subsets/multi-spectra-chart/validation/metadata.jsonl

{"file_name":"images/validation_atomic-layer-deposition_experimental-usecase_11_fig_8.jpg","caption":"Fig. 8. Auger depth profile of the nanolaminate film stack  $(9 \\times (\\mathrm{WN}_{\\mathrm{x}} \\mathrm{C}_{\\mathrm{y}} (2 \\mathrm{~nm}) + \\mathrm{TiN} (2 \\mathrm{~nm}))$ .","id":"validation/atomic-layer-deposition/experimental-usecase/11/fig_8","sample_id":"atomic-layer-deposition/experimental-usecase/11/fig_8","subset":"multi-spectra-chart","split":"validation","classification":[{"panel_id":"a","label":"multi spectra chart"}],"summarization":"[{\"panel_id\":\"a\",\"text\":\"The plot shows atomic concentrations of W, C, N, Ti, O, F and Si as a function of sputter time through the 9×(WNₓCᵧ (2 nm) + TiN (2 nm)) nanolaminate. W and C are high and oscillatory (peaks at the WNₓCᵧ layers), Ti and N show complementary oscillations (peaks at the TiN layers), and the periodic waveform confirms the multilayer architecture is preserved. Fluorine is essentially negligible, oxygen is low in the bulk but rises at the surface (air exposure), and silicon sharply increases at the end when the substrate is reached — together indicating well-defined interfaces, low contamination, and minimal interdiffusion.\"}]","data_extraction":"[{\"panel_id\":\"a\",\"text\":\"| Sputter Time (min)|W (%)|C (%)|N (%)|Ti (%)|O (%)|F (%)|Si (%)|\\n|-------------------|-----|-----|-----|------|-----|-----|------|\\n|0|~10|~15|~8|~5|~2|~0.5|~0|\\n|5|~48|~30|~10|~6|~1|~0.3|~0|\\n|10|~52|~32|~11|~7|~1|~0.3|~0|\\n|15|~50|~30|~10|~6|~1|~0.2|~0|\\n|20|~45|~25|~9|~5|~1|~0.2|~0|\\n|25|~2|~5|~3|~1|~10–50 rising|~0.2|sharply rising|\"}]","vqa":"[{\"panel_id\":\"d\",\"items\":[{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The repeating elemental peaks confirm that the alternating WNₓCᵧ and TiN layers remain well-defined throughout the depth of the film. Such structural periodicity creates numerous interfaces that disrupt continuous diffusion pathways, making it more difficult for copper or other species to penetrate the barrier. The low fluorine content and minimal intermixing further enhance chemical stability, leading to reliable performance in semiconductor interconnect applications.\"}]},{\"panel_id\":\"b\",\"items\":[{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"W and Ti show repeated peaks and valleys corresponding to the nanolaminate layering, while O and Si remain low until the surface or substrate is reached, where they rise sharply.\"}]},{\"panel_id\":\"a\",\"items\":[{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"Yes, the periodic oscillations in W, C, N, and Ti concentrations clearly confirm the alternating multilayer structure.\"}]},{\"panel_id\":\"c\",\"items\":[{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"List\",\"answer\":\"Very low fluorine levels throughout the stack, Stable, repeating concentration oscillations, Sharp rise of Si only at the substrate interface, Low oxygen in the bulk with expected surface oxidation\"}]}]","bbox":[{"panel_id":"a","x":0,"y":0,"width":658,"height":619}],"source":"icdar2026-competition-data/dev/atomic-layer-deposition/experimental-usecase/11/images/fig_8.jpg","provenance":{"source_annotation":"icdar2026-competition-data/dev/atomic-layer-deposition/experimental-usecase/11/images/fig_8.json","source_content":"icdar2026-competition-data/dev/atomic-layer-deposition/experimental-usecase/11/content.json","source_pdf":["icdar2026-competition-data/dev/atomic-layer-deposition/experimental-usecase/11/K.-E. Elers et al.pdf"],"main_category":"atomic-layer-deposition","sub_category":"experimental-usecase","paper_id":"11","first_classification_panel_id":"a","first_classification_label":"multi spectra chart","caption_source":"content.json:image_caption"},"width":658,"height":619,"image_format":"jpeg","image_sha256":"a5b7c42f58ad8e2691fefdcfb70c7a8f94737e1fa95c6999413edca27591a9b4","metadata_license":"CC BY 4.0","image_license":"source_publisher_rights_reserved","image_reuse_status":"non_commercial_research_use_only","schema_version":"1.0.0"}
{"file_name":"images/validation_atomic-layer-deposition_experimental-usecase_58_fig_2.jpg","caption":"FIG. 2. XPS spectrum of PE-ALD Co for silicon core-level region after selective etching of Co film.","id":"validation/atomic-layer-deposition/experimental-usecase/58/fig_2","sample_id":"atomic-layer-deposition/experimental-usecase/58/fig_2","subset":"multi-spectra-chart","split":"validation","classification":[{"panel_id":"a","label":"multi spectra chart"}],"summarization":"[{\"panel_id\":\"a\",\"text\":\"The figure displays a Si core level spectrum for PE-ALD Co/Si(001) with raw data, deconvoluted components, and peak sum.\"}]","data_extraction":"[{\"panel_id\":\"a\",\"text\":\"| Binding Energy (eV) | Intensity (a.u.) |\\n|---|---|\\n| 94 | 0 |\\n| 96 | 0 |\\n| 98 | 0.5 |\\n|99|1|\\n| 100 | 0.4 |\\n| 102 | 0.4 |\\n| 104 | 0 |\\n| 106 | 0 |\\n| 108 | 0 |\"}]","vqa":"[{\"panel_id\":\"a\",\"items\":[{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"No this is not the case, as the pure silicon peal is just the sharp peak and not the shoulder.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The shoulder extends from 104 to 100 eV, this is usually a range in which there is also SiO2.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"It could be that you are overfitting the data resulting in contributions of composition that are not accurate.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"}]}]","bbox":[{"panel_id":"a","x":3,"y":2,"width":600,"height":466}],"source":"icdar2026-competition-data/dev/atomic-layer-deposition/experimental-usecase/58/images/fig_2.jpg","provenance":{"source_annotation":"icdar2026-competition-data/dev/atomic-layer-deposition/experimental-usecase/58/images/fig_2.json","source_content":"icdar2026-competition-data/dev/atomic-layer-deposition/experimental-usecase/58/content.json","source_pdf":["icdar2026-competition-data/dev/atomic-layer-deposition/experimental-usecase/58/Lee et al.pdf"],"main_category":"atomic-layer-deposition","sub_category":"experimental-usecase","paper_id":"58","first_classification_panel_id":"a","first_classification_label":"multi spectra chart","caption_source":"content.json:image_caption"},"width":602,"height":470,"image_format":"jpeg","image_sha256":"8895b2fcb15f599106b32e838dac14622e94290a91150375d36cda7f3f0f808e","metadata_license":"CC BY 4.0","image_license":"source_publisher_rights_reserved","image_reuse_status":"non_commercial_research_use_only","schema_version":"1.0.0"}
