FiG. 2. (a) Thermogravimetric analysis and (b) vapor pressures of the  $\mathrm{Zr}$  precursors.

The chart shows the thermogravimetric analysis curves (weight loss percentage as a function of temperature) for the Zr precursors. Zr(Cp)(ᵗBuDAD)(OⁱPr) evaporates with minimal residue, two other precursors show decomposition.

The chart illustrates the vapor pressure of Zr complexes (Zr(Cp)(ᵗBuDAD)(OⁱPr),Zr(MeCp)(TMEA), Zr(Me₅Cp)(TEA))  at different temperatures. Zr(Cp)(ᵗBuDAD)(OⁱPr) achieves highest vapor pressures at low temperatures.

| Temperature (°C) | Weight loss (%) | Reagent + Conditions |
|---|---|---|
| 6 | 100.8 | Zr(Me_5Cp)(TEA) (vac) |
| 98 | 100.8 | Zr(Me_5Cp)(TEA) (vac) |
| 189 | 82.9 | Zr(Me_5Cp)(TEA) (vac) |
| 231 | 15.3 | Zr(Me_5Cp)(TEA) (vac) |
| 299 | 13.0 | Zr(Me_5Cp)(TEA) (vac) |
| 406 | 7.6 | Zr(Me_5Cp)(TEA) (vac) |
| 498 | 6.8 | Zr(Me_5Cp)(TEA) (vac) |
| 6 | 100.8 | Zr(Me_5Cp)(TEA) (atm) |
| 98 | 100.8 | Zr(Me_5Cp)(TEA) (atm) |
| 205 | 92.6 | Zr(Me_5Cp)(TEA) (atm) |
| 270 | 68.9 | Zr(Me_5Cp)(TEA) (atm) |
| 347 | 63.1 | Zr(Me_5Cp)(TEA) (atm) |
| 423 | 34.8 | Zr(Me_5Cp)(TEA) (atm) |
| 497 | 29.3 | Zr(Me_5Cp)(TEA) (atm) |
| 6 | 100.8 | Zr(MeCp)(TMEA) (atm) |
| 98 | 100.8 | Zr(MeCp)(TMEA) (atm) |
| 202 | 98.4 | Zr(MeCp)(TMEA) (atm) |
| 285 | 68.5 | Zr(MeCp)(TMEA) (atm) |
| 317 | 14.6 | Zr(MeCp)(TMEA) (atm) |
| 418 | 11.8 | Zr(MeCp)(TMEA) (atm) |
| 498 | 11.5 | Zr(MeCp)(TMEA) (atm) |
| 6 | 100.8 | Zr(Cp)(tBuDAD)(O^iPr) (atm) |
| 98 | 100.8 | Zr(Cp)(tBuDAD)(O^iPr) (atm) |
| 183 | 94.6 | Zr(Cp)(tBuDAD)(O^iPr) (atm) |
| 234 | 56.5 | Zr(Cp)(tBuDAD)(O^iPr) (atm) |
| 263 | 2.9 | Zr(Cp)(tBuDAD)(O^iPr) (atm) |
| 409 | 2.1 | Zr(Cp)(tBuDAD)(O^iPr) (atm) |
| 498 | 1.4 | Zr(Cp)(tBuDAD)(O^iPr) (atm) |

| Temperature (°C) | Vapor pressure (Torr) | Reagent |
|---|---|---|
| 100 | 0.6 | Zr(Cp)(tBuDAD)(O^iPr) |
| 109 | 0.8 | Zr(Cp)(tBuDAD)(O^iPr) |
| 119 | 1.2 | Zr(Cp)(tBuDAD)(O^iPr) |
| 129 | 1.5 | Zr(Cp)(tBuDAD)(O^iPr) |
| 139 | 2.0 | Zr(Cp)(tBuDAD)(O^iPr) |
| 128 | 0.2 | Zr(Me_5Cp)(TEA) |
| 138 | 0.3 | Zr(Me_5Cp)(TEA) |
| 149 | 0.5 | Zr(Me_5Cp)(TEA) |
| 159 | 0.7 | Zr(Me_5Cp)(TEA) |
| 168 | 0.7 | Zr(Me_5Cp)(TEA) |
| 178 | 0.8 | Zr(Me_5Cp)(TEA) |
| 188 | 1.4 | Zr(Me_5Cp)(TEA) |
| 127 | 0.2 | Zr(MeCp)(TMEA) |
| 137 | 0.2 | Zr(MeCp)(TMEA) |
| 147 | 0.3 | Zr(MeCp)(TMEA) |
| 157 | 0.5 | Zr(MeCp)(TMEA) |
| 167 | 0.7 | Zr(MeCp)(TMEA) |
| 178 | 1.6 | Zr(MeCp)(TMEA) |
| 188 | 2.5 | Zr(MeCp)(TMEA) |

Answer: Zr(Cp)(ᵗBuDAD)(OⁱPr)

Answer: Applying vacuum conditions significantly reduces decomposition compared to atmospheric pressure. The thermogravimetric analysis shows a residue of ~30% at the highest temperature studied. Under vacuum, the residue is ~ 6%. The reduction in residue is a sign of reduced thermal decomposition.

Answer: Zr(Me₅Cp)(TEA) under vacuum.

Answer: Zr(Cp)(ᵗBuDAD)(OⁱPr) achieves highest vapor pressures at lower temperatures.

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


FiG. 3. (a) Film growth rates at different temperatures with (a) water and (b) ozone as the oxygen source. Pulse times for  $\mathrm{Zr}$  precursors,  $\mathrm{H}_2\mathrm{O}$  and  $\mathrm{O_3}$  were  $1.0\mathrm{s}$  and purge times for all pulses  $1.5\mathrm{s}$

The chart shows the growth rates against temperatures for Zr precursors when using water as the oxygen source. The growth rate of films with Zr(Cp)(tBuDAD)(O^Pr), Zr(MeCp)(TMEA), and Zr(Me_5Cp)(TEA) compounds increases with temperature, with Zr(Cp)(tBuDAD)(O^Pr) showing the highest growth rate.

The chart shows the growth rates against temperatures for Zr precursors when using ozone as the oxygen source. The growth rate of a film with Zr(MeCp)(TMEA) as precursor sligthtly decreases with temperatures. The growth rate with Zr(Cp)(tBuDAD)(O^Pr) and Zr(Me_5Cp)(TEA) compounds increases with temperature, with Zr(Cp)(tBuDAD)(O^Pr) it is showing the highest growth rate.

| Temperature (°C) | Growth rate (Å/cycle) | Reagent |
|---|---|---|
| 198 | 0,22 | Zr(MeCp)(TMEA) |
| 252 | 0,26 | Zr(MeCp)(TMEA) |
| 300 | 0,25 | Zr(MeCp)(TMEA) |
| 348 | 0,27 | Zr(MeCp)(TMEA) |
| 373 | 0,32 | Zr(MeCp)(TMEA) |
| 398 | 0,09 | Zr(Me_5Cp)(TEA) |
| 424 | 0,20 | Zr(Me_5Cp)(TEA) |
| 250 | 0,17 | Zr(Cp)(tBuDAD)(O^iPr) |
| 300 | 0,43 | Zr(Cp)(tBuDAD)(O^iPr) |
| 324 | 0,62 | Zr(Cp)(tBuDAD)(O^iPr) |
| 350 | 0,59 | Zr(Cp)(tBuDAD)(O^iPr) |
| 375 | 0,63 | Zr(Cp)(tBuDAD)(O^iPr) |
| 398 | 0,68 | Zr(Cp)(tBuDAD)(O^iPr) |
| 425 | 0,94 | Zr(Cp)(tBuDAD)(O^iPr) |

| Temperature (°C) | Growth rate (Å/cycle) | Reagent |
|---|---|---|
| 250 | 0,09 | Zr(Me_5Cp)(TEA) |
| 275 | 0,19 | Zr(Me_5Cp)(TEA) |
| 300 | 0,29 | Zr(Me_5Cp)(TEA) |
| 350 | 0,38 | Zr(Me_5Cp)(TEA) |
| 374 | 0,36 | Zr(Me_5Cp)(TEA) |
| 400 | 0,38 | Zr(Me_5Cp)(TEA) |
| 426 | 0,39 | Zr(Me_5Cp)(TEA) |
| 252 | 0,39 | Zr(Cp)(tBuDAD)(O^iPr) |
| 300 | 0,66 | Zr(Cp)(tBuDAD)(O^iPr) |
| 377 | 1,28 | Zr(Cp)(tBuDAD)(O^iPr) |
| 198 | 0,64 | Zr(MeCp)(TMEA) |
| 250 | 0,57 | Zr(MeCp)(TMEA) |
| 300 | 0,57 | Zr(MeCp)(TMEA) |
| 352 | 0,52 | Zr(MeCp)(TMEA) |
| 375 | 0,52 | Zr(MeCp)(TMEA) |

