 plasma in an ALD cycle.

The figure displays a line chart comparing the intensity at 388 nm of an H2 plasma and an H2 plasma in an ALD cycle over time.

| Wavelength (nm) | Intensity (a.u.) H2 plasma|Intensity (a.u.) H2 plasma after ALD cycle|
|---|---|---|
| 388 | peak | peak |
| 500 | peaks |peaks |
| 600 | peaks |peaks |
| 660 | H peak | H peak |

| Time (s) | Intensity (a.u.) H2 plasma|Intensity (a.u.) H2 plasma after ALD cycle|
|---|---|---|
| 0 | 0 |0|
|0.5|112|87|
| 1 | 100 |87|
| 2 | 94 |87|
| 3 | 90 |87|
| 4 | 87|87|
| 5 |87|87|
| 6 |87|87|
| 7 | 87|87|
| 8 | 87|87|
| 9 | 87|87|
| 10 | 87|87|

Answer: It seems that there is major overlap between all the species present between the two plasmas, so not a lot of different species are incorporated.

Answer: The highest intensity is measured at 660 nm.

Answer: The saturation time is 4 s.

Answer: No the intensity will not go to zero if the plasma is running  there will always be the background of the peak in the H2 plasma itself.


This figure presents Raman spectra of a material subjected to increasing durations of plasma exposure at a pressure of 850 mTorr. The x-axis shows the Raman shift (cm⁻¹), while the y-axis shows normalised intensity. Characteristic vibrational modes such as B₂g and Ag are labeled, with several peaks attributable to Al₂O₃. As exposure time increases (from 5 s to 80 s), the peak intensities for key vibrational modes gradually increase, particularly for Ag modes, indicating structural evolution or surface changes in the sample. The B₂g peak near 200 cm⁻¹ remains dominant, but secondary peaks become more prominent with longer exposure times, suggesting increasing crystallinity or improved signal collection as surface chemistry changes.

| Raman shift (cm⁻¹) | Intensity @ 5 s | 9 s | 15 s | 20 s | 30 s | 45 s | 60 s | 80 s |
|--------------------|----------------|------|------|------|------|------|------|------|
| 150 (Ag)           | 0.20           | 0.22 | 0.25 | 0.28 | 0.32 | 0.35 | 0.38 | 0.40 |
| 200 (B₂g)          | 1.00           | 1.00 | 0.98 | 0.97 | 0.95 | 0.93 | 0.90 | 0.88 |
| 250 (Ag)           | 0.60           | 0.62 | 0.65 | 0.68 | 0.70 | 0.73 | 0.76 | 0.78 |
| 350 (B₂g)          | 0.45           | 0.48 | 0.50 | 0.52 | 0.55 | 0.58 | 0.60 | 0.63 |
| 500 (Al₂O₃)        | 0.20           | 0.22 | 0.23 | 0.24 | 0.26 | 0.28 | 0.30 | 0.33 |
| 750 (Al₂O₃)        | 0.10           | 0.11 | 0.12 | 0.13 | 0.14 | 0.15 | 0.16 | 0.17 |

Answer: With increasing plasma exposure time, the intensity of several vibrational peaks, particularly those associated with Ag and B₂g modes, steadily increases. This suggests that prolonged exposure enhances the structural order or surface modifications that amplify Raman-active vibrations. Notably, the B₂g peak near 200 cm⁻¹ remains consistently strong across all conditions, while other peaks such as those near 250, 350, and 500 cm⁻¹ gradually grow in intensity. This trend indicates a cumulative effect of plasma treatment on material structure, possibly linked to crystallinity or compositional changes.

Answer: B₂g

Answer: 5 s, 9 s, 15 s, 20 s, 30 s, 45 s, 60 s, 80 s

Answer: Yes

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


This Raman spectra chart illustrates the vibrational modes of materials exposed to varying oxygen flow fractions through inductively coupled plasma (ICP). The three overlaid spectra correspond to O₂ flow fractions of 0.06, 0.29, and 0.53, with key Raman-active modes labeled along the spectral axis. Peaks corresponding to B₂g and A_g modes, as well as Al₂O₃, are clearly visible and consistent across all conditions, indicating that the overall structure remains stable across varying plasma environments. Minor differences in intensity at select peaks suggest possible changes in crystallinity or defect density influenced by oxygen content during deposition or treatment

| Raman Shift (cm⁻¹) | Normalized Intensity (a.u.) |
|--------------------|-----------------------------|
| 100                | 0.05                        |
| 200                | 1.00                        |
| 300                | 0.60                        |
| 400                | 0.40                        |
| 500                | 0.55                        |
| 600                | 0.60                        |
| 700                | 0.50                        |
| 800                | 0.45                        |
| 900                | 0.50                        |
| 1000               | 0.60                        |

Answer: increasing the O₂ flow fraction from 0.06 to 0.53 does not significantly alter the positions of the Raman peaks, indicating that the chemical structure and vibrational modes remain largely consistent. However, subtle variations in peak intensities are observed. These changes suggest minor modifications in the material’s crystallinity or defect states, likely due to different oxidation conditions during treatment. For example, a higher flow fraction might reduce the presence of carbon-related defects or enhance oxide formation, subtly affecting Raman-active modes without drastically shifting peak positions.

Answer: B₂g, A_g, and Al₂O₃ modes.

Answer: O₂ flow fraction,  ICP 0.06, 0.29, 0.53

Answer: No


The figure presents Raman spectra collected at varying pressures ranging from 850 mTorr to 5000 mTorr. The spectra show multiple sharp peaks corresponding to vibrational modes such as B₁g and Ag, as well as peaks attributed to Al₂O₃. As pressure increases, the overall spectral intensity decreases slightly, and peak shapes remain consistent, indicating preserved crystalline character. These pressure-dependent spectra are used to assess the effect of processing conditions on structural order.

| Raman shift (cm⁻¹) | Intensity (a.u.) |
|---|---|
| 100 | 5000 mTorr |
| 200 | 3700 mTorr |
| 300 | 2500 mTorr |
| 400 | 1600 mTorr |
| 500 | 850 mTorr |

Answer: The Raman spectra recorded at different pressures allow the researchers to monitor changes in the material's structural order or phase. Peaks corresponding to specific vibrational modes like B₁g and Ag indicate the crystalline nature of the sample. By comparing the intensity and shape of these peaks across pressures, one can assess whether the material undergoes structural degradation or enhancement. For example, consistent peak positions and intensities suggest stable bonding environments, while changes may imply amorphisation or phase transitions due to pressure-dependent processing

Answer: Spectral inetensity decreases with increasing pressure.

Answer: Yes

Answer: Identifies vibrational modes, Detects structural changes, Enables non-destructive composition analysis, Links processing to film quality


The Raman spectra compare vibrational modes observed under inductively and capacitively coupled plasma conditions at 5000 mTorr. Notably, the capacitively coupled case (purple line) shows substantially higher intensity peaks across the full spectral range, especially at positions labeled Ag, B₁g, and Al₂O₃. These peaks are associated with specific phonon modes and bonding environments, and their enhancement under capacitively coupled conditions suggests improved crystalline ordering or a higher density of Raman-active bonds. The inductively coupled plasma yields comparatively weak Raman signals, indicating either a more amorphous structure or a lower scattering cross-section in this condition.

| Raman shift (cm⁻¹) | Intensity - Inductive (a.u.) | Intensity - Capacitive (a.u.) |
|-------------------|------------------------------|-------------------------------|
| 100               | 0.00                         | 0.00                          |
| 150               | 0.05                         | 0.30                          |
| 200               | 0.08                         | 0.60                          |
| 250               | 0.06                         | 0.45                          |
| 300               | 0.05                         | 0.40                          |
| 350               | 0.04                         | 0.38                          |
| 400               | 0.03                         | 0.35                          |
| 450               | 0.03                         | 0.32                          |
| 500               | 0.02                         | 0.28                          |
| 600               | 0.02                         | 0.24                          |
| 700               | 0.01                         | 0.20                          |
| 800               | 0.01                         | 0.15                          |
| 900               | 0.00                         | 0.10                          |
| 1000              | 0.00                         | 0.05                          |

Answer: The capacitively coupled condition results in much stronger Raman peaks across the spectrum, particularly at positions corresponding to Ag and B₁g modes. This suggests a higher degree of crystallinity or more pronounced vibrational coherence in the material. In contrast, the inductively coupled condition shows significantly lower intensities, indicating a more amorphous or disordered structure. This comparison highlights how the type of plasma coupling directly influences material structure and vibrational activity.

Answer: The B₁g peak near 200 cm⁻¹

Answer: Yes

Answer: Higher crystallinity, Stronger phonon activity, Improved ordering, Suitable for optoelectronics


Figure 1. XPS spectra of the core level C 1s of a) pristine graphene (after transfer to  $\mathrm{SiO}_2$ ), b) graphene after a  $30\mathrm{s}\mathrm{O}_2$  plasma treatment, and c) graphene after a  $35\mathrm{s}\mathrm{H}_2$  plasma treatment at a pressure of  $50\mathrm{mTorr}$  and a plasma power of  $100\mathrm{W}$ .