{"file_name":"images/validation_atomic-layer-deposition_simulation-usecase_13_fig10.jpg","caption":"Fig.10 (a) XPS C 1s spectrum of pristine and graphene treated with 5 min  $\\Omega_2$  plasma; (b-f) SEM images showing the Pt coverage after 500 ALD cycles using  $\\mathrm{MeCpPtMe}_3$  as the Pt precursor on (b) pristine graphene and graphene treated with (c) 1 min, (d) 2 min, (e) 3 min and (f) 5 min  $\\Omega_2$  plasma.","id":"validation/atomic-layer-deposition/simulation-usecase/13/fig10","sample_id":"atomic-layer-deposition/simulation-usecase/13/fig10","subset":"multi-spectra-chart","split":"validation","classification":[{"panel_id":"a","label":"multi spectra chart"},{"panel_id":"b","label":"image panel"},{"panel_id":"c","label":"image panel"},{"panel_id":"d","label":"image panel"},{"panel_id":"e","label":"image panel"},{"panel_id":"f","label":"image panel"}],"summarization":"[{\"panel_id\":\"a\",\"text\":\"XPS C 1s spectra comparing pristine graphene and graphene exposed to 5 min O₂ plasma, showing formation of C–O and C=O bonds and partial conversion of sp² carbon to sp³.\"},{\"panel_id\":\"b\",\"text\":\"SEM image of Pt deposition after 500 ALD cycles on pristine graphene (0 min O₂ plasma), showing limited nucleation and sparse Pt coverage.\"},{\"panel_id\":\"c\",\"text\":\"SEM image of Pt deposition after 500 ALD cycles on graphene treated with 1 min O₂ plasma, showing increased Pt nucleation and partial coverage.\"},{\"panel_id\":\"d\",\"text\":\"SEM image of Pt deposition after 500 ALD cycles on graphene treated with 2 min O₂ plasma, showing further enhancement of Pt coverage.\"},{\"panel_id\":\"e\",\"text\":\"SEM image of Pt deposition after 500 ALD cycles on graphene treated with 3 min O₂ plasma, showing near-continuous Pt domains forming.\"},{\"panel_id\":\"f\",\"text\":\"SEM image of Pt deposition after 500 ALD cycles on graphene treated with 5 min O₂ plasma, showing a nearly continuous Pt layer with uniform coverage across the graphene surface.\"}]","data_extraction":"[{\"panel_id\":\"a\",\"text\":\"| Binding Energy (eV) | sp² | C–O | C=O | Plasmon 1 | Plasmon 2 | Sample |\\n|---|---|---|---|---|---|---|\\n| 284.4 | Major | Minor | 0 | 0 | 0 | Pristine graphene |\\n| 286.4 | 0 | Minor | 0 | 0 | 0 | Pristine graphene |\\n| 290.4 | 0 | 0 | 0 | Minor | 0 | Pristine graphene |\\n| 293.2 | 0 | 0 | 0 | 0 | Minor | Pristine graphene |\\n| 284.6 | Minor | Minor | 0 | 0 | 0 | 5 min O₂ plasma graphene |\\n| 286.4 | 0 | Minor | 0 | 0 | 0 | 5 min O₂ plasma graphene |\\n| 289.0 | 0 | 0 | Minor | 0 | 0 | 5 min O₂ plasma graphene |\"},{\"panel_id\":\"b\",\"text\":\"| Sample | Pristine | 1 min O₂ Plasma |\\n|---|---|---|\\n| SEM Image | image_path | image_path |\"},{\"panel_id\":\"c\",\"text\":\"| Sample | 2 min O₂ Plasma |\\n|---|---|\\n| SEM Image | image_path |\"},{\"panel_id\":\"d\",\"text\":\"| Sample | 3 min O₂ Plasma |\\n|---|---|\\n| SEM Image | image_path |\"},{\"panel_id\":\"e\",\"text\":\"| Sample | 5 min O₂ Plasma |\\n|---|---|\\n| SEM Image | image_path |\"},{\"panel_id\":\"f\",\"text\":\"| Sample | 1000 ALD cycles on 5 min O₂ Plasma |\\n|---|---|\\n| SEM Image | image_path |\"}]","vqa":"[{\"panel_id\":\"a\",\"items\":[{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"Yes. O₂ plasma functionalizes the graphene surface, creating C–O and C=O groups that promote Pt nucleation and increase coverage during ALD.\"}]},{\"panel_id\":\"b\",\"items\":[{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The SEM images show that Pt coverage progressively increases with longer O₂ plasma exposure. After 1 minute, small Pt particles are sparsely distributed. With 2–3 minutes, coverage becomes more uniform, and after 5 minutes, the Pt forms an almost continuous layer, indicating that longer plasma treatment enhances surface functionalization and facilitates nucleation.\"}]},{\"panel_id\":\"d\",\"items\":[{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"List\",\"answer\":\"Introduces oxygen-containing functional groups (C–O, C=O) that enhance precursor adsorption, Increases surface reactivity and Pt coverage, Facilitates formation of a nearly continuous Pt layer after sufficient plasma exposure, Reduces the dependence on defect sites alone for Pt nucleation, improving uniformity\"}]},{\"panel_id\":\"c\",\"items\":[{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"Partial conversion of sp² to sp³ carbon, formation of C–O (286.4 eV) and C=O (289.0 eV) bonds, and the appearance of plasmon features at 290.4 eV and 293.2 eV.\"}]}]","bbox":[{"panel_id":"a","x":3,"y":4,"width":371,"height":282},{"panel_id":"b","x":379,"y":4,"width":355,"height":266},{"panel_id":"c","x":746,"y":5,"width":359,"height":265},{"panel_id":"d","x":4,"y":286,"width":355,"height":254},{"panel_id":"e","x":377,"y":288,"width":353,"height":254},{"panel_id":"f","x":751,"y":285,"width":353,"height":255}],"source":"icdar2026-competition-data/dev/atomic-layer-deposition/simulation-usecase/13/images/fig10.jpg","provenance":{"source_annotation":"icdar2026-competition-data/dev/atomic-layer-deposition/simulation-usecase/13/images/fig10.json","source_content":"icdar2026-competition-data/dev/atomic-layer-deposition/simulation-usecase/13/content.json","source_pdf":["icdar2026-competition-data/dev/atomic-layer-deposition/simulation-usecase/13/Bora Karasulu et al.pdf"],"main_category":"atomic-layer-deposition","sub_category":"simulation-usecase","paper_id":"13","first_classification_panel_id":"a","first_classification_label":"multi spectra chart","caption_source":"content.json:img_caption"},"width":1108,"height":541,"image_format":"jpeg","image_sha256":"652c94cf0c11785a58d6dd234b64d9653960db31499bfb0b6d3f96a1117304df","metadata_license":"CC BY 4.0","image_license":"source_publisher_rights_reserved","image_reuse_status":"non_commercial_research_use_only","schema_version":"1.0.0"}