Answer: Zr(Me₅Cp)(TEA) displays the lowest growth rates among 3 precursors. It features bulky ligands that sterically shield the central zirconium atom, preventing efficient access for reactants and resulting in significantly slower growth rates. Additionally, the TEA ligand coordinates through three oxygen atoms to form chelating bonds that are  stronger than the nitrogen-based bonds in the other complexes, which reduces reactivity toward weak oxidants like water.

Answer: Zr(Me₅Cp)(TEA) (did not react to water below 400 °C).

Answer: Zr(MeCp)(TMEA) at approx. 250-350 °C.

Answer: Zr(MeCp)(TMEA), Zr(Me₅Cp)(TEA).


FIG. 4. Film densities at different deposition temperatures with (a) water and (b) ozone as the oxygen source.

The chart shows the density of films deposited with water and Zr(Cp)(ᵗBuDAD)(OⁱPr), Zr(MeCp)(TMEA), or Zr(Me₅Cp)(TEA) as a function of temperature.

The chart shows the density of films deposited with ozone and Zr(Cp)(ᵗBuDAD)(OⁱPr), Zr(MeCp)(TMEA), or Zr(Me₅Cp)(TEA) as a function of temperature.

| Temperature (°C) | Density (g/cm³) | Precursor |
|---|---|---|
| 398 | 4.7 | Zr (Me_5Cp) (TEA) |
| 423 | 4.7 | Zr (Me_5Cp) (TEA) |
| 200 | 3.8 | Zr (MeCp) (TMEA) |
| 249 | 4.4 | Zr (MeCp) (TMEA) |
| 300 | 5.2 | Zr (MeCp) (TMEA) |
| 325 | 5.6 | Zr (MeCp) (TMEA) |
| 347 | 5.8 | Zr (MeCp) (TMEA) |
| 375 | 5.8 | Zr (MeCp) (TMEA) |
| 248 | 4.7 | Zr (Cp) (tBuDAD) (O^iPr) |
| 299 | 5.1 | Zr (Cp) (tBuDAD) (O^iPr) |
| 324 | 5.1 | Zr (Cp) (tBuDAD) (O^iPr) |
| 347 | 5.2 | Zr (Cp) (tBuDAD) (O^iPr) |
| 374 | 5.7 | Zr (Cp) (tBuDAD) (O^iPr) |
| 397 | 5.7 | Zr (Cp) (tBuDAD) (O^iPr) |
| 424 | 5.8 | Zr (Cp) (tBuDAD) (O^iPr) |

| Temperature (°C) | Density (g/cm³) | Precursor |
|---|---|---|
| 249 | 5,4 | Zr(Me_5Cp)(TEA) |
| 275 | 5,6 | Zr(Me_5Cp)(TEA) |
| 301 | 5,8 | Zr(Me_5Cp)(TEA) |
| 350 | 5,9 | Zr(Me_5Cp)(TEA) |
| 375 | 5,9 | Zr(Me_5Cp)(TEA) |
| 399 | 5,9 | Zr(Me_5Cp)(TEA) |
| 426 | 5,9 | Zr(Me_5Cp)(TEA) |
| 201 | 3,8 | Zr(MeCp)(TMEA) |
| 250 | 4,5 | Zr(MeCp)(TMEA) |
| 302 | 5,6 | Zr(MeCp)(TMEA) |
| 350 | 5,9 | Zr(MeCp)(TMEA) |
| 375 | 5,9 | Zr(MeCp)(TMEA) |
| 375 | 5,9 | Zr(MeCp)(TMEA) |
| 250 | 5,1 | Zr(Cp)(tBuDAD)(O^iPr) |
| 298 | 5,7 | Zr(Cp)(tBuDAD)(O^iPr) |
| 375 | 5,9 | Zr(Cp)(tBuDAD)(O^iPr) |

Answer: Zr(MeCp)(TMEA) (due to higher density).

Answer: 300°C would lead to the higher amount of deposited material. Although the growth rates are equal, the film density increased from ~4.5 g/cm3 to ~5.5 g/cm3, as the temperature rises from 250°C to 300°C. The increase in density means that more atoms are packed into the film at the higher temperature.

Answer: After ~350 °C at ~ 5.8 g/cm3.

Answer: ~350 °C and above.


FIG. 9. Leakage current density curves of the  $\mathrm{ZrO_2}$  films deposited with  $\mathrm{O_3}$  at  $300^{\circ}\mathrm{C}$ . The polarity of the electric field indicates the potential applied to the top electrode.

The chart shows the leakage current density versus electric field for films deposited at 300°C using ozone and 3 different Zr precursors (Zr(Cp)(ᵗBuDAD)(OⁱPr), Zr(MeCp)(TMEA)  and Zr(Me₅Cp)(TEA))