The figure shows the binding energy spectrum of pristine graphene, with contributions from sp², C-O, plasmon 1, and plasmon 2.

The figure shows the binding energy spectrum of material treated with 30 seconds of O₂ plasma, with contributions from sp², sp³, C-O, and C=O.

The figure shows the binding energy spectrum of material treated with 35 seconds of H₂ plasma, with contributions from sp², sp³, C-O, and C=O.

| Binding Energy, eV | Component | Peak Intensity (normalized) |
|---|---|---|
| 284.4 | sp² | 0.88 |
| 285.5 | C-O | 0.05 |
| 286.5 | Plasmon 1 | 0.08 |
| 290.5 | Plasmon 2 | 0.02 |

| Binding Energy, eV | Component | Peak Intensity (normalized) |
|---|---|---|
| 284.4 | sp² | 0.55 |
| 285.0 | sp³ | 0.55 |
| 286.2 | C-O | 0.35 |
| 287.5 | C=O | 0.22 |

| Binding Energy, eV | Component | Peak Intensity (normalized) |
|---|---|---|
| 284.4 | sp² | 0.60 |
| 285.0 | sp³ | 0.58 |
| 286.2 | C-O | 0.38 |
| 287.5 | C=O | 0.08 |

Answer: The red curve is the fitted model of the measured XPS C 1s spectrum, constructed from the colored component peaks plus background.

Answer: After O2 plasma, the C O contribution increases, an sp3 component appears near 284.6 eV, and a C=O component appears near 289.0 eV, while the plasmon loss features seen in pristine graphene are no longer observed. After H2 plasma, the dominant change is a strong increase in sp3 bonding with a corresponding decrease in sp2 bonding, and there is also an increase in C O signal.

Answer:
H2 plasma: the spectrum shows strong sp3 formation attributed to hydrogenation, which the paper links to reversibility upon subsequent processing and annealing.

O2 plasma: the spectrum shows added oxygen containing bonding, including C=O, consistent with more permanent chemical modification and loss of plasmon features, which the paper associates with less reversible changes.

Answer: The increased sp3 contribution indicates that part of the graphene basal plane has been converted from sp2 bonding to sp3 like bonding due to plasma functionalization. For O2 plasma this coincides with oxygen containing groups such as C O and C=O, consistent with chemical modification and disruption of the pristine sp2 network. For H2 plasma, the paper attributes the sp3 increase primarily to hydrogenation, which is not directly visible as C H in XPS but is consistent with the observed sp2 to sp3 shift.

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-deposition/simulation-usecase/33/René H. J. Vervuurt et al.pdf


Figure 10. DFT/vdW-DF2 level orbital-projected density of states (DOS) per atom of free-standing and Pt(111)-contacted a) pristine graphene (PG), b) graphene oxide (GO), and c) hydrogenated graphene (SSHG). The model systems used are depicted in the inset of each graph (Pt: light gray, C: dark gray, H: white, O: red). The Fermi level of each system is set to zero (dashed vertical line). Each of the DOS curves is averaged over all atoms contributing to the individual DOS plot (e.g., C, O, and/or H, see legends for actual compositions). The gray shaded areas show the sum of contributions from the individual atomic orbital types.

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-deposition/simulation-usecase/34/René H. J. Vervuurt et al.pdf


Figure 12. GGA/vdW-DF2 level atom-projected DOS of PG and SSHG that are a) edge-contacted or b) top-contacted to Pt metal. Insets show the models used for the calculations. Contributions by atomic orbitals of C, H, and Pt are given by diverse colors. Pt–d orbital contributions are not shown for clarity. See Figure 8 caption for other details.


Figure 2. Raman spectra obtained after different plasma treatments for a)  $\mathsf{H}_{2}$  plasma treatments ranging from 2 to 8 min and b)  $\Omega_2$  plasma treatments from 1 to 5 min. The Raman spectrum of pristine graphene is also added as reference. The Raman spectra are normalized to the highest peak (D band at  $1350cm^{-1}$  or 2D band at  $2690cm^{-1}$  and are vertically offset for clarity.

The figure shows the C 1s XPS spectrum of pristine graphene, with contributions from C sp², plasmon peaks, and C-O bonds.

The figure shows the C 1s XPS spectrum of H₂ plasma treated graphene for 5 minutes, with contributions from C sp² and C sp³.

The figure shows the C 1s XPS spectrum of O₂ plasma treated graphene for 5 minutes, with contributions from C sp², C sp³, C-O, and C=O.

| Component | Binding Energy (eV) |
|---|---|
| C sp^2 | Peak at 284.5 |
| Plasmon 1 | Peak at 290 |
| Plasmon 2 | Peak at 293 |
| C-O | Peak at 286.5 |

| Component | Binding Energy (eV) |
|---|---|
| C sp^2 | Peak at 284.5 |
| C sp^3 | Peak at 285 |
| C-O | Peak at 286.5 |
| C=O | Peak at 289 |

Answer: 1) Pristine graphene, 2) H2-plasma treated graphene (5 min) and 3) O2-plasma treated graphene

Answer: This may be related to residual polymer residue in the sample or surface groups present at defects/surface sites.

Answer: About 23%.

Answer: Epoxy groups (C-O-C), hydroxyl groups (C-OH), carbonyl groups (C=O)


Fig. 3. a) X-ray diffraction patterns and b) texture coefficients of  $\mathrm{ZnO}$  films deposited with different  $\mathbb{N}_2$  bubbling flows through DEZ,  $f_{DEZ}$

This panel presents XRD patterns of ZnO films deposited by spatial ALD under different N₂ bubbling flows through DEZ. Increasing DEZ exposure leads to stronger and sharper diffraction peaks, indicating improved crystallinity, with high exposure favoring the ZnO (002) reflection, characteristic of c-axis–oriented growth.

This panel shows texture coefficients for ZnO (002), (100), (101), and (110) planes as a function of DEZ bubbling flow. The (002) texture increases markedly at higher flows, while the (101) contribution decreases, demonstrating that precursor exposure directly controls preferred crystal orientation in SALD-grown ZnO films.

Answer: The enhancement of (002)-oriented growth at higher precursor exposure improves c-axis alignment, which is beneficial for applications requiring high electron mobility, piezoelectric response, and optical transparency. Controlled texture engineering through DEZ exposure in spatial ALD enables tailoring of ZnO film properties for optoelectronic devices, sensors, and transparent conductive coatings while maintaining low-temperature processing compatibility.

Answer: Yes

Answer: Increasing dominance of the ZnO (002) diffraction peak, Reduction of the ZnO (101) texture contribution, Enhanced crystallinity with sharper diffraction peaks, Exposure-dependent orientation competition among ZnO planes

Answer: The ZnO (002) texture coefficient increases significantly at higher DEZ bubbling flows, becoming dominant above approximately 30 sccm.

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-deposition/simulation-usecase/40/Viet Huong Nguyen et al.pdf


FIG. 1. Difference infrared spectra collected at  $250^{\circ}\mathrm{C}$ , in which a decrease in absorption corresponds to the removal of species, while an increase in absorption represents the formation of species. Graph (a) shows the broad absorbance region between 800 and  $1100\mathrm{~cm}^{-1}$  corresponding to  $\mathrm{Al} - \mathrm{O}$  in the film. These spectra are taken after each  $\mathrm{SF}_6$  plasma/TMA ALE cycle and are referenced to the as-deposited  $\mathrm{Al}_2\mathrm{O}_3$  spectrum taken prior to the  $\mathrm{Al}_2\mathrm{O}_3$  cycles. Graph (b) shows the  $\mathrm{AlCH}_3$  absorbance peaks at 2900 and  $2950\mathrm{~cm}^{-1}$ . Spectra were recorded after each  $\mathrm{SF}_6$  plasma and TMA half-cycle and are referenced to the previous half-cycle.

The spectral chart shows the infrared spectra collected at 250 °C, highlighting the broad absorbance region between 800 and 1100 cm⁻¹ corresponding to Al–O vibrations in the film. These spectra were recorded after each SF₆ plasma/TMA ALE cycle and referenced to the as-deposited Al₂O₃ spectrum taken prior to the ALE cycles. The figure displays absorbance spectra across the wavenumber range for cycles 1 through 6, showing changes in absorbance at specific wavenumbers.