{"file_name":"images/validation_atomic-layer-etching_experimental-usecase_24_figure_10.jpg","caption":"Figure 10. Infrared absorbance showing the loss of  $\\mathrm{Al - O}$  stretching vibration in bulk  $\\mathrm{Al}_2\\mathrm{O}_3$  versus number of  $\\mathrm{Al}_2\\mathrm{O}_3$  ALE cycles at  $300^{\\circ}\\mathrm{C}$ . These FTIR spectra were referenced to the initial  $\\mathrm{ZrO}_2$  nanoparticles.","id":"validation/atomic-layer-etching/experimental-usecase/24/figure_10","sample_id":"atomic-layer-etching/experimental-usecase/24/figure_10","subset":"multi-spectra-chart","split":"validation","classification":[{"panel_id":"a","label":"multi spectra chart"}],"summarization":"[{\"panel_id\":\"a\",\"text\":\"This in situ FTIR spectroscopy measurement shows the progressive loss of infrared absorbance from Al–O stretching vibrations (800–1000 cm⁻¹) during Al₂O₃ ALE at 300°C. The spectra are referenced to the initial ZrO₂ nanoparticle substrate. As the number of ALE cycles increases from 0 to 4, 6, and 8, the absorbance peak centered around 900 cm⁻¹ systematically decreases in intensity, directly confirming the removal of Al₂O₃ material. The Al₂O₃ film was initially grown using 15 cycles of Al₂O₃ ALD with TMA and H₂O at 150°C, then etched using sequential TMA and HF exposures at 300°C.\"}]","data_extraction":"[{\"panel_id\":\"a\",\"text\":\"| Wavenumber (cm⁻¹) | Absorbance (0 cycles) | Absorbance (4 cycles) | Absorbance (6 cycles) | Absorbance (8 cycles) |\\n|---|---:|---:|---:|---:|\\n| 1300 | ~0.06 | ~0.05 | ~0.04 | ~0.03 |\\n| 1100 | ~0.06 | ~0.05 | ~0.04 | ~0.03 |\\n| 940  | ~0.59 | ~0.56 | ~0.50 | ~0.40 |\\n| 900  | ~0.53 | ~0.52 | ~0.42 | ~0.38 |\\n| 800  | ~0.00 | ~0.00 | ~0.00 | ~0.00 |\\n| 700  | ~0.00 | ~0.00 | ~0.00 | ~0.00 |\"}]","vqa":"[{\"panel_id\":\"a\",\"items\":[{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"The absorbance intensity is studied as a function of the number of cycles of etching applied to the Al2O3 films.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"The etch rate is higher with 8 cycles, which is why the spectra show the lowest absorbance intensity.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"As the number of cycles increases, the absorbance peak of Al2O3 decreases slightly  and shifts towards higher wavenumber values.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The trend in absorbance is non-linear. This does not mean that the etching is non-linear, to conclude this, the integrated absorbance of the full peak must be considered.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"Al-F is a bond with permanent dipole so it will vibrate upon IR absorption.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"For thicker films, generally broader peaks are observed, by decreasing the film thickness with the etch process, the peak gets more narrow.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"No the composition does not change based on the given data, as the peak shape remains constant.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The Al–O stretching peak in the ~900–1000 cm⁻¹ region systematically decreases as the ALE cycle count increases from 0 to 8. Because FTIR absorbance is proportional to the amount of the corresponding bonding environment, this monotonic decrease indicates a reduction in Al–O content. This directly implies progressive thinning or removal of the Al₂O₃ film during the ALE process.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"- Acquire a reference spectrum (here: referenced to the initial ZrO2 nanoparticles) before ALE begins.\\n- Record spectra after defined numbers of ALE cycles (e.g., 0, 4, 6, 8).\\n- Identify the Al2O3/Al–O stretching region (here centered around ~900–1000 cm⁻¹).\\n- Compare peak height/area across cycles to check for a monotonic decrease.\\n- Confirm that the baseline regions (outside the Al–O band) remain relatively stable to rule out simple scaling artifacts.\\n- Interpret the decreasing Al–O band intensity as reduced Al–O content consistent with material removal.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"The Al–O stretching vibration in bulk Al2O3.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The Al–O band intensity provides a chemically specific indicator of the remaining Al₂O₃ material. An ALE endpoint could be defined when the Al–O absorbance falls below a predetermined threshold or approaches the baseline. Monitoring the rate of absorbance decrease per cycle can also reveal changes in etch efficiency, enabling real-time adjustment of exposure or cycle count to achieve consistent material removal.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"ZrO₂ nanoparticles were chosen as the substrate because they provide a high surface area that enhances the FTIR signal from the deposited Al₂O₃ film and subsequent surface reactions. Critically, ZrO₂ absorbs infrared radiation only between approximately 400–800 cm⁻¹, leaving an open spectral window above 800 cm⁻¹ where the Al–O stretching vibrations of Al₂O₃ can be monitored without interference. This allows clear observation of the Al₂O₃ absorbance changes during the ALE process. The nanoparticles were pressed into a tungsten grid that could be resistively heated for temperature control.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"The absorbance between 800 and 1000 cm⁻¹ progressively decreases with increasing ALE cycles, confirming the removal of Al₂O₃ material.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The broad absorbance peak between 800 and 1000 cm⁻¹ corresponds to Al–O stretching vibrations in the bulk Al₂O₃ film. The intensity of infrared absorbance is directly proportional to the amount of the absorbing species present, following Beer-Lambert principles. As the Al₂O₃ film is etched away through the sequential TMA and HF reactions, there are fewer Al–O bonds available to absorb infrared radiation at these frequencies. The progressive decrease in peak intensity from 0 to 8 ALE cycles therefore provides direct spectroscopic evidence that the Al₂O₃ material is being removed from the substrate.