| Electric field (MV/cm) | Current density (A/cm²) | Reagent |
|---|---|---|
| -2,5 | 0,000034413049869757 | Zr(Cp)(tBuDAD)(O^iPr) |
| -2,4 | 0,000043492871235381 | Zr(Cp)(tBuDAD)(O^iPr) |
| -2,3 | 0,000021544346900319 | Zr(Cp)(tBuDAD)(O^iPr) |
| -2,3 | 0,000029439237258586 | Zr(Cp)(tBuDAD)(O^iPr) |
| -2,3 | 0,000017957144943716 | Zr(Cp)(tBuDAD)(O^iPr) |
| -2,2 | 0,000022695105366947 | Zr(Cp)(tBuDAD)(O^iPr) |
| -2,2 | 0,000013141473626118 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,0 | 0,000000030610872343 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,1 | 0,000000033095885951 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,1 | 0,000000016394163633 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,2 | 0,000000026186598892 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,3 | 0,000000004581597669 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,4 | 0,000000012971623961 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,4 | 0,000000001153843460 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,4 | 0,000000006768750009 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,5 | 0,000000015163203393 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,6 | 0,000000005355666918 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,6 | 0,000000017269832907 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,7 | 0,000000001384340542 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,8 | 0,000000015562895291 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,8 | 0,000000001660882783 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,9 | 0,000000001916398735 | Zr(Cp)(tBuDAD)(O^iPr) |
| 0,9 | 0,000000010534134765 | Zr(Cp)(tBuDAD)(O^iPr) |
| 1,0 | 0,000000026876860122 | Zr(Cp)(tBuDAD)(O^iPr) |
| 1,1 | 0,000000008120906678 | Zr(Cp)(tBuDAD)(O^iPr) |
| 1,1 | 0,000000021265892581 | Zr(Cp)(tBuDAD)(O^iPr) |
| 1,3 | 0,000000029058743813 | Zr(Cp)(tBuDAD)(O^iPr) |
| 1,4 | 0,000000044062364278 | Zr(Cp)(tBuDAD)(O^iPr) |
| 1,5 | 0,000000060208944933 | Zr(Cp)(tBuDAD)(O^iPr) |
| 1,7 | 0,000000086666869037 | Zr(Cp)(tBuDAD)(O^iPr) |
| 2,5 | 0,000097431763878509 | Zr(Cp)(tBuDAD)(O^iPr) |
| -1,8 | 0,000014582829828531 | Zr(Me_5Cp)(TEA) |
| -0,8 | 0,000000068573796153 | Zr(Me_5Cp)(TEA) |
| -0,6 | 0,000000134878740803 | Zr(Me_5Cp)(TEA) |
| -0,5 | 0,000000005355666918 | Zr(Me_5Cp)(TEA) |
| -0,2 | 0,000000007414066842 | Zr(Me_5Cp)(TEA) |
| -0,1 | 0,000000000901160733 | Zr(Me_5Cp)(TEA) |
| 0,0 | 0,000000048895122296 | Zr(Me_5Cp)(TEA) |
| 0,1 | 0,000000000501839650 | Zr(Me_5Cp)(TEA) |
| 0,4 | 0,000000037693909754 | Zr(Me_5Cp)(TEA) |
| 0,5 | 0,000000004581597669 | Zr(Me_5Cp)(TEA) |
| 0,6 | 0,000000031417754461 | Zr(Me_5Cp)(TEA) |
| 0,6 | 0,000000008554672536 | Zr(Me_5Cp)(TEA) |
| 0,8 | 0,000000084441059201 | Zr(Me_5Cp)(TEA) |
| 0,9 | 0,000000010000000000 | Zr(Me_5Cp)(TEA) |
| 1,2 | 0,000000040753929659 | Zr(Me_5Cp)(TEA) |
| 1,3 | 0,000000012638482029 | Zr(Me_5Cp)(TEA) |
| 1,4 | 0,000000066812659151 | Zr(Me_5Cp)(TEA) |
| 1,5 | 0,000000004463931423 | Zr(Me_5Cp)(TEA) |
| 1,9 | 0,000097431763878509 | Zr(Me_5Cp)(TEA) |
| -1,4 | 0,000001772505414982 | Zr(MeCp)(TMEA) |
| -1,0 | 0,000000248588037617 | Zr(MeCp)(TMEA) |
| -0,4 | 0,000000007414066842 | Zr(MeCp)(TMEA) |
| -0,1 | 0,000000001916398735 | Zr(MeCp)(TMEA) |
| 0,0 | 0,000000041828175983 | Zr(MeCp)(TMEA) |
| 0,1 | 0,000000000397072725 | Zr(MeCp)(TMEA) |
| 1,3 | 0,000002182644728397 | Zr(MeCp)(TMEA) |

Answer: Zr(MeCp)(TMEA)

Answer: No, it is different. The graph shows that when the electric field is negative, the leakage current is low and similar to the other compounds. When electric field is positive, the leakage current spikes compared to other precursors.

Answer: Yes

Answer: The curve shoots vertically upward at approx. 1.5 - 1.7 MV/cm.


Figure 10.  $JV$  sweeps for the best solar cells using the same RBF PDT ACIGS absorber and either TGO 0.077, ZGO 0.32, ZTO 0.2, or CdS as the ESL. Scans of solar cells using a pretreatment of either one cycle of ALD  $\mathrm{Al}_2\mathrm{O}_3$ $\mathrm{(TMA + H_2O)}$  or three cycles of ALD ZnS (DEZ  $+\mathrm{H}_2\mathrm{S})$  prior to the deposition of TGO 0.077 are also shown.

The PV characteristics is illustrated in the chart where the current density (in mA/cm²) is plotted as a function of bias voltage (in V) for various materials, including TGO 0.077, TGO 0.077 TMA, TGO 0.077 ZnS, ZGO 0.32, ZTO 0.20, and CdS.

| Bias (V) | TGO 0.077 | TGO 0.077 TMA | TGO 0.077 ZnS | ZGO 0.32 | ZTO 0.20 | CdS |
|----------|-----------|---------------|---------------|----------|----------|-----|
| -0.5     | -35       | -35           | -35           | -35      | -35      | -35 |
| 0.0      | 0         | 0             | 0             | 0        | 0        | 0   |
| 0.3      | 0         | 0             | 0             | 0        | 0        | 0   |
| 0.5      | 10        | 12            | 8             | 6        | 5        | 4   |
| 0.6      | 20        | 22            | 18            | 15       | 12       | 10  |
| 0.7      | 30        | 32            | 28            | 25       | 22       | 18  |
| 0.8      | 38        | 40            | 36            | 32       | 30       | 25  |
| 0.9      | 40        | 42            | 40            | 36       | 34       | 28  |
| 1.0      | 40        | 42            | 40            | 36       | 34       | 28  |

Answer: ZGO 0.32 with a Voc of 704 ± 8 mV. The solar cells with ZGO 0.32 ESLs had almost the same Voc as those with ZTO 0.2 but, on average, worse FF.

Answer: The TGO 0.077 ESL clearly gave lower Voc and FF compared to the ZnO or Cd-containing alternatives, just like in a previous study on TGAO ESL.

Answer: Aside from the blue losses in EQE for the devices with 2.4 eV Eg CdS, all of the solar cells showed good collection with some variation in the interference peak positions due to the difference in their ZnO:Al/ZnO/ESL stack thicknesses

Answer:
One thing that clearly distinguishes the TGO process from the more successful ALD ESL is that it does not contain Zn or its very reactive precursor DEZ. In the first test, the initial ALD conditions of Zn-containing ESLs were therefore mimicked by using three ALD cycles of ZnS (DEZ and H2S) before
continuing on with a TGO 0.077 ESL. The resulting JV data for these solar cells show that Voc improved to values comparable to using ZGO 0.32 ESL.

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


Figure 2. (a) Cation ratio measured by XRF/RBS for TGO and ZGO films in Table 1 as a function of the pulse ratio of the supercycle process. (b) GPC measured by XRR for the TGO and ZGO films (Table S2).

The line chart shows the relationship between pulse ratio and cation ratio measured from RBF/XPS for TGO and ZGO.

The line chart illustrates the growth per cycle against pulse ratio for TGO and ZGO.

| Pulse Ratio Ge/(Ge + Sn or Zn) | Cation Ratio (TGO) | Cation Ratio (ZGO) |
|--------------------------------|---------------------|---------------------|
| 0.0                            | 0.00               | 0.00               |
| 0.1                            | 0.08               | 0.02               |
| 0.2                            | 0.15               | 0.03               |
| 0.4                            | 0.30               | 0.05               |
| 0.6                            | 0.45               | 0.10               |
| 0.8                            | 0.70               | 0.40               |
| 1.0                            | 1.00               | 1.00               |

| Pulse Ratio Ge/(Ge + Sn or Zn) | Growth per Cycle (TGO) [Å/cycle] | Growth per Cycle (ZGO) [Å/cycle] |
|--------------------------------|-----------------------------------|-----------------------------------|
| 0.0                            | 1.10                              | 2.00                              |
| 0.1                            | 1.05                              | 1.80                              |
| 0.2                            | 1.00                              | 1.60                              |
| 0.4                            | 0.95                              | 1.40                              |
| 0.6                            | 0.90                              | 1.20                              |
| 0.8                            | 0.85                              | 1.00                              |
| 1.0                            | 0.80                              | 0.80                              |

Answer: The GPC for these films decreased for an increasing Ge pulse ratio of the ALD ZGO process, even to such an extent that it became substantially lower than  for the binary GeOy and ZnO processes. The QCM data in the SI also showed that the MPC for each GeOy or ZnO subcycle decreased in the ternary ZGO process. All of these trends suggest that the GeOy and ZnO subcycles were not fully compatible with each other due to unfavorable surface conditions.