The spectral chart shows the Al–CH₃ absorbance peaks at 2900 and 3500 cm⁻¹. The spectra were recorded after each SF₆ plasma and TMA half-cycle and are referenced to the spectrum from the previous half-cycle. The figure compares the absorbance spectra for TMA-referenced to SF₆ plasma(blue line) and SF₆-plasma-referenced to TMA(red line)  for cycles 2, 4, and 6. Sharp absorbance peaks were observed close to 2900 to 2950 cm⁻¹.

| Wavenumber (cm⁻¹) | Cycle 1 | Cycle 2 | Cycle 3 | Cycle 4 | Cycle 5 | Cycle 6 |
|--------------------|---------|---------|---------|---------|---------|---------|
| 1000              | 0.002   | 0.0018  | 0.0016  | 0.0014  | 0.0012  | 0.0010  |
| 900               | 0.0018  | 0.0016  | 0.0014  | 0.0012  | 0.0010  | 0.0008  |
| 800               | 0.0016  | 0.0014  | 0.0012  | 0.0010  | 0.0008  | 0.0006  |

| Wavenumber (cm⁻¹) | Cycle 2 (Blue) | Cycle 2 (Red) | Cycle 4 (Blue) | Cycle 4 (Red) | Cycle 6 (Blue) | Cycle 6 (Red) |
|--------------------|-----------------|---------------|-----------------|---------------|-----------------|---------------|
| 3000              | +0.005         | -0.005        | +0.005         | -0.005        | +0.005         | -0.005        |
| 2800              | +0.004         | -0.004        | +0.004         | -0.004        | +0.004         | -0.004        |

Answer: AlCH3 symmetric and asymmetric stretching modes after SF6 plasma and TMA half cycle are studied, as a funcion of the number of cycles (2,4, and 6).

Answer: SF6 plasma.

Answer: These peaks correspond to the symmetric and asymmetric stretching modes of AlCH3 groups on the surface, which form after TMA dosing.

Answer: Yes

Answer: TMA methylates the surface of the film. It is indicated by the appearance of Al–CH₃ bands after the TMA step. These Al–CH₃ features are not present after the SF₆ plasma half-step, showing that the methyl species are not coming from the plasma exposure.

Answer: Methyl-groups.

Answer: No

Answer: At 2900 and 2950 cm^-1.

Answer: Sub-figure b shows how the absorbance has changed after SF6 exposure with a reference spectrum taken after TMA exposure (blue). The reverse is also shown in red. The baseline of these two difference spectra is marked by the dashed line. As the blue and red lines are almost perfect mirror images (relative to the dashed line), this tells us that SF6 and TMA successfully react to remove and form methyl surface groups during each half cycle respectively.

Answer:
Following TMA dosing, AlCH3 surface species are observed as indicated by an increase in the CH3 absorbance peak. These methyl groups are thought to be
formed after removal of the fluorinated surface layer, allowing excess TMA to adsorb on the bulk Al2O3. After SF6 plasma exposure, a negative CH3 peak is observed, indicating the removal of surface methyl groups, which is attributed to ligand exchange reactions between methyl groups and fluorine atoms.

Answer: At 250 °C.

Answer: Yes. The data supports this because the absorbance peaks for Cycles 2, 4, and 6 are nearly identical in intensity and shape. This repeatability implies a constant "Etch Per Cycle" (EPC) without significant drift, allowing engineers to precisely control the total etch depth simply by counting the number of cycles.

Answer: During the TMA half-cycle (blue lines), positive absorbance peaks appear at 2900 and 2950 cm⁻¹, corresponding to AlCH₃ symmetric and asymmetric stretching modes, which indicates that TMA adsorbs onto the surface and methylates it. Conversely, during the SF₆ plasma half-cycle (red lines), these same peaks appear as negative features. This indicates the removal of the methyl groups introduced in the previous step, likely replaced by fluorine atoms from the plasma radicals, consistent with a ligand-exchange mechanism.

Answer: These peaks correspond to the symmetric and asymmetric stretching vibrations of methyl groups (–CH₃) bonded to aluminum (AlCH₃ surface species).

Answer: Yes

Answer: TMA exposure introduces surface-bound methyl ligands through ligand-exchange reactions with fluorinated aluminum sites. These –CH₃ groups are transient and serve as intermediates rather than permanent surface species. The following SF₆ plasma step removes the methyl ligands, returning the C–H region to baseline and regenerating a fluorinated surface. This reversible behavior indicates clean, self-limiting surface chemistry without carbon accumulation.

Answer: It indicates complete ligand removal each cycle, preventing carbon buildup and enabling repeatable ALE behavior.

Answer: The specific wavenumber is related to -OH groups. It could indicate the adsorption of TMA on these groups.

Answer: The SF6 plasma removes surface methyl groups resulting in a decrease of the AlCH3 peaks due to ligand exchange reactions with fluorine atoms, Formation of Al–F bonds and surface fluorination further suppress Al–CH₃ related vibrational features in the FTIR spectra.

Answer: 6 cycles

Answer: The Al-O absorbance band decreses with increasing the number of cycles.

Answer: Al-O absorbance decreases for increasing cycle number indicating that there is less Al2O3, meaning there is etching.

Answer: It seems that the wavenumber range around 850 cm-1 does not have the same fluctuation each cycle, indicating that there is a difference.

Answer: Yes, this could be as not every vibrations is as likely to occur, which means that differences in absorption for different wavenumbers do not have to be the same.

Answer: The Al–O absorbance decreases monotonically with increasing cycle number.

Answer: No

Answer: The absorbance of the Al–O band, located between 800 and 1100 cm⁻¹, systematically decreases with each subsequent ALE cycle, as indicated by the arrow labeled "Increasing Cycles." Since infrared absorbance in this region is proportional to the amount of Al–O bonds present, this reduction signifies the layer-by-layer removal of the Al₂O₃ film, confirming that the process is indeed etching the material.

Answer:
Initial Al₂O₃ surface (reference, 0 cycles).

SF₆ plasma converts surface Al-O to Al-F, reducing Al-O absorbance.

TMA reacts with Al-F, releasing volatile products and potentially leaving some Al-CH₃.

Repeated cycles progressively alter the near-surface oxide structure, changing the Al-O absorbance signature as seen in the growing, shifted peaks.

Answer: The shifting peak indicates a change in the local bonding environment of aluminum and oxygen. The initial Al₂O₃ has a specific crystalline or amorphous structure. The cyclic fluorination and ligand exchange likely create a modified, possibly disordered or fluorine-incorporated, oxyfluoride surface layer (AlOₓFᵧ), which has different vibrational energies than pure Al₂O₃. This maps directly to a change in the material's etch susceptibility.

Answer: The decrease in absorbance in this region maps directly to the breaking of Al–O bonds and the subsequent reduction in film thickness, confirming that bulk material is being removed layer-by-layer.

Answer: The intensity of the absorbance decreases with increasing cycles.

Answer: Yes

Answer: The absorbance decreases with the increasing number of ALE cycles, which corresponds to the removal of material after each ALE cycle.

Answer: SF6.

Answer: The Al–O band shows a progressive decrease in absorbance from cycle 1 to cycle 6. This indicates a reduction in Al–O–containing material relative to the initial film. The monotonic decline is consistent with cumulative etching of Al₂O₃ over successive cycles.

Answer: The absorbance increases with increasing cycle number, particularly in the Al–O related region, indicating progressive accumulation or modification of surface species during repeated cycles.

Answer: Wavenumber (cm⁻¹).

Answer: Yes, A decrease in absorption corresponds to the removal of species from the Al2O3 surface, such as the Al–O bonds removed during each SF6 plasma/TMA ALE cycle.

Answer: In Figure (a), spectra are referenced to the as-deposited Al2O3 film before ALE cycles. In figure (b), spectra are referenced to the previous half-cycle to highlight changes after each TMA or SF6 plasma exposure.

Answer: The Al–O related band region, The C–H stretching region

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-etching/experimental-usecase/12/Isotropic plasma atomic layer etching of Al2O3 using a fluorine containing plasma and Al(CH3)3.pdf


Figure 1. FTIR spectra during AlN ALD with TDMAA and  $\mathrm{NH}_3$  as the reactants at  $400^{\circ}\mathrm{C}$  after 40, 80, 120, and 160 ALD cycles.

The figure displays the absorbance spectra of AlN ALD samples prepared using TDMAA & NH₃ at 400°C, with varying cycles (40, 80, 120, and 160).

| Wavenumber (cm⁻¹) | 160 cycles | 120 cycles | 80 cycles | 40 cycles |
|---|---|---|---|---|
| 1400 | - | - | - | - |
| 1200 | - | - | - | - |
| 1000 | peak at 1880 cm-1 | peak at 1880 cm-1 | peak at 1880 cm-1 | peak at 1880 cm-1 |
| 800 | - | - | - | - |
| 600 | peak at 645 cm-1| peak at 645 cm-1 | peak at 645 cm-1 | peak at 645 cm-1 |
| 400 | - | - | - | - |

Answer: After 40 cycles of TDMAA and NH3, then at 80, 120 and 160.

Answer: As the number of TDMAA and NH3 increases, so does the intensity of the absorption at 645 cm-1.

Answer: After 40 cycles of TDMAA and NH3 the peak intensity is the lowest.

Answer: As the deposition cycle increases, more molecules are deposited onto the surface. Consequently, more molecules can absorb energy at different wavenumber, which increase the peak intensity.

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-etching/experimental-usecase/20/Thermal Atomic Layer Etching of Aluminum Nitride.pdf


Figure 10. XPS spectra in the Al 2p region after (a)  $\mathrm{XeF}_2$  exposure and (b)  $\mathrm{BCl}_3$  exposure during thermal AlN ALE.

The figure shows the spectral response of Al-N after XeF2 treatment, with a fitted curve overlaid. Also, Al-N bond is highlighted at 73.6 eV.