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"Yes. While QCM measures mass changes, FTIR provides chemical-specific information by tracking the loss of Al–O bonds and can also identify surface intermediates such as AlF* and AlCH₃* species formed after HF and TMA exposures, respectively.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"List\",\"answer\":\"1) Expose the Al₂O₃ surface to a fluorinating reactant (e.g., HF).\\n\\n2) Purge with inert gas to remove excess reactant and byproducts.\\n\\n3) Expose to a second reactant (e.g., TMA) to form volatile species.\\n\\n4) Purge again to clear the chamber.\\nReferencing to the initial ZrO₂ nanoparticles subtracts the strong infrared absorption background of the substrate, isolating the signal from the Al₂O₃ film and allowing accurate measurement of the Al–O bond removal.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"ALE is superior for 3D nanostructures because it offers anisotropic, self-limiting etching with perfect conformality. Wet etching is isotropic and difficult to control at the nanometer scale. The trade-off is that ALE is significantly slower and requires more complex equipment than a simple wet etch.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The Al–O bond concentration decreases linearly with each ALE cycle, as shown by the diminishing peak absorbance. This occurs because each cycle converts a self-limiting layer of surface Al₂O₃ into volatile aluminum fluoride and aluminum methyl species, which are purged away, systematically etching the film.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"This implies that ALE can precisely tune the gate dielectric thickness with atomic-scale accuracy. Such control is essential for setting the exact threshold voltage and leakage current in scaled transistors, enabling performance optimization and device matching across a wafer.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"It describes the number of ALE cycles and how the FTIR spectra changes after 4 ALE cycles, 6 ALE cycles and 8 ALE cycles.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"Al-O stretching is observed between 800 cm-1 and 1000 cm−1\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"the sample temperature was raised to 300 °C, and the Al2O3 film was etched using sequential exposures of TMA and HF. FTIR spectra recorded during the TMA and HF exposures at 300 °C. The progressive loss in absorbance between 800 and 1000 cm−1 with ALE cycles is in agreement with the etching of the Al2O3 film.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"Yes. These FTIR spectra were referenced to the initial ZrO2 nanoparticles\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The Al-O peak decreases  as the cycle count increases from 0 to 8. This indicates that the amount of material contributing to that vibration is decreasing with each cycle. Overall, the spectra are consistent with progressive etching of the Al₂O₃ layer during ALE.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"Systematic shift in peak position (from about 930 to ~921 cm⁻¹).\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"Peak shape\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"It decreases more slowly at the beginning.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"List\",\"answer\":\"0,4,6, 8.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"300 °C\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The peak near 1000 cm^-1 steadily decreases in height with increasing ALE cycles. The 0-cycle spectrum shows the strongest feature, and each followingspectrum is progressively lower. This indicates that repeated ALE steps remove or change the surface species responsible for this absorption.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"The absorbance progressively decreases with increasing ALE cycles.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"List\",\"answer\":\"Al–O stretching vibrations in bulk Al₂O₃, Surface hydroxyl (Al–OH) groups, indicating surface reactions during ALE\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The progressive loss of Al–O absorbance indicates effective etching of the Al₂O₃ film during ALE cycles. This confirms that the sequential TMA and HF exposures at 300 °C can selectively remove Al₂O₃ layers on ZrO₂ nanoparticles, which is critical for controlled layer-by-layer modification in atomic layer etching applications.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"}]}]","bbox":[{"panel_id":"a","x":0,"y":0,"width":664,"height":619}],"source":"icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/images/figure_10.jpg","provenance":{"source_annotation":"icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/images/figure_10.json","source_content":"icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/content.json","source_pdf":["icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/Trimethylaluminum as the Metal Precursor for the Atomic LayerEtching.pdf"],"main_category":"atomic-layer-etching","sub_category":"experimental-usecase","paper_id":"24","first_classification_panel_id":"a","first_classification_label":"multi spectra chart","caption_source":"content.json:img_caption"},"width":664,"height":619,"image_format":"jpeg","image_sha256":"cc176a3f88b42586cf2564d95daeda8a1b2b04caf52cc15862a44378cf800f06","metadata_license":"CC BY 4.0","image_license":"source_publisher_rights_reserved","image_reuse_status":"non_commercial_research_use_only","schema_version":"1.0.0"}