Answer: The measured RBS/XRF [Ge]/([Ge] + [Sn]) cation ratio, x-value, for TGO films on fused silica is just a bit lower than the ALD Ge/(Ge + Sn) pulse ratio. The measured growth per cycle (GPC) for these films decreases as the pulse ratio increases (b) . This trend appears almost as a linear combination of the lower GPC GeOy subcycle and the larger GPC SnOy subcycle. Both the trend in the cation ratio and the trend in GPC are also supported by QCM data suggest that the SnOy and GeOy subcycles affect each other only to a minor extent.

Answer: No

Answer:
Varying the Ge/(Ge + Zn) pulse ratio of the ALD process varied the XRF/RBS [Ge]/([Ge] +[Zn]) cation ratio, the x-value, measured for films on fused
silica, but the film cation ratio severely lags behind the ALD pulse ratio


Figure 8. Schematic illustration of the roughly estimated  $E_{c}$  and  $E_{v}$  trends as a function of the cation ratio,  $x_{i}$  of a TGO and b ZGO. The estimations are based on the optical absorption and the XPS  $E_{v}$  spectra from this study and from the  $\mathrm{SnO}_{y} / \mathrm{CIGS}$ , and  $\mathrm{ZnO} / \mathrm{CIGS}$  band offset and ACIGS band position data from previous studies. The cation ratio where the ACIGS solar cells (see the next section) start showing FF losses is also indicated.

The line chart shows the energy difference between conduction bands and valence bands of ACIGS and TGO materials as a function of TGO cation ratio.

The line chart illustrates the energy difference between conduction bands and valence bands of ACIGS and ZGO materials as a function of ZGO cation ratio.

| TGO cation ratio (x) | E_c (TGO) [eV] | E_v (TGO) [eV] | E_c (ACIGS) [eV] | E_v (ACIGS) [eV] |
|-----------------------|-----------------|-----------------|-------------------|-------------------|
| 0.00                   | +0.2            | -3.0            | 0.0               | -1.0              |
| 0.10                   | +0.3            | -3.0            | 0.0               | -1.0              |
| 0.20 (FF loss) | +0.4            | -3.0            | 0.0               | -1.0              |
| 0.30                   | +0.6            | -3.0            | 0.0               | -1.0              |

| ZGO cation ratio (x) | E_c (ZGO) [eV] | E_v (ZGO) [eV] | E_c (ACIGS) [eV] | E_v (ACIGS) [eV] |
|-----------------------|-----------------|-----------------|-------------------|-------------------|
| 0.00                 | +0.2            | -3.5            | 0.0               | -1.0              |
| 0.10                 | +0.3            | -3.6            | 0.0               | -1.0              |
| 0.20                 | +0.4            | -3.7            | 0.0               | -1.0              |
| 0.30 (FF loss) | +0.5            | -3.8            | 0.0               | -1.0              |
| 0.40                 | +0.6            | -4.0            | 0.0               | -1.0              |

Answer: The estimations are based on the optical absorption and the XPS Ev spectra from this study and from the SnOy/CIGS, and ZnO/CIGS band offset and ACIGS band position data from previous studies

Answer:
While the low-cation-ratio ZGO films likely have direct Eg, there was a transition toward X-ray amorphous films for higher cation ratios, which are likely
to give them indirect Eg. For simplicity, all of the Eg values of ZGO were therefore estimated using an indirect Eg model.

Answer:
1. For ZGO, FF losses occur at a cation ratio of 0.32
2. For TGO, FF losses occur at a cation ratio of 0.16

Answer:
The TGO sample set also showed a noteworthy correlation between the large tailing observed in the optical absorption and XPS Ev spectra, the high resistivity, and the amorphous nature of these films. Compared to the previous study using a high-temperature ALD process, the films in this
study are similar in terms of being amorphous, showing tails in the optical absorption and an increasing Ec position with increasing Ge content.


Figure 9.  $JV$  sweeps of representative solar cells using (a) TGO and (b) ZGO ESLs.

The figure shows the JV characteristics of devices using TGO as ESL with varying doping values.

The figure shows the JV characteristics of devices using ZGO as ESL with varying doping values.

| Bias (V) | CdS | x = 0 | x = 0.065 | x = 0.077 | x = 0.10 | x = 0.16 | x = 0.30 |
|----------|-----|-------|-----------|-----------|----------|----------|----------|
| -0.5     | -35  | -35    | -35       | -35        | -35       | -35       | -30      |
| 0.0      | 0   | 0     | 0         | 0         | 0        | 0        | -3       |
| 0.3      |-35  | -35    | -35       | -35        | -35       | -35       | 0   |
| 0.5      | -35  | -10    | -15        | -18        | -20       | -18       |0       |
| 0.7      | 0  | 20    | 25        | 28        | 30       | 20       | 0      |

| Bias (V) | CdS | x = 0 | x = 0.032 | x = 0.12 | x = 0.19 | x = 0.26 | x = 0.32 | x = 0.37 |
|----------|-----|-------|-----------|----------|----------|----------|----------|----------|
| -0.4     | -35   | -35      | -40         | -35        | -35        | -35         | -35         | -35        |
| 0.0      |  -35   | -35      | -35         | -35        | -35        | -35         | -35         | -35      |
| 0.2      | -35   | -30     | -28         | -32        | -34        | -35        | -35        | -35        |
| 0.4      | 0   | 20    | 30        | 35       | -34       | -35       | 25       | -10       |
| 0.6      | 0   | -    | -        | -       | 0       | 0      | 0      | 0       |
| 0.8      | -   | -    | -        | -      |20       | 20       | 40       | 20       |

Answer: As the Ge content was increased for the ZGO films, the solar cells showed a decrease in Voc, compared to solar cells using ZnO . When the Ge content increased further, there was an increase in Voc up to ZGO 0.37.

Answer: From figure a it appears, the device characteristics of CdS is better than device b as the Voc seems higher in case a than case b.

Answer:
1. ZnO:Al/ZnO/TGO/ACIGS/Mo/SLG solar cell stacks
, 2. ZnO:Al/ZnO/ZGO/ACIGS/Mo/SLG solar cell stacks

Answer: Until TGO 0.10, the Voc of the solar cells increased with increasing Ge content. At the same time, the short circuit current density (Jsc) remained unchanged. For TGO 0.16, both the Voc and the FF started to drop off due to a kink in the J−V curve around Voc. Finally, the solar cells with TGO 0.30 show low FF, low Voc and a tiny Jsc, suggesting that the transport of photoexcited electrons has been almost completely hampered.


Figure 1. ALD growth rates for  $\mathrm{In}_2\mathrm{O}_3$ $(\Delta)$ $\mathrm{SnO_2}$ $(\Omega)$  and ITO  $(\bullet)$  versus deposition temperature. Potential ALD window for ITO growth is indicated.

The multiple line chart compares the growth rate per cycle of Tin Oxide, Indium Oxide, and ITO films as a function of deposition temperature. Both Tin and Indium Oxide show a general increase in growth rate with temperature, while ITO exhibits a stable region between ~200 - 300 °C, identified as the “ITO Window,” where optimal co-deposition occurs.

| Deposition Temperature (°C) | Tin Oxide (Å/Cycle) | Indium Oxide (Å/Cycle) | ITO (Å/Cycle) |
|-----------------------------|--------------------|-------------------------|---------------|
| 100                         | 0.5                | 1.2                     | 1.3           |
| 150                         | 0.8                | 1.3                     | 1.2           |
| 200                         | 1.5                | 1.4                     | 1.3           |
| 250                         | 2.0                | 1.5                     | 1.4           |
| 300                         | 2.8                | 1.6                     | 1.5           |
| 350                         | 2.9                | 2.5                     | 1.6           |
| 400                         | 3.0                | 2.7                     | 1.6           |

Answer: Tin Oxide shows a steep increase in growth rate with temperature, Indium Oxide increases more moderately, and ITO remains stable between 200–300 °C, forming a defined “ITO Window.”

Answer: Growth rate (Å/Cycle).