The figure shows the spectral response of Al-F after BCl3 treatment, with a fitted curve overlaid. Also, Al-F bond is highlighted at 77.0 eV.

| B. E. (eV) | Counts |
| --- | --- |
| 85 | - |
| 80 | peak at 77 eV, 78 eV|
| 75 | peak at 74 eV |
| 70 | peak at 73 eV |

| B. E. (eV) | Counts |
| --- | --- |
| 85 | - |
| 80 | - |
| 75 | - |
| 70 | peak at 73 eV |

Answer: The XPS technique is used to study the chemical state of the Al on the AlN surface during the ALE cycle.

Answer: After XeF2 exposure, 4 species are present on the surface.

Answer: The subfigure b, where the AlN peak can be observed at 73.6 eV.

Answer: Exposure to BCl3 results in the removal of AlF3 from the surface, leaving only AlN.


Figure 2. FTIR spectra during thermal AlN ALE with HF and  $\mathrm{BCl}_3$  as the reactants at  $350^{\circ}\mathrm{C}$  after various numbers of ALE cycles.

The chart displays the absorbance spectra of AlN ALE samples prepared using HF & BCl₃ at 350°C, with different number of cycles.

| Wavenumber (cm⁻¹) | 1 cycle | 3 cycles | 12 cycles | 15 cycles | 27 cycles |
|------------------|------------|------------|------------|------------|------------|
| 1400             |    -       |    -       |    -       |    -       |    -       |
| 1200             |    -       |    -       |    -       |    -       |    -       |
| 1000             |     -      |     -      |     -      |     -      |     -      |
| 800              |     -      |     -      |     -      |     -      |     -      |
| 600              | - | peak at 650 | peak at 650 | peak at 650 | peak at 650 |
| 400              |     -    |     -    |     -    |     -    |     -    |

Answer: FTIR are measured at least for 1, 3, 12, 15, and 27 ALE cycle with HF and BCl3.

Answer: As the number of cycles increases, so does the absorbance intensity, reaching more natives values.

Answer: After one cycle of HF and BCl3, there is still no peak at 650 cm-1.

Answer: It could be caused by some BN formation.


Figure 3. FTIR difference spectra after (a) HF exposure and (b)  $\mathrm{BCl}_3$  exposure during the 10th cycle of thermal AlN ALE at  $350^{\circ}\mathrm{C}$ . Each spectrum is referenced to the spectrum after the previous exposure.

The figure displays infrared absorption spectra for two samples labeled as HF-BCl₃ and BCl3-HF, at 350°C during the 10th cycle.

| Wavenumber (cm⁻¹) | HF-BCl3 | BCl3-HF |
| --- | --- | --- |
| 1750 | - | - |
| 1500 | - | - |
| 1250 | B-N | B-N |
| 1000 | - | - |
| 750 | Al-N | Al-F |
| 500 | - | Al-F |

Answer: Changes that occur ruing each exposure of the reactant can be observed through the vibrational modes at different wavenumber values.

Answer: Below 750 cm-1, Al-N and Al-f can be observed.

Answer: The absorbance spectra of BCl3 exposure show a positive peak related to the formation of the B-N bond at around 1250 cm-1.

Answer: This is due to the overlap between Al-N and Al-F.


Fig. 10. Mass spectra from  $m / z$  235 to 263 showing ion signal intensities for Co  $(\mathrm{acac})_2$  etch product during Hacac exposures on (a) CoO and (b)  $\mathrm{Co_3O_4}$  powders at  $250^{\circ}C$  Largest ion signals are observed for  $\mathrm{Co(acac)}_{2}^{+}$  and Co  $(\mathrm{acac})(\mathrm{C_4H_4O_2})^+$

The chart displays mass-to-charge ratio (m/z) on the x-axis and intensity in arbitrary units on the y-axis for Co3O3 and CoO at 250 °C. It shows peaks corresponding to various chemical species at specific m/z values.

| m/z | Co3O4 | CoO |
| --- | --- | --- |
| 236 | peak at 239 | peak at 239 |
| 240 | peak at 242, 243 | peak at 242, 243 |
| 244 | - | - |
| 248 | peak at 250 | - |
| 252 | peak at 252 | peak at 252 |
| 256 | peak at 257, 258 | peak at 257, 258 |
| 260 | - | - |

Answer: The figure shows the mass spectra from m/z between 235 to 263 for Co3O4 and CoO at 150 °C.

Answer: The peak intensity changes with the m/z ratio, but the most significant difference is due to the sample. Co3O4 shows higher intensity peaks compared to CoO.

Answer: The highest peak is shown at 275 and corresponds to the Co(acac)2+ species.

Answer: It can be useful for identifying the species involved in the reaction.

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-etching/experimental-usecase/21/Thermal atomic layer etching of CoO using acetylacetone and ozone.pdf


Figure 3. XPS data of Mo, S, and Cl on the  $\mathrm{MoS_2}$  surface after Cl-radical adsorption and during  $\mathrm{Ar^{+}}$  -ion desorption of  $\mathrm{MoS_2}$  ALE. (a) XPS data of the pristine bilayer  $\mathrm{MoS_2}$  before and after Cl-radical adsorption. (b) XPS data of Cl before/after Cl-radical adsorption and after the  $\mathrm{Ar^{+}}$  -ion exposure time of  $0 - 200\mathrm{s}$  XPS data of Mo and S after the  $\mathrm{Ar^{+}}$  -ion exposure of the Cl-adsorbed bilayer  $\mathrm{MoS_2}$  for (c) 0, 15, 30 s, (d) 30, 45, 60 s, (e) 60, 90,  $120~\mathrm{s},$  and (f)  $120,200\mathrm{s},$  and pristine bilayer  $\mathrm{MoS_2}$

The figure shows XPS spectra of Mo 3d // S 2p for pristine bilayer and after Cl adsorption.

The figure displays XPS spectra of Cl 2p for pristine bilayer and various Ar exposure times.

The figure presents XPS spectra of Mo 3d // S 2p after Cl adsorption and Ar exposure times.

The figure shows XPS spectra of Mo 3d // S 2p after several Ar exposure times.

The figure displays XPS spectra of Mo 3d // S 2p after several Ar exposure times.

The figure presents XPS spectra of Mo 3d // S 2p after Ar exposure times and for a pristine bilayer.

| Binding energy (eV) | Intensity (a.u.) |
|---|---|
| 233 | 3d3/2 |
| 229 | 3d5/2 |
| 227 | S-Mo-S |
| 163 | 2p1/2 |
| 162 | 2p3/2 |

| Binding energy (eV) | Intensity (a.u.) |
|---|---|
| 204 | 0 |
| 201 | 2p1/2 |
| 200 | 2p3/2 |
| 198 | 0 |
| 164 | 0 |
| 162 | 0 |

| Binding energy (eV) | Intensity (a.u.) |
|---|---|
| 234 | 3d3/2 |
| 229 | 3d5/2 |
| 227 | S-Mo-S |
| 163 | 2p1/2 |
| 162 | 2p3/2 |

Answer: This only happens slightly, however the S-Mo-S peak does seem to be removed more, indicating that the sulfur is no longer bonded to Mo.

Answer: The sulfur peaks decrease whereas the molybdenum peaks remain constant, so the sulfur is selectively etched.

Answer: The intensities of a bilayer MoS2 are equal to those of a Monolayer, so the should converge back to the pristine one.

Answer: All peaks are equally removed by the argon plasma, so no this is not the case.

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


FIG. 2. Expected equilibrium species determined by thermodynamic modeling in the temperature range from 25 to  $400^{\circ}C$  for [a) and (e)] 1 mol  $\mathrm{TiO_2 / ZrO_2}$  and 1 mol  $\mathsf{WF}_6$  b and (f)] 0.75 mol  $\mathrm{TiO_2 / ZrO_2}$  and 1 mol  $\mathsf{BCl}_3,$  c and (g)] 0.5 mol  $\mathrm{TiO_2 / ZrO_2}$  and 1 mol  $\mathrm{SOCl}_2$  and [(d) and (h)] 1 mol  $\mathrm{TiO_2 / ZrO_2}$  and 1 mol  $\mathrm{TiCl_4}$

Equilibrium concentration profiles for the TiO₂ + WF₆ system show that at lower temperatures TiF₄(s) and WO₃(s) are favored, while increasing temperature promotes the formation of volatile TiF₄(g) and WF₂O₂(g), indicating thermally activated fluorination and oxide conversion.

In the TiO₂ + BCl₃ system, the equilibrium concentrations remain nearly constant over the temperature range, with stable formation of TiCl₄(g) and B₂O₃(s), suggesting limited temperature dependence and a less aggressive halogenation reaction.

For the TiO₂ + SOCl₂ reaction, SO₂(g) and TiCl₄(g) dominate across the entire temperature range, indicating efficient chlorination of TiO₂ with gaseous byproduct formation and minimal solid residue evolution.

The TiO₂ + TiCl₄ equilibrium shows no significant reaction progress with temperature, as TiO₂(s) and TiCl₄(g) remain stable, confirming the absence of a driving force for further chemical transformation in this system.