{"file_name":"images/validation_atomic-layer-etching_experimental-usecase_24_figure_11.jpg","caption":"Figure 11 displays the FTIR difference spectra at 800-1300  $\\mathrm{cm}^{-1}$  after consecutive TMA and HF exposures during the fifth","id":"validation/atomic-layer-etching/experimental-usecase/24/figure_11","sample_id":"atomic-layer-etching/experimental-usecase/24/figure_11","subset":"multi-spectra-chart","split":"validation","classification":[{"panel_id":"a","label":"multi spectra chart"}],"summarization":"[{\"panel_id\":\"a\",\"text\":\"The FTIR spectra compare TMA and HF exposures on Al2O3 at 300 °C. The TMA trace shows a strong positive peak near 1230 cm^-1 associated with CH3 deformation, while the HF trace shows a negative feature at the same position. HF also produces additional negative bands in the 1100–900 cm^-1 region that are linked to AlF3 formation but the TMA spectrum remains close to baseline in this range.\"}]","data_extraction":"[{\"panel_id\":\"a\",\"text\":\"| Wavenumber (cm⁻¹) | Absorbance | Condition |\\n| ----------------- | ---------- | --------- |\\n|       ~1230       |  ~+0.065   |   TMA     |\\n|       ~1230       | ~-0.055    |   HF      |\\n|       ~1100       | ~+0.010    |   TMA     |\\n|       ~1100       | ~-0.015    |   HF      |\\n|       ~950        | ~+0.005    |   TMA     |\\n|       ~950        | ~-0.020    |   HF      |\"}]","vqa":"[{\"panel_id\":\"a\",\"items\":[{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"During the cycles, TMA provides the film with CH3 groups  but removes AlF3 from the surface, in accordance with the negative value between 800 and 950 cm⁻¹. Also, after exposure to HF, it is possible to observe, the an increased peak in AlF3 band, due to the formation of AlF3.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"No, in this case, the TMA provides the film with CH3 groups based on the positive absorbance peaks.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"The HF exposure produces the surface etching, resulting in the desorption of CH3 groups and the provision of AlF3 to the surface.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"A positive peak means that bonds with corresponding vibrations are added to the surface, whereas a negative peak indicates the removal of bonds from the surface.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"Yes, the positive and negative CH3 absorption peak are equaly big.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"If AlF3 is added, this would result in a positive peak above 0, this is not observed, indicating that the baseline should likely be a bit higher.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"List\",\"answer\":\"Yes, FTIR is an option on powder samples, and RAIRS can be used on planar reflective substrates.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"Because these are FTIR difference spectra, the sign of a feature indicates whether a vibrational mode is being created or removed relative to the reference state. After TMA exposure, the positive δₛ(CH₃) peak near ~1225 cm⁻¹ shows that methyl groups are added to the surface, producing a methyl-terminated Al₂O₃ surface. After HF exposure, the same feature becomes negative, indicating that these CH₃ species are consumed or removed. This sign inversion directly demonstrates the self-limiting alternation between methylation and demethylation that underpins the ALE cycle.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"After TMA (blue):\\n-Strong positive CH₃ band at ~1225 cm⁻¹\\n-Negative deviation mainly centered near ~960–900 cm⁻¹\\n-Perturbation of oxide vibrations due to surface methylation\\nAfter HF (red):\\n-CH₃ band becomes negative (methyl removal)\\n-Negative features extend more strongly into ~900–800 cm⁻¹\\n-Spectral evolution consistent with fluorination and AlFₓ-like surface formation\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The TMA half-cycle converts surface Al sites into methyl-terminated species, which is clearly reflected by the strong positive δₛ(CH₃) feature near ~1225 cm⁻¹. This methyl termination modifies the local Al–O bonding environment, producing negative deviations in the oxide-related spectral region. The HF half-cycle reverses this chemistry by removing methyl groups and introducing fluorine, leading to disappearance or inversion of the CH₃ band and stronger negative features in the lower-wavenumber region associated with fluorinated Al–O or AlFₓ-like structures. Structurally, this alternating termination is essential for achieving self-limiting ALE rather than uncontrolled etching.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"-The ~1225 cm⁻¹ δₛ(CH₃) band can serve as a cycle-completion marker: positive after TMA and negative after HF.\\n-Residual positive CH₃ signal after HF would indicate incomplete HF reaction or insufficient purge.\\n-Growth of negative features in the ~900–800 cm⁻¹ region confirms effective fluorination during HF exposure.\\n-Consistent alternation between CH₃ and AlFₓ spectral signatures verifies that the process is operating in a true ALE regime rather than continuous etching.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"After the TMA exposure, AlCH₃* surface species are identified (as AlF₂(CH₃)* or –OAl(CH₃)₂*) via the methyl deformation mode at ~1212 cm⁻¹. After the HF exposure, AlF* surface species are formed, and the AlCH₃* species are removed.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The spectral changes in the 800–1000 cm⁻¹ region are opposite for TMA and HF exposures, reflecting their complementary roles in the ALE mechanism. After TMA exposure, a decrease in absorbance is observed in this region, corresponding to the loss of Al–F stretching vibrations as TMA removes the AlF₃ surface layer through the ligand-exchange reaction. After HF exposure, the spectrum shows a complex pattern: a broad absorbance loss from Al₂O₃ being converted to AlF₃, with a smaller absorbance increase between ~850–950 cm⁻¹ superimposed, indicating formation of the new AlF₃ layer. This cyclic behavior confirms the fluorination/ligand-exchange mechanism.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"Although all these species would exhibit a methyl deformation mode near 1212 cm⁻¹, the vibrational feature is attributed to surface-bound AlF₂(CH₃)* or –OAl(CH₃)₂* rather than AlF(CH₃)₂ because AlF(CH₃)₂ is a volatile species with a vapor pressure of 80 Torr at 100°C. At the 300°C reaction temperature, any AlF(CH₃)₂ formed would rapidly desorb from the surface and would not be detected in the FTIR spectrum. The observed 1212 cm⁻¹ peak therefore corresponds to methyl-containing species that remain bound to the surface after TMA exposure.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"No\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"List\",\"answer\":\"1. HF exposure (fluorination)\\n\\n2. Purge\\n\\n3. TMA exposure (ligand exchange)\\n\\n4.  