Answer: Tin Oxide, Indium Oxide, ITO (Indium Tin Oxide)

Answer: Yes

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


Figure 3.  $\mathrm{SnO_2}$  content versus percentage of  $\mathrm{SnO_2}$  cycles for ALD ITO films determined by XRF. Dashed line shows expected  $\mathrm{SnO_2}$  content as calculated using a rule-of-mixtures formula.

The line chart shows the increase in SnO₂ content (mol %) as a function of SnO₂ cycle percentage, as measured by XRF. A dashed line indicates the expected values from the Rule of Mixtures. The measured data rises faster than predicted, suggesting non-linear incorporation.

| % SnO₂ Cycles | SnO₂ Content (mol %) |
|---------------|----------------------|
| 0             | 0                    |
| 5             | 2                    |
| 10            | 12                   |
| 15            | 26                   |
| 25            | 40                   |

Answer: The measured SnO₂ content increases faster than the Rule of Mixtures prediction, indicating a non-linear trend in incorporation.

Answer: No

Answer: Enhanced SnO₂ uptake, Possible non-ideal mixing behavior, Deviations from theoretical assumptions

Answer: No


Figure 8. Representative magnetization versus external field curves of doped iron oxide films deposited from  $\mathrm{CpFeC_5H_4CHN(CH_3)_2}$  at  $375^{\circ}C$  Mg/Fe atomic ratios, film thicknesses, hysteresis parameters and measurement temperatures are given by labels. Annealing was carried out in forming gas at  $450^{\circ}C$  for  $30\mathrm{min}$  (Color online)

The figure shows hysteresis loops of magnetic material Mg/Fe = 0.017 at various temperatures (10, 50, 100, 200, 300 K) with as deposited condition , the thickness of the film ~425 nm

The figure shows hysteresis loops of magnetic material Mg/Fe = 0.061 at various temperatures (10, 50, 100, 200, 300 K) with as deposited condition , the thickness of the film ~411 nm

The figure shows hysteresis loops of magnetic material Mg/Fe = 0.017 at various temperatures after annealing at 450◦C

The figure shows hysteresis loops of magnetic material Mg/Fe = 0.061 at various temperatures after annealing at 450◦C.  The hysteresis loops shows noticable magnetic behavior with high magnetic saturations and low coercive fields.

| Temperature (K) | Saturation Magnetization Ms (emu/cm³) | Coercivity Hc (Oe) |
|-----------------|---------------------------------------|-------------------|
| 300 | ~200 | 300 |
| 200 | ~200 | ~300 |
| 100 | ~200 | ~300 |
| 50 | ~200 | ~300 |

| Temperature (K) | Saturation Magnetization Ms (emu/cm³) | Coercivity Hc (Oe) |
|-----------------|---------------------------------------|-------------------|
| 300 | 491 | 150 |
| 200 | ~500 | ~150 |
| 100 | ~500 | ~150 |
| 50 | ~500 | ~150 |
| 10 | ~500 | ~150 |

| Temperature (K) | Saturation Magnetization Ms (emu/cm³) | Coercivity Hc (Oe) |
|-----------------|---------------------------------------|-------------------|
| 300 | 280 | 280 |
| 200 | ~290 | ~280 |
| 100 | ~290 | ~280 |
| 50 | ~290 | ~280 |
| 10 | ~290 | ~280 |

| Temperature (K) | Saturation Magnetization Ms (emu/cm³) | Coercivity Hc (Oe) |
|-----------------|---------------------------------------|-------------------|
| 300 | 274 | 200 |
| 200 | ~280 | ~200 |
| 100 | ~280 | ~200 |
| 50 | ~280 | ~200 |
| 10 | ~280 | ~200 |

Answer: As the Mg content increases, the Hc value tends to decrease.

Answer: In the as-deposited state, increasing Mg/Fe from 0.017 to 0.061 increases Ms from about 200 to about 491 emu/cm³. Over the same change, Hc decreases from about 300 to about 150 Oe. This matches the broader trend described in the paper that higher Mg in this range reduces coercivity while increasing saturation magnetization up to a limit.

Answer: The best room-temperature magnetization in this figure is the as-deposited Mg/Fe = 0.061 film (panel b). It shows Ms ≈ 491 emu/cm³ at 300 K, substantially higher than the Mg/Fe = 0.017 film and higher than either annealed case. This directly supports the process-optimization message that moderate Mg levels can strongly enhance magnetic performance (while other processing steps can change Ms and Hc in different directions).

Answer: Mg incorporation and FGA alter the cation distribution in the spinel lattice. At moderate Mg levels, magnetite formation is favored, increasing Mₛ and lowering Hc. At higher Mg levels, Mg²⁺ substitutes Fe³⁺ in octahedral sites, reducing magnetic exchange interactions and introducing lattice strain, which increases coercivity and decreases magnetization. Annealing further modifies grain boundaries and defect density, influencing domain wall motion.

Answer:
1. In the nondoped and as-deposited films the HC ranged from 485 to 1950 Oe between 300 and 10 K.
2. In the films with Mg/Fe atomic ratio of 0.017 the HC was in the range of 300–1260 Oe between 300 and 10 K.
3. With  increase in the Mg content to Mg/Fe ratio of 0.062 the HC decreased toward the range of 150–460 Oe between 300 and 10 K.

Answer: At 10 K.

Answer: Increasing temperature reduces both the coercive field and the saturation magnetisation. The hysteresis loops become narrower at higher temperatures, indicating weaker magnetic ordering.

Answer: The coercive field decreases as the Mg/Fe ratio increases.

Answer: Mg/Fe=0.017 and the film as-deposited

Answer: The hysteresis parameter Hc seems to decrease for increasing measurement temperature. This is seen in all subfigures, however the trend is less big for the highly doped films.

Answer: The Hc is 1500 Oe.

Answer: Saturation magnetization increases from ~200 emu cm⁻³ at low Mg content to ~491 emu cm⁻³ at higher Mg content.

Answer:
x-axis: magnetic field (Oe)

y-axis: magnetization, M (emu/cm³)

curves: measurements at 300, 200, 100, 50, and 10 K for the same sample/state

Answer: In each panel, Hc increases as temperature decreases (loops widen at low T), which is typical for ferri/ferromagnetic films. After forming-gas annealing, Hc is generally reduced at higher temperatures compared with the as-deposited state for these kinds of samples. The paper attributes the anneal-driven reduction in coercivity to crystal growth and increased average magnetic domain size.

Answer: FGA modifies both saturation magnetization (Mₛ) and coercivity (Hc). For low Mg content (Mg/Fe = 0.017), Mₛ increases from 200 → 280 emu/cm³, and Hc slightly decreases from 300 → 280 Oe, indicating improved magnetite crystallinity and reduced pinning. For higher Mg content (Mg/Fe = 0.061), Mₛ decreases from 491 → 274 emu/cm³, while Hc increases from 150 → 200 Oe, suggesting that excess Mg and annealing lead to cation redistribution and reduced magnetic Fe content.

Answer:
As-deposited: Increasing Mg/Fe from 0.017 to 0.061 significantly raises Mₛ (200 → 491 emu/cm³) and lowers Hc (300 → 150 Oe), indicating that moderate Mg promotes magnetite formation and soft magnetic behavior.
After FGA: Low Mg films gain magnetization (Mₛ = 280 emu/cm³), while high Mg films lose magnetization (Mₛ = 274 emu/cm³) and become harder (Hc rises to 200 Oe).
Mg doping initially enhances magnetization, but excessive Mg combined with annealing reduces Fe magnetic sites and increases anisotropy.

Answer: Yes, only up to a certain limit.

Answer: The coercive field (Hc) decreases systematically with increasing Mg doping, indicating that Mg addition softens the magnetic behaviour. For instance, Hc drops from roughly 485-1950 Oe in undoped films to 150-460 Oe at a Mg/Fe ratio of 0.062. Annealing further reduces Hc, consistent with structural relaxation and grain coarsening. Meanwhile, the saturation magnetization (μs) increases with moderate Mg incorporation, suggesting improved ferromagnetic ordering and a higher proportion of reduced iron oxide phases such as magnetite. However, excessive Mg content diminishes μs again, likely due to the formation of a nonmagnetic ternary phase like magnesioferrite.