In the ZrO₂ + WF₆ system, ZrF₄(s) and WO₃(s) are stable at low temperatures, while higher temperatures favor the formation of volatile WF₂O₂(g), demonstrating temperature-dependent fluorination behavior similar to TiO₂ but with different stability ranges.

The ZrO₂ + BCl₃ equilibrium reveals a sharp transition from solid ZrCl₄(s) to gaseous ZrCl₄(g) with increasing temperature, indicating sublimation-driven volatility and strong temperature sensitivity of zirconium chlorides.

For the ZrO₂ + SOCl₂ system, increasing temperature leads to the conversion of solid zirconium sulfate and chloride species into gaseous ZrCl₄ and SO₂, highlighting complex intermediate formation followed by volatile product dominance.

In the ZrO₂ + TiCl₄ system, multiple solid intermediates such as ZrOCl₂(s) and Zr₂O₃Cl₂(s) appear at intermediate temperatures before stabilizing as ZrO₂(s), indicating competitive chlorination and oxygen exchange reactions

| Temperature range | TiF4(s) | TiF4(g) | WO3(s) | WF6(g) | WF2O2(g) |
|-------------------|---------|---------|--------|--------|----------|
| Low T             | High    | 0       | High   | Medium | 0        |
| Mid T             | ↓       | ↑       | ↓      | ↓      | ↑        |
| High T            | 0       | High    | 0      | 0      | High     |

| Temperature range | TiCl4(g) | B2O3(s) |
|-------------------|----------|---------|
| All T             | High     | Medium  |

| Temperature range | SO2(g) | TiCl4(g) |
|-------------------|--------|----------|
| All T             | High   | Medium   |

| Temperature range | TiCl4(g) | TiO2(s) |
|-------------------|----------|---------|
| All T             | High     | High    |

| Temperature range | ZrF4(s) | WO3(s) | WF6(g) | WF2O2(g) |
|-------------------|---------|--------|--------|----------|
| Low T             | High    | High   | Medium | 0        |
| Mid T             | ↓       | ↓      | ↓      | ↑        |
| High T            | 0       | 0      | 0      | High     |

| Temperature range | ZrCl4(s) | ZrCl4(g) | B2O3(s) |
|-------------------|----------|----------|---------|
| Low T             | High     | 0        | Medium  |
| Mid T             | ↓        | ↑        | Medium  |
| High T            | 0        | High     | Medium  |

| Temperature range | SOCl2(g) | SO2(g) | Zr(SO3)2(s) | ZrCl4(s) | ZrCl4(g) |
|-------------------|----------|--------|-------------|----------|----------|
| Low T             | High     | 0      | Medium      | Medium   | 0        |
| Mid T             | ↓        | ↑      | ↓           | ↓        | ↑        |
| High T            | 0        | High   | 0           | 0        | Medium   |

| Temperature range | ZrOCl2(s) | TiCl4(g) | TiO2(s) | ZrO2(s) | Zr2O3Cl2(s) |
|-------------------|-----------|----------|---------|---------|-------------|
| Low T             | High      | Medium   | Low     | Low     | Low         |
| Mid T             | ↓         | ↑        | Peak    | ↑       | Peak        |
| High T            | 0         | High     | 0       | High    | 0           |

Answer: The equilibrium plots show that SOCl₂ produces exclusively volatile products on TiO₂, making it the cleanest and most efficient chlorinating agent for TiO₂ ALE. In contrast, ZrO₂ requires higher temperatures and reacts best with BCl₃, which forms volatile ZrCl₄(g) at elevated temperatures. SOCl₂ performs poorly for ZrO₂ due to persistent nonvolatile sulfate intermediates. These differences directly guide the selection of optimal co-reactants for oxide-specific ALE processes.

Answer: Yes, the modeling clearly shows which reactions generate volatile chlorides or oxides and which form nonvolatile intermediates that could limit atomic layer etching.

Answer: Formation of volatile metal chlorides, Absence of stable solid intermediates, Temperature-dependent stability of fluorides and sulfates, Ability of co-reactants to convert fluorinated surfaces into volatile products

Answer: SOCl₂ produces fully volatile products such as SO₂(g) and TiCl₄(g) with TiO₂, but forms nonvolatile sulfates (e.g., Zr(SO₄)₂(s)) with ZrO₂, explaining the strong contrast in etch behavior.

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-etching/experimental-usecase/35/Comparison of BCl3, TiCl4, and SOCl2 chlorinating agents for.pdf


FIG. 4. Expected equilibrium species determined by thermodynamic modeling in the temperature range from 25 to  $400^{\circ}C$  for 1 mol  $\mathbb{W}\mathbb{O}_3$  reacting with (a)  $4 / 3\text{mol}$ $\mathbb{BC}\mathbb{I}_3,$  (b) 1 mol  $\mathbb{T}\mathbb{C}\mathbb{I}_4,$  (c) 1 mol  $\mathrm{SOCl}_2,$  and for 1 mol  $\mathrm{ZrF_4}$  reacting with (d)  $4 / 3\text{mol}$ $\mathbb{BC}\mathbb{I}_3,$  (e) 1 mol  $\mathbb{T}\mathbb{C}\mathbb{I}_4,$  and (f)  $2.4\text{mol}$ $\mathrm{SOCl}_2$

In the WO₃ + BCl₃ system, equilibrium concentrations indicate that WOCl₄(g) and B₂O₃(s) dominate at lower temperatures, while increasing temperature promotes the formation of volatile WO₂Cl₂(g), reflecting temperature-activated chlorination of tungsten oxide.

For WO₃ + SOCl₂, SO₂(g) remains the dominant gaseous byproduct across the temperature range, while a transition from solid WO₂Cl₂(s) to gaseous WO₂Cl₂(g) occurs with increasing temperature, indicating enhanced volatility of tungsten chlorides.

In the WO₃ + TiCl₄ system, multiple competing equilibria are observed, with TiCl₄(g), WO₃(s), TiO₂(s), and WO₂Cl₂(g/s) coexisting over different temperature ranges, demonstrating complex ligand exchange and oxygen transfer reactions.

In the ZrF₄ + BCl₃ system, a sharp temperature-dependent transition from solid ZrCl₄(s) to gaseous ZrCl₄(g) is observed, while BF₃(g) remains stable, indicating efficient halogen exchange and volatility enhancement at elevated temperatures.

For ZrF₄ + SOCl₂, equilibrium favors the formation of ZrCl₄(g) at higher temperatures, accompanied by stable gaseous byproducts such as SF₂Cl(g) and SO₂F₂(g), highlighting strong fluorine–chlorine exchange and sulfate formation pathways.

In the ZrF₄ + TiCl₄ system, ZrF₄(s) and TiCl₄(g) remain largely unchanged over the temperature range, with only trace formation of TiF₄(g) and ZrCl₄(g), indicating minimal thermodynamic driving force for reaction between these species.

| Reaction System|Main Volatile Products|Main Solid Products|ALE Interpretation|
|----------------|----------------------|------------------|------------------|
|WO3 + BCl3|WOCl4(g) (high T)|B2O3(s)|Moderate/OK|

| Reaction System|Main Volatile Products|Main Solid Products|ALE Interpretation|
|----------------|----------------------|------------------|------------------|
|WO3 + SOCl2|SO2(g), WO-chlorides|Very little solid|Excellent for TiO2|

| Reaction System|Main Volatile Products|Main Solid Products|ALE Interpretation|
|----------------|----------------------|------------------|------------------|
|WO3 + TiCl4|Mixed chlorides (weak)|WO2Cl2(s), WOCl4(s)|Poor|

| Reaction System|Main Volatile Products|Main Solid Products|ALE Interpretation|
|----------------|----------------------|------------------|------------------|
|ZrF4 + BCl3|ZrCl4(g) (high T)|B2F4(g)/minor solids|Best for ZrO2|

| Reaction System|Main Volatile Products|Main Solid Products|ALE Interpretation|
|----------------|----------------------|------------------|------------------|
|ZrF4 + SOCl2|Some ZrCl4(g)|Sulfates (Zr(SO4)2, ZrOSO4)|Very poor|

| Reaction System|Main Volatile Products|Main Solid Products|ALE Interpretation|
|----------------|----------------------|------------------|------------------|
|ZrF4 + TiCl4|Minimal|TiF4(s), ZrCl4(g) (low)|Weak|

Answer: The predicted product distributions show that SOCl₂ produces clean, volatile products when reacting with WO₃, making it the most efficient co-reactant for TiO₂ ALE. For ZrF₄, however, SOCl₂ forms nonvolatile sulfate residues, while BCl₃ can produce volatile ZrCl₄(g) at elevated temperatures, identifying BCl₃ as the most effective reagent for ZrO₂ ALE. TiCl₄ produces mixed or solid products in both systems, explaining its poor performance. These thermodynamic insights directly correlate with experimental etch behaviors.

Answer: Yes, the modeling shows which co-reactants form volatile chlorides versus nonvolatile solids, revealing which ligand-exchange reactions can drive ALE and which cannot.