Purge\\nThe purge removes volatile byproducts and unreacted precursors, preventing gas-phase reactions and ensuring each subsequent half-cycle begins with a clean, well-defined surface.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"If the Red loss peak were smaller than the Blue gain peak, it would imply incomplete removal of methyl ligands during the HF step. This accumulation of organic residue would eventually contaminate the surface, blocking active sites and causing the etch rate to slow down or stop entirely over time (drift), rather than maintaining the constant rate required for manufacturing.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"Thermal ALE is preferable for temperature-sensitive substrates. It operates at a defined, moderate temperature (300°C) without ion bombardment, minimizing substrate damage and defect generation. Plasma ALE, while potentially faster, risks ion-induced damage and requires careful management of UV/VUV photon effects.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"This implies the process will be perfectly conformal in high-aspect-ratio structures. The self-limiting surface reactions ensure etching proceeds layer-by-layer uniformly on all exposed surfaces, regardless of geometry, enabling precise depth control and profile retention in complex 3D architectures.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"del(CH3) = AlCH3* species may be present as either\\n1. AlF(CH3)2*\\n2. AlF2(CH3)*\\n3. −OAl(CH3)2*.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"AlCH3* represents methyl deformation mode and species may be present as either\\n1. AlF(CH3)2*\\n2. AlF2(CH3)*\\n3. −OAl(CH3)2*.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"AlF(CH3)2 is expected to have a higher volatility than other species, the vibrational feature at 1212 cm−1 is likely attributed to AlF2(CH3)* or −OAl(CH3)2* . In addition, a decrease in absorbance between ∼850 and 975 cm−1 is observed that is consistent with the loss of absorbance from Al−F stretching vibrations as TMA removes the AlF3 surface layer. The absorbance is completely removed for the vibrational feature attributed to the addition of AlCH3* species after HF exposure. This loss of absorbance is in accord with the conversion of AlCH3* surface species to AlF* species. This is in agreement with the conversion of Al2O3 into AlF. Hence alternating the exposure eventually leads to removal/etching.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"An increase in absorbance at 1212 cm^-1 is observed and a decrease between 850 and 975 cm^-1. The increase at 1212 cm^-1 is attributed to the formation of AlCH3* surface species, which may be present as either AlF(CH3)2*, AlF2(CH3)*, or −OAl(CH3)2*. Given the high volatility of AlF(CH3)2, the most likely species are AlF2(CH3)* or −OAl(CH3)2*. The loss of absorbance between 850 and 975 cm^-1 is consistent with the loss of Al-F bonds as TMA removes the AlF3 surface layer.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"As the magnitudes of absorbance loss and increase are the same, it means that all AlCH3* surface species get converted to AlF* surface species during HF exposure (and vice versa during TMA exposure).\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"800 to 1100 cm^-1.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"800 to 975 cm^-1.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"Methyl groups, as indicated by the gain in the δs(CH₃) region.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"AlF₃\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"Methyl groups, as indicated by the loss in the δs(CH₃) region.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The TMA half-cycle appears to drive the Al₂O₃ removal. It shows a clear negative change in the Al₂O₃ band region (~900–1000 cm⁻¹), consistent with loss of Al–O absorbance during that step. In contrast, the HF half-cycle mainly removes CH₃ (negative CH₃ band) and increases AlF₃-related bands (~800–950 cm⁻¹), suggesting surface fluorination rather than the main oxide-removal step.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"300 °C.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The TMA spectrum shows a strong positive peak at this position, while the HF spectrum displays a negative feature of similar magnitude. This indicates that TMA adds CH₃ containing species to the surface,  where HF removes or changes them. The opposite signs reflect contrasting surface reactions during each exposure.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"List\",\"answer\":\"TMA exposure,  HF exposure.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"The absorbance at ~1212 cm⁻¹ decreases after HF exposure, indicating conversion of AlCH₃* to AlF* species.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"List\",\"answer\":\"Al–O stretching vibrations (~850–975 cm⁻¹), AlCH₃ methyl deformation (~1212 cm⁻¹), Al–F stretching and AlF₃ formation (~850–1100 cm⁻¹)\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The FTIR difference spectra demonstrate that the ALE process effectively modifies the Al₂O₃ surface. TMA exposures form AlCH₃* species, while subsequent HF exposures remove these species and convert Al₂O₃ to AlF₃, as indicated by broad absorbance changes. This confirms that the sequential, self-limiting reactions are working as intended, enabling controlled layer-by-layer etching of Al₂O₃ on ZrO₂ nanoparticles.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"}]}]","bbox":[{"panel_id":"a","x":0,"y":0,"width":666,"height":608}],"source":"icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/images/figure_11.jpg","provenance":{"source_annotation":"icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/images/figure_11.json","source_content":"icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/content.json","source_pdf":["icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/Trimethylaluminum as the Metal Precursor for the Atomic LayerEtching.pdf"],"main_category":"atomic-layer-etching","sub_category":"experimental-usecase","paper_id":"24","first_classification_panel_id":"a","first_classification_label":"multi spectra chart","caption_source":"content.json:img_caption"},"width":666,"height":608,"image_format":"jpeg","image_sha256":"3b8d2c3e7e53c19a54c0c681768b6929dcf23dbc35c6f9129914d3fc56c7d670","metadata_license":"CC BY 4.0","image_license":"source_publisher_rights_reserved","image_reuse_status":"non_commercial_research_use_only","schema_version":"1.0.0"}