Answer: Between 820 and 895 K.

Answer: The Curie temperatures remain between 820 and 895 K, close to that of bulk magnetite, confirming that the dominant phase retains strong ferrimagnetic character.

Answer: Annealing of all films was carried out at 450 °C for 30 minutes.

Answer: Yes

Answer: Magnetic field (Oe).

Answer: Yes

Answer: The loop becomes wider as the temperature drops.

Answer: At 300 K.

Answer: The annealing seems to have the effect to create films with roughly the same saturation magnetization, even if the as-deposited films deviate from this level.

Answer: Coercivity decreases slightly from ~300 Oe to ~280 Oe after annealing.

Answer: Annealing likely reduces structural disorder and improves cation distribution within the iron-oxide lattice. This suppresses antiferromagnetic coupling and enhances net magnetic alignment. The increase in saturation magnetization therefore reflects improved magnetic ordering rather than thickness effects.

Answer: The as-deposited film with Mg/Fe = 0.061 offers the best performance for sensors and spintronics due to its high Mₛ (491 emu/cm³) and low Hc (150 Oe), enabling strong magnetic response and easy switching. FGA-treated low-Mg films (Mg/Fe = 0.017) are suitable for applications requiring moderate coercivity and thermal stability, while high-Mg annealed films may be useful for data storage where higher Hc provides stability against demagnetization.

Answer: The coercivity and magnetic moment decreased with increase in magnesium content. Therefore, high amounts of magnesium may not be advantageous in terms of increasing both HC and μS, maybe due to the formation of an additive ternary phase, e.g. magnesioferrite, in the film bulk.

Answer: The as-deposited sample ,The Mg = 0.001 doped sample ,The Mg = 0.017 doped sample.

Answer: The main affected properties are the coercive field, Saturation magnetization, Loop shape of the hysteresis curves, Temperature dependence of magnetization

Answer: 280 emu/cm^3.

Answer: The Hc value is higher for the annealed samples than for the as-deposited one.

Answer: The annealed film

Answer: The as-deposited films show that with increasing dopant level the saturated magnetization increases significantly, whilst the Hc parameter decreases.

Answer: Measuring hysteresis down to 10 K reduces thermal activation of domain walls, making intrinsic magnetic anisotropy more apparent. This helps separate temperature-driven loop broadening from composition-dependent effects. The comparison clarifies how Mg content and annealing influence intrinsic magnetic ordering.

Answer: The annealing procedure also decreased the HC.

Answer: Adjusting the Mg content allows fine control over the balance between coercivity and saturation magnetization, which is crucial for practical magnetic applications. Moderate Mg doping can soften the magnetic response by lowering coercivity while maintaining or slightly improving magnetization, making the films more suitable for applications such as magnetic sensors or spintronic components. However, excessive Mg incorporation can introduce secondary phases like magnesioferrite, which limits further performance gains. This figure shows that careful compositional tuning, combined with annealing and temperature control, is essential for optimizing magnetic behavior.

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/30/Kaupo Kukli et al.pdf


Figure 9. Magnetization versus measurement temperature curves of selected samples after forming gas annealing measured under FGD field cooling (ZFC) and field cooling (FC) regimes. The composition, growth temperatures and film thicknesses are described by labels. The peaks associated with the Verwey transition of magnetite are denoted by  $\mathrm{T_V}$

The plot shows the temperature dependence of magnetic susceptibility for Fe₂O₃ nanoparticles grown at 450 °C with an average diameter of 705 nm. Measurements were carried out using a field gradient apparatus (FGA) under an applied magnetic field of 1000 Oe, following zero-field-cooled (ZFC) and field-cooled (FC) protocols after forming gas annealing. Features associated with the Verwey transition temperature (T𝑉) of magnetite are indicated.

This plot presents the temperature dependence of magnetic moment per gram for a composite consisting of 100 × Fe₂O₃ and 4 × (3 × MgO + 100 × Fe₂O₃), grown at 425 °C with an average diameter of 183 nm. Measurements were performed using an FGA under a magnetic field of 1000 Oe in both ZFC and FC modes after forming gas annealing. The Verwey transition temperature (TV) is marked.

The plot shows the temperature dependence of magnetic moment per gram for a composite composed of 100 × Fe₂O₃ and 15 × (10 × MgO + 100 × Fe₂O₃), grown at 375 °C with an average diameter of 411 nm. Magnetization measurements were conducted using an FGA with an applied magnetic field of 1000 Oe under ZFC and FC conditions following forming gas annealing, with the Verwey transition temperature (T𝑉) indicated.

| Temperature (K) | FC (emu/g) | ZFC (emu/g) |
| --------------- | ---------- | ----------- |
| 10              | ~0.10      | ~0.01       |
| 50              | ~0.10      | ~0.03       |
| 100             | ~0.10      | ~0.07       |
| 125             | ~0.10      | ~0.10       |
| 200             | ~0.10      | ~0.09       |
| 300             | ~0.10      | ~0.08       |

| Temperature (K) | FC (emu/g) | ZFC (emu/g) |
| --------------- | ---------- | ----------- |
| 10              | ~0.055     | ~0.030      |
| 50              | ~0.055     | ~0.040      |
| 100             | ~0.055     | ~0.050      |
| 120             | ~0.055     | ~0.055      |
| 200             | ~0.055     | ~0.050      |
| 300             | ~0.055     | ~0.045      |

| Temperature (K) | FC (emu/g) | ZFC (emu/g) |
| --------------- | ---------- | ----------- |
| 10              | ~0.069     | ~0.068      |
| 50              | ~0.069     | ~0.069      |
| 100             | ~0.069     | ~0.070      |
| 150             | ~0.068     | ~0.069      |
| 200             | ~0.067     | ~0.068      |
| 300             | ~0.066     | ~0.067      |

Answer: Growth temperature and composition.

Answer: For all three graphs, samples with different thickness are used. So it could be that this thickness plays a factor in the different magnetizations.

Answer: It suggests increased magnetic disorder and weakened long-range ordering.

Answer: In (a) a pronounced anomaly is marked at ~125 K. In (b) a similar anomaly remains visible around ~120 K. In (c) the anomaly is much less prominent, consistent with the stated trend that the Verwey signature weakens in films that are more disordered and/or contain higher MgO amounts.

Answer: A Verwey-type transition near ~120 K is a characteristic low-temperature transformation associated with magnetite (Fe₃O₄) (cubic-to-monoclinic symmetry change tied to cation ordering). Observing a step/jump in M–T around 120–125 K is therefore used as supporting evidence for the presence of magnetite in mixed-phase samples. In this paper, that interpretation is explicitly noted for selected annealed films showing the jump.

Answer: The Verwey transition depends on stoichiometric magnetite with ordered Fe²⁺/Fe³⁺ distribution. Mg substitution and oxygen vacancies disrupt this order, lowering or smearing Tᵥ. Grain size and strain also matter: larger, well-crystallized grains show sharp Tᵥ and strong ZFC/FC splitting, while smaller or defect-rich grains broaden the transition and reduce irreversibility.

Answer: The transition lost its prominence in as-deposited films, in relatively disordered films grown at the lowest temperatures examined and in films containing relatively higher amounts of magnesium oxide

Answer: Verwey transition visible near 120–125 K for composition variations, Lower growth temperatures reduce the transition magnitude, Thicker films show minor decreases in magnetization but overall similar trends

Answer: Yes

Answer: 120 K.

Answer: Either the growth temperature could be lowered, or the Mg/Fe ratio could be increased.

Answer: The dopant level is Mg/Fe = 0.062.

Answer: It implies well-preserved magnetite-like ordering.