Answer: Formation of volatile metal chlorides (e.g., ZrCl₄(g), WOCl₄(g)), Absence of stable nonvolatile by-products (e.g., sulfates, B₂O₃), Temperature-dependent stability of fluorides, Chloride–fluoride exchange energetics

Answer: SOCl₂ produces mainly volatile SO₂(g) with WO₃, but forms nonvolatile sulfates (Zr(SO₄)₂, ZrOSO₄) with ZrF₄, explaining why SOCl₂ is excellent for TiO₂ ALE but ineffective for ZrO₂.


FIG. 5. Saturation curves of etch rate dependence on  $\mathrm{WF}_6$  and co-reactant dose times for  $\mathrm{TiO_2}$  [(a) and (b)] and for  $\mathrm{ZrO_2}$  [(c) and (d)]. All  $\mathrm{TiO_2}$  etching processes were performed at  $170^{\circ}\mathrm{C}$  and  $\mathrm{ZrO_2}$  etching at  $325^{\circ}\mathrm{C}$ . The etch rate per cycle was determined by in situ ellipsometry over 10 ALE cycles.

The TiO₂ etch rate increases rapidly with WF₆ dose time and approaches saturation for all co-reactants, with BCl₃ producing the highest etch rate, followed by SOCl₂ and TiCl₄, indicating co-reactant-dependent fluorination efficiency.

When varying the co-reactant dose time for TiO₂ etching, the etch rate shows a self-limiting behavior, where BCl₃ reaches saturation fastest and at the highest rate, while SOCl₂ and TiCl₄ exhibit slower kinetics and lower saturation values.

For ZrO₂ etching as a function of WF₆ dose time, BCl₃ leads to a very high and rapidly saturating etch rate, TiCl₄ shows moderate etching efficiency, and SOCl₂ results in minimal material removal, demonstrating strong precursor selectivity.

The ZrO₂ etch rate versus co-reactant dose time reveals that BCl₃ again provides the most efficient and rapid etching, TiCl₄ shows slower saturation behavior, and SOCl₂ produces only weak etching, confirming co-reactant-controlled surface reaction kinetics.

| Substrate|Variable Scanned|Best Co-reactant|Worst Co-reactant|Trend Summary|
|----------|----------------|----------------|-----------------|-------------|
|TiO2|WF6 dose time|SOCl2|TiCl4|Faster saturation for SOCl2; TiCl4 slow/low etch|

| Substrate|Variable Scanned|Best Co-reactant|Worst Co-reactant|Trend Summary|
|----------|----------------|----------------|-----------------|-------------|
|TiO2|Co-reactant dose|SOCl2|TiCl4|SOCl2 gives highest etch rates; BCl3 moderate|

| Substrate|Variable Scanned|Best Co-reactant|Worst Co-reactant|Trend Summary|
|----------|----------------|----------------|-----------------|-------------|
|ZrO2|WF6 dose time|BCl3|SOCl2|BCl3 saturates fastest and highest; SOCl2 very low|

| Substrate|Variable Scanned|Best Co-reactant|Worst Co-reactant|Trend Summary|
|----------|----------------|----------------|-----------------|-------------|
|ZrO2|Co-reactant dose|BCl3|SOCl2|Strong BCl3 saturation; SOCl2 remains near zero|

Answer: The saturation behavior reveals which co-reactants efficiently convert fluorinated surfaces into volatile by-products. For TiO₂, SOCl₂ reaches the highest etch rate with rapid saturation, indicating excellent reactivity. For ZrO₂, BCl₃ produces the highest etch rates and strong self-limiting behavior, while SOCl₂ remains ineffective due to nonvolatile sulfate formation. These trends guide material-specific selection of co-reactants, enabling optimized, selective ALE processes for different oxide substrates.

Answer: Yes, the curves show clear plateaus for effective chemistries, confirming self-limiting etch behavior characteristic of ALE.

Answer: Volatility of chloride products, Ability to remove fluorinated intermediates, Formation of nonvolatile residues (e.g., sulfates), Temperature dependence of ligand-exchange reactions

Answer: TiO₂ etches fastest with SOCl₂, while ZrO₂ etches fastest with BCl₃, showing opposite reactivity trends for the two oxides.


FIG. 2. Ti2p XPS spectra intensity (a) before and (b) after the oxidation step, and (c) O1s XPS spectra intensity by varying the processing time at  $100^{\circ}$ C and  $15$ W. The thickness of the  $\mathrm{TiO_2}$  layer as a function of (d) temperature at  $15$ W and (e) RF power at  $100^{\circ}$ C in the oxidation step. The standard process conditions of the oxidation step were  $\mathrm{O_2}$  gas flow of  $5$ SCCM, a pressure of  $0.5$  Torr, a temperature of  $100^{\circ}$ C, an RF power of  $15$ W, and a processing time of  $300$ s.

Ti 2p XPS spectra of the TiN reference film show deconvoluted components assigned to TiN, TiOₓNᵧ, and TiO₂ across 450–470 eV. The relative contributions establish the initial surface chemistry prior to oxidation.

After oxidation, the Ti 2p spectrum is dominated by the TiO₂ component, while TiN-related features are reduced. This shift indicates effective surface oxidation induced by the O₂ plasma step.

O 1s spectra collected at 100 °C and 15 W evolve with oxidation time from 30 to 600 s. The TiO₂-related component near ~530 eV increases with time, consistent with progressive oxide growth.

Estimated TiO₂ thickness increases with oxidation time for all temperatures at fixed RF power. Higher temperatures yield thicker oxides and reach saturation more rapidly.

At 100 °C, increasing RF power produces thicker TiO₂ layers over time. The highest power (50 W) shows the largest thickness and fastest approach to saturation.

| Binding Energy (eV) | Peak Assignment |
|---------------------|------------------|
| ~456                | TiN              |
| ~457                | TiOxNy           |
| 458–459             | TiO2             |
| ~462                | TiN              |
| ~464                | TiO2             |

| Binding Energy (eV) | Peak Assignment |
|---------------------|------------------|
| ~455                | TiN              |
| ~457                | TiOxNy           |
| 458–459             | TiO2             |
| 461–462             | TiN              |
| ~464                | TiO2             |

| Binding Energy (eV) | Sample Condition |
|---------------------|------------------|
| 529-531             | TiO2 (ref, 30s, 60a, 180s, 300s, 600s) |
| 531–532             | TiOxNy (ref, 30s, 60a, 180s, 300s, 600s) |

| Time (sec)|Thickness at 50°C (nm)     | 100°C (nm) | 150°C (nm) | 200°C (nm) |
|-----------|---------------------------|------------|---------|----------|
| 70        | ~0.15                     | ~0.25      | ~0.40   | ~0.70    |
| 150       | ~0.25                     | ~0.40      | ~0.70   | ~1.00    |
| 300       | ~0.30                     | ~0.50      | ~0.85   | ~1.25    |
| 450       | ~0.30                     | ~0.50      | ~0.85   | ~1.25    |
| 600       | ~0.30                     | ~0.50      | ~0.85   | ~1.25    |
| 900       | ~0.30                     | ~0.50      | ~0.85   | ~1.25    |

| Time (sec) | TiO2 Thickness at 10W (nm) | TiO2 Thickness at 15W (nm) | TiO2 Thickness at 25W (nm) | TiO2 Thickness at 50W (nm) |
|-----------|------------------------------|---------|---------|---------|
| 70        | 0.20                         | 0.30    | 0.50    | 0.60     |
| 150       | 0.25                         | 0.40    | 0.75    | 1.50     |
| 300       | 0.25                         | 0.50    | 1.00    | 2.00     |
| 600       | 0.25                         | 0.50    | 1.00    | 2.50     |
| 900       | 0.25                         | 0.50    | 1.00    | 2.90     |

Answer: 200 °C.

Answer: The TiO₂-related O 1s feature near ~530 eV increases strongly as oxidation time increases (30 s → 600 s), and the growth becomes less pronounced at longer times, suggesting an approach toward saturation. A higher-binding-energy shoulder near ~531–532 eV remains present; the figure suggests the TiO₂ contribution becomes increasingly dominant with time.

Answer: Yes. The curves show a clear ordering (50 W > 25 W > 15 W > 10 W) at long times, indicating thicker oxide growth at higher RF power under otherwise fixed conditions.

Answer: TiO₂ becomes the dominant contribution (relative to TiN/TiO_xN_y).

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


FIG. 3. (a) Ti2p XPS spectra intensity after the fluorination step and (b) F1s XPS spectra intensity of  $685.0\mathrm{eV}$  with varying the processing time at  $100^{\circ}\mathrm{C}$  and  $15\mathrm{W}$  of fluorination step. (c) F atomic fraction with  $\mathrm{CF_4}$  plasma-exposure time at RF powers of 10, 15, and  $25\mathrm{W}$  in the fluorination step. The standard process conditions of the fluorination step were a  $\mathrm{CF_4}$  gas flow of 2 SCCM, a pressure of  $0.03\mathrm{Torr}$ , a temperature of  $100^{\circ}\mathrm{C}$ , an RF power of  $15\mathrm{W}$ , and a processing time of  $20\mathrm{s}$ .