{"file_name":"images/validation_atomic-layer-etching_experimental-usecase_24_figure_12.jpg","caption":"Figure 12. Difference infrared absorbance spectra from 2500 to 4000  $\\mathrm{cm}^{-1}$  during  $\\mathrm{Al}_2\\mathrm{O}_3$  ALE at  $300^{\\circ}\\mathrm{C}$ . The difference spectra recorded after the (a) TMA and (b) HF exposures were referenced using the spectra after the previous HF and TMA exposures, respectively.","id":"validation/atomic-layer-etching/experimental-usecase/24/figure_12","sample_id":"atomic-layer-etching/experimental-usecase/24/figure_12","subset":"multi-spectra-chart","split":"validation","classification":[{"panel_id":"a","label":"multi spectra chart"}],"summarization":"[{\"panel_id\":\"a\",\"text\":\"The FTIR spectra compare TMA and HF exposures on Al2O3 at 300 °C in the 4000–2500 cm^-1 region. The TMA spectrum shows a positive CH3 stretching feature near 2950 cm^-1, while the HF spectrum shows negative absorbance changes at this position. HF also produces a broader negative band near 3200 cm^-1, whereas the TMA trace remains close to baseline there. These differences show opposite surface reactions during the two exposures.\"}]","data_extraction":"[{\"panel_id\":\"a\",\"text\":\"| Wavenumber (cm⁻¹) | Absorbance | Condition |\\n| ----------------- | ---------- | --------- |\\n|      ~2950        |  ~+0.010   |    TMA    |\\n|      ~2950        |  ~-0.005   |    HF     |\\n|      ~3200        |  ~+0.002   |    TMA    |\\n|      ~3200        |  ~-0.010   |    HF     |\\n|      ~3600        |  ~0.000    |    TMA    |\\n|      ~3600        |  ~-0.003   |    HF     |\"}]","vqa":"[{\"panel_id\":\"a\",\"items\":[{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"300 °C\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"TMA\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"TMA, based on the positive absorbance value.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"In this case, positive values represent groups being supplied to the surface. Conversely, negative values show groups being lost from the surface.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"All the CH3 seems to be removed as the peaks have similar height.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"No, there is no HF formed as there is no positive peak visible in the HF IR active region.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"At least three can be observed. The main peak consists of two sharp peaks close together, with a shoulder to the right.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"No, in general there must be a certain signal to noise ratio to be able to identify actual peaks. In this region, the signal seems to be fully comprised of noise.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"In FTIR difference spectra, a positive signal indicates formation of a vibrational species relative to the reference state, while a negative signal indicates its removal. The positive band at ~2950–2900 cm⁻¹ after TMA shows that CH₃/C–H-containing surface species are formed during the TMA half-cycle. After HF, the same region becomes strongly negative, indicating that these species are consumed or removed. This sign inversion directly demonstrates cyclic surface termination changes that are characteristic of Al₂O₃ ALE.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"The HF half-cycle produces the larger magnitude change (≈ −0.010) compared with the TMA half-cycle (≈ +0.007).\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"-CH₃/C–H region (~2950–2900 cm⁻¹):\\n1) After TMA: positive (≈ +0.0070)\\n2) After HF: negative (≈ −0.0100)\\n\\n-Lower C–H tail (~2750–2500 cm⁻¹):\\n1) After TMA: small positive (≈ +0.0020)\\n2) After HF: small negative (≈ −0.0030)\\n\\n-ν(HF)-marked higher wavenumbers (~4000–3250 cm⁻¹):\\n1) After TMA: ~0.0000 (near baseline)\\n2) After HF: slightly negative (≈ −0.0015)\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"A robust acceptance criterion is the behavior of the CH stretching region around 2950–2900 cm⁻¹. A healthy process should show a reproducible positive excursion after TMA and a reproducible negative excursion after HF. Loss of the positive CH signal after TMA would suggest incomplete methylation, while failure of the signal to invert after HF would indicate insufficient HF reaction or purge issues. Monitoring both sign and magnitude provides a simple, chemistry-specific indicator of cycle completeness.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The absence of HF* surface species at 300°C is critical for enabling etching rather than deposition. At lower temperatures, HF* species remain adsorbed on the surface and react with incoming TMA to form AlF₃, leading to AlF₃ ALD growth. At 300°C, HF* species desorb from the surface, which allows TMA to instead accept fluorine directly from the underlying AlF₃ layer through the ligand-exchange transmetalation reaction, producing volatile AlF(CH₃)₂ etch products. Temperature therefore determines whether the TMA/HF chemistry leads to AlF₃ ALD or Al₂O₃ ALE.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"The C–H stretching peaks at ~2900 and ~2950 cm⁻¹ show positive absorbance (gain) after TMA exposure and negative absorbance (complete loss) after HF exposure.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"These peaks correspond to the symmetric (~2900 cm⁻¹) and asymmetric (~2950 cm⁻¹) C–H stretching vibrations of AlCH₃* surface species.