Answer: Cryogenic sensors: Prefer films with a sharp Verwey transition and strong ZFC/FC separation (e.g., thick, low-Mg film), as these provide distinct low-temperature magnetic signatures. 2. Room-temperature devices: Favor films with suppressed or broadened Tᵥ (e.g., high-Mg film), ensuring stable magnetic behavior across 150–300 K without abrupt changes.

Answer: The temperature dependence of magnetic moment was measured at a magnetic moment of 1000 Oe

Answer: No

Answer: The undoped Fe₂O₃ sample shows a clear ZFC peak near 125 K, indicating strong blocking behavior. The Mg-containing sample grown at 425 °C shows a similar but weaker peak near 120 K. In contrast, the sample grown at 375 °C exhibits minimal FC–ZFC separation, suggesting suppressed or absent blocking.

Answer: 1000 Oe.

Answer: The Fe₂O₃ sample grown at 450 °C, The Fe₂O₃–MgO composite grown at 425 °C

Answer: Around 120–125 K.

Answer: 450 °C.

Answer: The temperature is 125 K.

Answer: It seems that increasing the doping level, slightly increases the magnetic moment.

Answer: The separation reflects irreversible magnetic behavior caused by domain pinning or blocked magnetic moments. A strong divergence indicates a magnetically ordered phase with thermal history dependence. The convergence of FC and ZFC curves marks the temperature where magnetic domains become thermally unpinned.

Answer: It rises sharply and reaches a peak near 125 K.

Answer:
ZFC: zero-field cooling measurement curve

FC: field-cooling measurement curve

Applied field during M–T: 1000 Oe

Answer: Magnetite-like content is linked to the stronger ferrimagnetic response desired in these films, while hematite-dominant films tend to show much weaker magnetization. A Verwey-type feature provides an additional, temperature-dependent indicator that reduced/spinel-like iron oxide is present after forming-gas anneal. This helps connect processing (growth temperature, Mg dosing, anneal) to the observed magnetic behavior.

Answer: The Verwey transition (Tᵥ ≈ 120–125 K) is a hallmark of magnetite (Fe₃O₄) with long-range charge ordering. Its appearance after FGA shows that annealing in a reducing atmosphere successfully converted hematite or maghemite phases into magnetite and improved crystallinity. This process also reduces oxygen content and stabilizes Fe²⁺/Fe³⁺ mixed valence states, essential for magnetite formation.

Answer:
Pure Fe₂O₃ film (450 °C, thick): Shows a sharp Tᵥ at ~125 K and strong ZFC/FC separation, indicating well-ordered magnetite after FGA.
Low Mg doping (Mg/Fe ≈ 0.021, 425 °C): Tᵥ shifts slightly lower (~120 K) and ZFC/FC separation narrows, suggesting smaller grains and mild disorder. High Mg doping (Mg/Fe ≈ 0.062, 375 °C): Tᵥ is broadened or suppressed, and ZFC/FC curves nearly overlap, indicating disrupted charge ordering and increased structural disorder due to Mg substitution and lower growth temperature

Answer: A jump in magnetization-versus-temperature curves is  known as the Verwey transition. At the Verwey transition temperature, TV, ca. 120 K, magnetite is supposed to transform from cubic (T > TV) to monoclinic (T < TV) symmetry. This transformation is related to changes in cation ordering and, at a slightly higher temperature (ca. 130 K) to changes in magnetocrystalline anisotropy as well as switching the easy and hard magnetization axes. The Verwey transition can be used for identification of magnetite in pure or mixed phase samples.

Answer: Yes

Answer: 1000 Oe.

Answer: At the Verwey transition temperature, TV, ca. 120 K, magnetite is supposed to transform from cubic (T > T_V) to monoclinic (T < T_V) symmetry.

Answer: As the Mg fraction in the film increases, T_V decreases. As the Mg fraction increases, the difference between ZFC and FC also becomes more pronounced, but the transition point becomes less clear. Finally, an increase in Mg content also causes an overall decrease of magnetization, which is consistent with earlier observations in this work.

Answer: For the undoped iron oxide film, it is 125 K and a magnetization of 0.11 emu/g; The iron oxide film with Mg/Fe = 0.021, T_V = 120 K, M = 0.055; The iron oxide film with Mg/Fe = 0.062, the T_V is not stated.

Answer: At 125 K, as indicated by the label Tv.

Answer: At 120 K.

Answer: At 125 K.

Answer: No

Answer: Composition strongly affects the Verwey transition, with magnetite-containing films showing a peak near 120–125 K. Growth temperature also influences magnetic behavior, as lower temperatures suppress the Verwey transition, leading to smaller differences between FC and ZFC magnetization. Film thickness has a subtler effect, slightly modifying magnetization magnitudes but not significantly altering the overall transition features. Together, these factors determine the magnetic phase evolution and the shape of the multi-line curves.


Figure 1. XPS depth profile of thermal ALD Co on Si(001) substrate from  $\mathrm{CoCp(CO)_2}$  and  $\mathrm{H}_2$  showing the Co, C, O, and Si contents in the film.

Figure shows an XPS depth profile of a thermal-ALD Co film deposited on Si(001) using CoCp(CO)₂ and H₂. The profile reveals a carbon-rich film with ~40–50 at% C and only ~45–50 at% Co throughout most of the depth, along with a few at% oxygen contamination. The sharp rise in Si near ~25–30 min sputtering marks the Co/Si interface, confirming the film thickness. Overall, the data demonstrate that thermal ALD produces a Co–C composite rather than pure metallic Co, indicating poor ligand removal.

| Element|Trend across film|Interpretation|
|--------|-----------------|--------------|
|Co|~45–50 at% throughout|Indicates incomplete metal formation|
|C|~40–50 at% throughout|Severe carbon contamination from ligands|
|O|Low, few at%|Minor oxidation/impurity|
|Si|Rises sharply at end|Marks Co/Si interface (film thickness)|

Answer: yes

Answer: Carbon

Answer: Interconnect applications require low-resistivity, high-purity metallic cobalt. The XPS depth profile reveals that the thermal-ALD film contains nearly equal amounts of cobalt and carbon, forming a carbon-rich Co–C composite rather than metallic Co. Such films exhibit very high electrical resistivity and poor reliability, making them unsuitable for device applications and motivating the need for plasma-enhanced ALD.

Answer: High carbon content (~40–50 at%), Relatively low cobalt content (~45–50 at%), Presence of oxygen impurities, Formation of a Co–C composite structure

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/31/Han-Bo-Ram Lee et al.pdf


Figure 5. Leakage current densities vs electric fields of thermal and PEALD (a)  $\mathrm{Ta}_2\mathrm{O}_5$  and (b)  $\mathrm{TiO_2}$  thin film. The film thickness was  $10\mathrm{nm}$  for all films, and the growth temperatures were  $250^{\circ}\mathrm{C}$  for  $\mathrm{Ta}_2\mathrm{O}_5$  and  $200^{\circ}\mathrm{C}$  for  $\mathrm{TiO_2}$  respectively.

Leakage current density versus electric field for 10 nm Ta₂O₅ films grown at 250°C. PE-ALD yields approximately two orders of magnitude lower leakage (~8×10⁻⁷ A/cm²) compared to thermal ALD (~6×10⁻⁵ A/cm²) at 1 MV/cm.