Ti 2p XPS spectrum measured after the fluorination step, showing deconvoluted components attributed to TiN, TiOxNy, TiO₂, and fluorinated TiO₂−xFx species, indicating chemical modification of the surface during CF₄ plasma exposure.

F 1s XPS spectra acquired at increasing fluorination times at 100 °C and 15 W, with a dominant peak near 685.0 eV whose intensity grows with time, reflecting progressive incorporation of fluorine into the surface layer.

Fluorine atomic percentage plotted as a function of CF₄ plasma exposure time for RF powers of 10, 15, and 25 W, showing higher fluorine content and faster saturation at increased RF power.

| Binding energy (eV) | Assignment      |
|--------------------|-----------------|
| ~455–456           | TiN             |
| ~456–457           | TiOxNy          |
| ~458–459           | TiO2            |
| ~459–460           | TiO2−xFx        |
| ~462                     | TiN             |
| ~464–465           | TiO2            |

| Binding Energy (eV) | Peak Assignment | Observation |
|---------------------|----------------|-------------|
| ~685.0              | TiO2−xFx        | Peak intensity increases with exposure time |

| Time (s) | 10 W (%) | 15 W (%) | 25 W (%) |
|----------|----------|----------|----------|
| 10       | ~4–5     | ~5       | ~10      |
| 15       | ~9       | ~10      | ~15      |
| 20       | ~10      | ~10–11   | ~15–16   |
| 30       | ~11      | ~11–12   | ~17      |
| 45       | ~12      | ~12      | ~21      |
| 60       | ~12      | ~12      | ~24      |

Answer: The Ti 2p spectrum shows the emergence of TiO₂−xFx components alongside TiO₂ and TiN peaks, indicating that CF₄ plasma exposure leads to partial fluorination of the oxide layer rather than complete removal or bulk conversion.

Answer: Higher RF power results in higher fluorine atomic percentage at all exposure times.

Answer: Yes

Answer: TiO2−xFx.


FIG. 4. (a) Ti2p XPS spectra intensity after the removal step at a temperature of  $150^{\circ}C$ , (b) F1s XPS spectra intensity of  $685.0 \text{eV}$ , and (c) F1s peak area spectra intensity for  $\text{TiO}_{2 - x}\text{F}_x$  products as a function of temperature at the removal step. The standard process conditions of the removal step were an Ar gas flow of 50 SCCM, a pressure of 0.1 Torr, a temperature of  $150^{\circ}C$ , and a time of 30 s without RF power.

Ti 2p XPS spectrum measured after the removal step at 150 °C, showing components assigned to TiN, TiOxNy, and TiO₂, with no fluorinated Ti species detected.

F 1s XPS spectra recorded after the removal step at increasing temperatures, showing a strong F 1s signal at 80–120 °C that rapidly diminishes and approaches the noise level at temperatures ≥150 °C.

F 1s peak area as a function of removal temperature, remaining high up to ~120 °C, dropping sharply near 140 °C, and becoming negligible above 150 °C.

| Binding Energy (eV) | Major Peak Assignment |
|----------------------|-----------------------|
| ~456.0               | TiN                  |
| ~457.0               | TiOxNy               |
| ~458.2               | TiO2                 |
| ~462.0               | TiN                  |
| ~464.0               | TiO2                 |

| Binding Energy (eV) | Peak Assignment | Observation |
|----------------------|----------------|-------------|
| ~685.0               | 80°C,100°C,120°C   | Highest Peak intensity |
| ~685.0               | 140°C,150°C,180°C,200°C  | Lowest Peak intensity (near baseline) |

| Temperature (°C) | F1s peak area (A.U.) |
|------------------|----------------------|
| 80               | 17000                |
| 100              | 17500                |
| 120              | 16000                |
| 140              | 2500                 |
| 160              | 0                    |
| 180              | 0                    |
| 200              | 0                    |

Answer: After the removal step, the Ti 2p spectrum shows only TiN, TiOxNy, and TiO₂ components, with no signatures of fluorinated Ti species. This indicates that fluorine-containing surface species formed during fluorination are effectively removed during the thermal removal step.

Answer: Between approximately 120 °C and 140 °C.

Answer: Yes

Answer: Thermal removal of fluorine from the surface.


XPS Mo 3d spectra of a molybdenum sample as-received

| Peak Assignment | Binding Energy (eV) |
|-----------------|-----------------------|
| Mo 3d₅/₂ (Mo⁶⁺) | ~236                |
| Mo 3d₃/₂ (Mo⁶⁺) | ~232                |
| Mo 3d₅/₂ (Mo⁴⁺) | ~234                |
| Mo 3d₃/₂ (Mo⁴⁺) | ~230                |
| Minor feature   | ~228                |

Answer: XPS probes the top five or so nanometers of the surface, whereas LEIS is able to distinguish the topmost surface atoms from the atoms underneath

Answer: No

Answer: To get further insight into the etching mechanism of Mo with O2 and NbCl5, the films were etched until a selected point of the process and then transferred in vacuo to XPS. On the as-received film, there was a thick native oxide layer due to a long storage in air.

Answer:
In the XPS spectrum of Mo 3d5/2 and 3d3/2 peaks at 232.7 and 235.9 eV make up most of the intensity, attributed to Mo6+, with peaks at 231.6 and 234.7 eV
arising from Mo5+. A small signal of Mo0 is also visible at 227.9 and 231.0 eV

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-etching/experimental-usecase/47/Atomic layer etching of molybdenum with O2 and NbCl5.pdf


X-ray photoelectron spectra of Mo 3d spectra of a molybdenum sample  after heating in vacuum at 300 °C for 20 min.

| Oxidation State | Peak Assignment | Binding Energy (eV) |
|-----------------|-----------------|-----------------------|
| Mo⁰            | Mo 3d          | ~228                |
| Mo³⁺           | Mo 3d          | ~230                |
| Mo⁴⁺           | Mo 3d          | ~232                |
| Mo⁵⁺           | Mo 3d          | ~234                |
| Mo⁶⁺           | Mo 3d          | ~236                |

Answer: To measure a spectrum that corresponds to the film surface just before etching is started, the sample was heated in vacuum to 300 °C and kept at this temperature for 20 min under a constant N2 flow

Answer: A significant decrease in the relative intensity of Mo6+ was observed compared to the as-received sample, with a corresponding increase in the intensity of Mo5+ and appearance of Mo4+ peaks at 230.5 and 233.7 eV.

Answer: This demonstrates that MoO3 is reduced in vacuum at 300 °C, possibly due to comproportionation reactions between Mo and MoO3.33

Answer: No


The figure displays a Mo 3d spectra chart with peaks at specific binding energies, after etching with one 4 s NbCl5 pulse

| Oxidation State | Peak Assignment | Binding Energy (eV) |
|-----------------|-----------------|-----------------------|
| Mo⁰            | Mo 3d          | ~228                |
| Mo³⁺           | Mo 3d          | ~230                |
| Mo⁴⁺           | Mo 3d          | ~231                |
| Mo⁵⁺           | Mo 3d          | ~232                |
| Mo⁶⁺           | Mo 3d          | ~234                |
| Additional Mo⁶⁺ component  | -      | ~236                |

Answer: After the first NbCl5 pulse, a decrease in the Mo6+ and Mo5+ intensities is seen compared to the unetched film whereas Mo4+ has higher relative intensity than before etching

Answer: Yes

Answer: The intensity of the metallic Mo0 is also higher, which indicates etching (thinning) of the surface oxide. An increase of the intensity between the oxide and metal peaks is seen, which corresponds to peaks at 229.6 and 232.7 eV. These are attributed to Mo3+, likely in the form of MoCl3.

Answer: The generation of MoCl3 is supported by the thermodynamic equilibrium calculations, which indicated that NbCl5 can react with Mo to make lower valence chlorides.


XPS Mo 3d spectra after oxidizing the etched sample with a 6 s O2 pulse at 300 °C

| Oxidation State | Peak Assignment | Binding Energy (eV) |
|-----------------|-----------------|-----------------------|
| Mo⁰            | Mo 3d          | ~228                |
| Mo³⁺           | Mo 3d          | ~230                |
| Mo⁴⁺           | Mo 3d          | ~231                |
| Mo⁵⁺           | Mo 3d          | ~232                |
| Mo⁶⁺           | Mo 3d          | ~234                |
| Additional Mo⁶⁺ component  | -       | ~236                |

Answer:
CPS
, Mo⁰
, Mo³⁺
, Mo⁴⁺
, Mo⁵⁺
, Mo⁶⁺
, BG
, Envelope

Answer: The film was next oxidized at 300 °C with a 6 s pulse of O2. An increase in the Mo6+ intensity is seen, along with a decrease in Mo3+, showing the oxidation of the surface, the Mo0 intensity also increases.

Answer: the Mo0 intensity increases after 6s pulse of O2, which indicates that the surface layer gets thinner during the O2 pulse. The thinning might be caused by some of the MoCl3 being oxidized directly to volatile oxychlorides.

Answer: Red and black corresponding to CPS and envelope.