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The two spectral regions provide complementary information about different aspects of the ALE surface chemistry. The 800–1300 cm⁻¹ region monitors the Al–O and Al–F stretching vibrations, revealing the removal of the AlF₃ surface layer during TMA exposure and fluorination of Al₂O₃ during HF exposure. The 2500–4000 cm⁻¹ region tracks the C–H stretching vibrations, confirming the cyclic addition and removal of methyl groups during TMA and HF half-cycles. Additionally, the higher wavenumber region allows detection of any HF* surface intermediates; their absence at 300°C explains why etching occurs rather than AlF₃ deposition. Together, these data provide a complete picture of the surface species involved in each half-reaction.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The FTIR measures the appearance of new C–H stretching vibrations (νₐₛ,ₛ(CH₃)) from methyl groups deposited by TMA. This confirms the ligand-exchange reaction where TMA replaces surface fluorides with –CH₃, a critical step in forming volatile etch products.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"FTIR provides direct chemical bonding information, identifying specific surface species like Al–CH₃ and adsorbed HF. A limitation is that it requires specialized transparent substrates or particles, whereas QCM works on any thin film but only measures mass change, not chemistry.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The ν(HF) feature indicates that molecular HF adsorbs onto the Al₂O₃ surface before dissociating. This adsorbed precursor state is essential for the subsequent fluorination reaction that converts surface Al–O bonds to Al–F bonds, enabling the etching mechanism.\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"No, While the self-limiting mechanism is confirmed, selectivity depends on the relative reactivity of HF/TMA with Al₂O₃ versus SiO₂. The spectra alone don't prove selectivity; a separate experiment comparing etch rates on both materials is required to guarantee selective removal.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"After the TMA exposure,  an increase in absorbance is observed at ∼2900 and 2950 cm−1 .\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"After TMA exposure, n increase in absorbance is observed at ∼2900 and 2950 cm−1, this absorbance gain is in accord with the formation of AlF2(CH3)* or −OAl(CH3)2* species .  After the HF exposure, an absorbance decrease at ∼2900 and ∼2950 cm−1 is consistent with the removal of the previously added AlCH3* species\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"At about 2900 and 2950 cm^-1.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"AlCH3* surface species, consistent with the formation of AlF2(CH3)* or -OAl(CH3)2*.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"The absorbance at those wavenumbers decreases, indicating the removal of AlCH3* surface species.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"No\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"HF removes methyl (–CH₃) species from the surface.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"TMA adds methyl (–CH₃) groups to the surface\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The spectra at 300 °C point to an ALE-like regime rather than AlF₃ ALD. The spectra indicate no clear change in the ν(HF) region. If HF surface species are required intermediates for ALD, then the lack of a clear HF-related band suggests those HF species are not persisting on the surface, and the ALD pathway is not favored at this temperature.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"CH₃ doesn't accumulate over repeated cycles, based on the magnitude of the absorbance during each half-cycle.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"List\",\"answer\":\"~2950cm^-1, ~3200cm^-1, ~3600cm^-1\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"300 °C.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The TMA spectrum shows a small positive peak at this position, consistent with CH3 stretching from methyl groups bonded to the surface. In contrast, the HF spectrum displays a negative feature at the same location, indicating removal or changeof these groups. This opposite behavior shows the different surface chemistry  caused by the two exposures.\"},{\"question_type\":\"Comparative/Trend\",\"questions\":\"\",\"answer_type\":\"Factoid\",\"answer\":\"The absorbance at ~2900 cm⁻¹ and ~2950 cm⁻¹ decreases after HF exposure, indicating removal of AlCH₃* species.\"},{\"question_type\":\"Structure-Property\",\"questions\":\"\",\"answer_type\":\"List\",\"answer\":\"Symmetric stretching of AlCH₃ (~2900 cm⁻¹), Asymmetric stretching of AlCH₃ (~2950 cm⁻¹), Absence of HF vibrational features between ~3000–3675 cm⁻¹\"},{\"question_type\":\"Application/Performance\",\"questions\":\"\",\"answer_type\":\"Paragraph\",\"answer\":\"The increase in absorbance at ~2900 and 2950 cm⁻¹ after TMA exposure and their subsequent removal after HF exposure demonstrate that the ALE process is effectively forming and removing AlCH₃* surface species. The absence of HF* features in this region indicates that at 300 °C, HF desorbs efficiently, enabling TMA to react with the underlying AlF₃ layer and produce controlled etching of Al₂O₃. These trends confirm the self-limiting nature and effectiveness of the ALE process under the described conditions.\"},{\"question_type\":\"Process-Oriented\",\"questions\":\"\",\"answer_type\":\"Yes/No\",\"answer\":\"Yes\"}]}]","bbox":[{"panel_id":"a","x":0,"y":0,"width":655,"height":580}],"source":"icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/images/figure_12.jpg","provenance":{"source_annotation":"icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/images/figure_12.json","source_content":"icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/content.json","source_pdf":["icdar2026-competition-data/dev/atomic-layer-etching/experimental-usecase/24/Trimethylaluminum as the Metal Precursor for the Atomic LayerEtching.pdf"],"main_category":"atomic-layer-etching","sub_category":"experimental-usecase","paper_id":"24","first_classification_panel_id":"a","first_classification_label":"multi spectra chart","caption_source":"content.json:img_caption"},"width":655,"height":580,"image_format":"jpeg","image_sha256":"d91ef7fcdae09c5b369aac167deb329f805abc5fb333cf480c618227a5f8e4e8","metadata_license":"CC BY 4.0","image_license":"source_publisher_rights_reserved","image_reuse_status":"non_commercial_research_use_only","schema_version":"1.0.0"}