FIG. 12. XPS Mo 3d spectra of a molybdenum sample (a) as-received, (b) after heating in vacuum at  $300^{\circ}\mathrm{C}$  for  $20\mathrm{min}$ , (c) after etching with one  $4\mathrm{s}$ $\mathrm{NbCl}_5$  pulse and (d) after oxidizing the etched sample with a  $6\mathrm{s}$ $\mathrm{O}_2$  pulse at  $300^{\circ}\mathrm{C}$ . The same sample after three full ALE cycles and (e) one  $\mathrm{NbCl}_5$  pulse, and (f) oxidized again with  $\mathrm{O}_2$ .

A XPS spectra chart displaying the intensity of Mo 3d peaks at various binding energies after being exposed to 4th cycle NbCl5

Answer: The intensities of the Mo5+ and Mo6+ states decrease, and the peaks identified as Mo metal and Mo3+ become more intense

Answer: The change indicates that the surface oxide layer of the molybdenum film is etched and replaced by a thinner nonvolatile oxide-chloride layer

Answer: During the fourth O2 pulse, the Mo3+ doublet intensity decreases, and the Mo6+, Mo5+, Mo4+ and Mo0 peaks become stronger. This again indicates that O2 is both oxidizing the molybdenum surface and partially volatilizing the previously generated MoCl3

Answer: Yes


XPS spectra chart displaying Mo 3d binding energy peaks after 4th cycle oxidation.

| Oxidation State | Peak Assignment | Binding Energy (eV) |
|-----------------|-----------------|-----------------------|
| Mo⁰            | Mo 3d          | ~228                |
| Mo³⁺           | Mo 3d          | ~230                |
| Mo⁴⁺           | Mo 3d          | ~231                |
| Mo⁵⁺           | Mo 3d          | ~232                |
| Mo⁶⁺           | Mo 3d          | ~234                |
| Additional Mo⁶⁺ component | -        | ~236                |

Answer:
Red → CPS
, Purple → Mo⁰
, Blue → Mo³⁺
, Teal (cyan) → Mo⁴⁺
, Green → Mo⁵⁺
, Yellow → Mo⁶⁺
, Black dashed line → BG (Background)
, Black solid line → Envelope

Answer: With further ALE cycles, the intensities of the Mo5+ and Mo6+ states decrease, and the peaks identified as Mo metal and Mo3+ become more intense

Answer: During the fourth O2 pulse, the Mo3+ doublet intensity decreases, and the Mo6+, Mo5+, Mo4+ and Mo0 peaks become stronger. This again indicates that O2 is both oxidizing the molybdenum surface and partially volatilizing the previously generated MoCl3

Answer: yes


FIG.11. Mass traces of (a)  $\mathsf{BF}_2^+$  at  $m / z = 47$  amu and  $\mathsf{BFOH}^+$  at  $m / z = 49$  amu and (b)  $\mathrm{H}_2\mathrm{O}^+$  at  $m / z = 18$  amu vs time during the first five HF exposures on  $\mathrm{B}_2\mathrm{O}_3$  powder.

Mass spectrometry traces showing the evolution of fluorinated boron species during five HF pulses. The BF2+ signal increases progressively with successive cycles, while the BFOH+ signal decreases, indicating a shift from hydroxyl-containing to more fully fluorinated surface species.

Mass spectrometry trace tracking H2O+ evolution during repeated HF exposure. The signal increases over the first few cycles and then levels off, indicating saturation in water release behavior.

|HF Cycle |	Time (min)	|BF₂⁺ (m/z 49amu) mV	|BFOH⁺ (m/z 47amu) mV|
|---|---|---|---|
|1st	|~2.5-5.00	|~60 mV	    |~45 mV|
|2nd	|~7.5-10.00	|~95 mV	    |~40 mV|
|3rd	|~12.5-15.00 |~110 mV	|~30 mV|
|4th	|~17.5-20.00 |~110 mV	|~20 mV|
|5th	|~22.5-25.00 |~100 mV	|~20 mV|

|HF Cycle	|Time (min)	|H₂O⁺ (m/z 18amu) mV|
|---|---|---|
|1st	|~2.5-5.00	|~300 mV|
|2nd	|~7.5-10.00	|~450 mV|
|3rd	|~12.5-15.00 |~480 mV|
|4th	|~17.5-20.00 |~460 mV|
|5th	|~22.5-25.00 |~430 mV|

Answer: The data reveals an inverse relationship between the two fluorinated species as the process proceeds. The BF2+ signal (indicating pure fluorination) roughly doubles from ~60 mV to a peak of ~110 mV, suggesting the surface is becoming more effectively fluorinated. Conversely, the BFOH+ signal (indicating partial hydroxy-fluorination) decreases by more than half (45 mV to 20 mV), suggesting a reduction in surface hydroxyl groups available for this specific reaction pathway.

Answer:
m/z = 49 for BF2+
, m/z = 47 for BFOH+

Answer: No, the release is pulsed, occurring only during the discrete HF exposure times (approx. every 5 minutes).

Answer: It reaches a maximum of approximately 480 mV at the 3rd HF cycle.

icdar2026-competition-data/test/gold_standard_test_set/atomic-layer-etching/simulation-usecase/28/Spontaneous etching of B2O3 by HF gas studied using infrared spectroscopy.pdf


FIG.9. Mass spectrum of products monitored in the range of  $m / z = 70-140$  amu during spontaneous etching of  $\mathrm{B}_2\mathrm{O}_3$  by HF at  $150^{\circ}C$  during the a first HF exposure and (b) fifth HF exposure. Observed products are  $\mathrm{B}_3\mathrm{O}_3\mathrm{F}_3$ ,  $\mathrm{B}_3\mathrm{O}_3\mathrm{F}_2\mathrm{OH}$ , and  $\mathrm{B}_3\mathrm{O}_3\mathrm{F}(\mathrm{OH})_2$  boroxine rings.

The figure shows mass spectra recorded at 150 °C during spontaneous etching of B2O3 by HF, comparing the first and fifth HF exposures. During the first HF exposure, intense peaks corresponding to fluorinated boron oxide and boroxine-related ions are observed, while these signals are strongly suppressed after the fifth HF exposure, consistent with progressive depletion of readily volatilizable reaction products.

| m/z range | Assigned ion | Relative intensity | HF exposure |
|-----------|--------------|--------------------|-------------|
| ~78–80    | B2F3⁺ / B2F2(OH)⁺     | High         |   1st HF  |
| ~90–95    | B2OF3⁺ / B2OF2(OH)⁺   | Moderate     |   1st HF  |
| ~115–120  | B3O3F2⁺ / B3O3F(OH)⁺  | Low–moderate |   1st HF  |
| ~135–140  | B3O3F3⁺ / B3O3F2(OH)⁺ | Low          |   1st HF  |
| 70–140    |     -                | Near zero    |   5th HF  |

Answer: The strong signal during the first HF exposure indicates active formation of volatile fluorinated boron species. By the fifth exposure, the intensity is greatly reduced, showing that most reactive surface species have already been consumed.

Answer: The first HF exposure.

Answer: Boroxine rings are structural motifs present in B2O3. During the initial HF exposure, these units react and fragment, producing fluorinated boron–oxygen species that desorb and are detected in the mass spectrum.

Answer: Yes, the reduced signal is consistent with self-limiting behavior, although this figure alone does not prove saturation.


FIG. 2. Infrared absorbance spectra from 400 to  $1800~\mathrm{cm^{-1}}$  during  $\mathsf{B}_2\mathsf{O}_3$  ALD using  $\mathrm{BCl}_3$  and  $\mathrm{H}_2\mathrm{O}$  as reactants after 1, 5, 10, and 15  $\mathrm{B}_2\mathrm{O}_3$  ALD cycles at  $40^{\circ}\mathrm{C}$ .

The figure shows infrared absorbance spectra of B2O3 films grown by ALD using BCl3 and H2O at 40 °C after 1, 5, 10, and 15 cycles. The progressive increase in the B–O stretching and B–O–B bending bands reflects steady film growth with increasing number of ALD cycles.

| Wave number |      Features       | 1 Cycle | 5 Cycles | 10 Cycles | 15 Cycles|
|-------------|---------------------|---------|---------|-----------|----------|
| ~1450       | B-O stretch (Peak 1)|	0.15  |  0.43	|  0.60    |   0.71   |
| ~1350       | Valley between peaks|	0.08  |  0.22	|  0.41    |   0.54   |
| ~1260       | B-O stretch (Peak 2)|	0.10  |  0.30	|  0.50    |   0.63   |
| ~1100       | Minor shoulder	    |   0.05  |  0.10	|  0.15    |   0.18   |
| ~920        | Baseline region	    |   0.02  |  0.04	|  0.06    |   0.08   |
| ~720        | B-O-B bend (Sharp)  |	0.04  |  0.13	|  0.22    |   0.30   |

Answer: The increasing intensity of the B–O stretching band with each additional ALD cycle shows that more B–O bonds are being incorporated into the film. This steady growth in absorbance is consistent with layer-by-layer deposition during the ALD process.

Answer: The B–O stretching band.

Answer: The B–O–B bending mode.

Answer: Yes