Leakage current density versus electric field for 10 nm TiO₂ films grown at 200°C. PE-ALD again shows lower leakage (~7×10⁻⁴ A/cm²) than thermal ALD (~5×10⁻³ A/cm²) at 1 MV/cm, though the difference is smaller than for Ta₂O₅.

| Electric Field, MV/cm | Thermal ALD (A/cm²) | PE-ALD (A/cm²) |
|---|---|---|
| 0 | 1×10⁻⁷ | 5×10⁻⁸ |
| 0.1 | 5×10⁻⁷ | 7×10⁻⁸ |
| 0.25 | 3×10⁻⁶ | 1×10⁻⁷ |
| 0.5 | 2×10⁻⁵ | 3×10⁻⁷ |
| 0.75 | 5×10⁻⁵ | 7×10⁻⁷ |
| 1.0 | 7×10⁻⁵ | 2×10⁻⁶ |
| 1.5 | 1×10⁻⁴ | 7×10⁻⁶ |
| 2.0 | 1.5×10⁻⁴ | 2×10⁻⁵ |

| Electric Field, MV/cm | Thermal ALD (A/cm²) | PE-ALD (A/cm²) |
|---|---|---|
| 0 | 2×10⁻³ | 5×10⁻⁵ |
| 0.1 | 3×10⁻³ | 8×10⁻⁵ |
| 0.25 | 3.5×10⁻³ | 2×10⁻⁴ |
| 0.5 | 4×10⁻³ | 4×10⁻⁴ |
| 0.75 | 5×10⁻³ | 5×10⁻⁴ |
| 1.0 | 6×10⁻³ | 6×10⁻⁴ |
| 1.5 | 8×10⁻³ | 8×10⁻⁴ |
| 2.0 | 1×10⁻² | 1×10⁻³ |

Answer: PE-ALD Ta₂O₅ exhibits a leakage current density of approximately 8×10⁻⁷ A/cm² at 1 MV/cm, which is about two orders of magnitude lower than thermal ALD Ta₂O₅ at approximately 6×10⁻⁵ A/cm². This substantial improvement makes PE-ALD Ta₂O₅ from PDMAT competitive with or better than previously reported values for PE-ALD Ta₂O₅ from ethoxide precursors.

Answer: Lower oxygen vacancy concentration, reduced carbon or silicon contamination, and smoother oxide/substrate interfaces observed by TEM.

Answer: PE-ALD Ta₂O₅, with the lowest leakage current density of approximately 8×10⁻⁷ A/cm² at 1 MV/cm.

Answer: The improvement is greater for Ta₂O₅. PE-ALD reduces the leakage current by approximately two orders of magnitude for Ta₂O₅ (from ~6×10⁻⁵ to ~8×10⁻⁷ A/cm²), whereas for TiO₂ the reduction is less than one order of magnitude (from ~5×10⁻³ to ~7×10⁻⁴ A/cm²).

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


Figure 1. Film thickness as function of number of cycles measured by in situ spectroscopic ellipsometry for ALD of Li-containing films using LiHMDS combined various coreactants at a table temperature of  $200^{\circ}\mathrm{C}$ .

The figure displays a multiple -line chart showing the film thickness growth as a function of ALD cycle number for different oxidant/reactant chemistries. The growth rates vary significantly depending on the species used: H₂O exhibits the highest growth rate, followed by H₂* + O₂*, then O₂* + H₂*, and finally O₂* alone, which shows the slowest growth. The chart highlights how the choice of oxidant or co-reactant can strongly influence the cumulative thickness achieved over the same number of ALD cycles..

| Cycle | O₂* (nm) | H₂O (nm) | H₂* + O₂* (nm) | O₂* + H₂* (nm) |
|-------|----------|----------|----------------|----------------|
| 0     | 0        | 0        | 0              | 0              |
| 50    | 10       | 30       | 20             | 15             |
| 100   | 20       | 60       | 40             | 30             |
| 150   | 30       | 90       | 60             | 45             |
| 200   | 40       | 120      | 80             | 60             |

Answer: The faster and steeper thickness increase observed for H₂O compared to O₂* implies that H₂O is significantly more reactive or efficient as an oxidant in this ALD process. This could be due to more favorable surface reactions, faster ligand removal, or a more complete reaction per cycle. In contrast, O₂* likely leads to slower surface reactions, incomplete ligand removal, or passivation effects that limit the growth per cycle. This highlights the importance of selecting appropriate co-reactants for achieving desired film thickness and deposition rates.

Answer: 60 nm.

Answer: Yes

Answer: O₂*, O₂* + H₂*, H₂* + O₂*, H₂O

icdar2026-competition-data/train/atomic-layer-deposition/experimental-usecase/34/M. J. Pieters et al.pdf


Figure 3. (a) Time-resolved QMS data of selected  $m / z$  values during the LiHMDS  $+\mathrm{H}_2\mathrm{O}$  process. The standard ALD recipe (SR) at the start and end of the deposition, corresponding to the slow and fast growth regimes (earlier defined in Figure 1) respectively, are compared to the recipe with only  $\mathrm{H}_2\mathrm{O}$  and the recipe with only LiHMDS. Zooms of the HMDS-related signals of  $m / z = 15$  amu (b) and 146 amu (c) during the LiHMDS dose step.

The figure presents ion current traces for various species monitored during sequential pulsing of LiHMDS and H₂O in an ALD process. Subfigure (a) shows the evolution of ion signals for multiple mass fragments (e.g., CH₃⁺, H₂O⁺, NH(SiMe₃)₂⁺) across time and marks key events such as precursor pulses and surface reaction (SR) start and end times. Subfigures (b) and (c) zoom in on the time-resolved ion currents for specific m/z values (15 and 146), further detailing the temporal behavior of key reaction byproducts during the LiHMDS pulse. Together, the data provide insight into precursor decomposition and reaction dynamics on the surface.

| Time (s) | LiHMDS | SR start | H₂O | SR end |
|----------|--------|----------|-----|--------|
| 0        | 1E-12  | 1E-12    | 1E-12| 1E-12  |
| 5        | 1E-11  | 1E-11    | 1E-11| 1E-11  |
| 10       | 1E-12  | 1E-12    | 1E-12| 1E-12  |
| 15       | 1E-12  | 1E-12    | 1E-12| 1E-12  |
| 20       | 1E-12  | 1E-12    | 1E-12| 1E-12  |
| 25       | 1E-12  | 1E-12    | 1E-12| 1E-12  |
| 30       | 1E-12  | 1E-12    | 1E-12| 1E-12  |
| 75       | 1E-12  | 1E-12    | 1E-12| 1E-12  |
| 80       | 1E-12  | 1E-12    | 1E-12| 1E-12  |

| Time (s) | Ion current (A) |
|----------|-----------------|
| 0        | 1E-11           |
| 2        | 1E-10           |
| 4        | 1E-10           |
| 6        | 1E-10           |
| 8        | 1E-10           |

Answer: The ion current profiles reveal the presence and intensity of specific species over time, corresponding to precursor introduction and reaction phases. In subfigure (a), CH₃⁺ and NH(SiMe₃)₂⁺ signals spike during the LiHMDS pulse, suggesting the release of ligand fragments due to surface reactions. The H₂O⁺ signal increases during the water pulse, indicating oxidant introduction. The timing of signal changes at SR start and SR end further supports surface-limited reactions consistent with ALD. Subfigures (b) and (c) confirm this by showing that key mass fragments peak during the precursor pulse, then decay rapidly, demonstrating self-limiting behavior and supporting the controlled nature of ALD chemistry.

Answer: Approx. 5 seconds.

Answer: No

Answer: CH₃⁺ (m/z = 15), H₂O⁺ (m/z = 18), NH(SiMe₃)₂⁺ (m/z = 146)


Figure 5. Time-resolved QMS data of selected  $m / z$  values during the LiHMDS  $+\mathrm{O}_2^*$  process. The standard ALD recipe (SR, red) is compared to the recipe with only  $\mathrm{O}_2^*$  (blue) and the recipe with LiHMDS and  $\mathrm{O}_2$  gas (black).

This figure presents time-resolved mass spectrometry data for various reaction by-products during exposure to LiHMDS, O₂ plasma (O₂*), and the surface reaction (SR) step. The top four subplots show ion current intensity for species including H₂O⁺ (m/z=18), SiH₃⁺ (m/z=30), CO₂⁺ (m/z=44), and HNSi₂Me₃⁺ (m/z=146), with clear changes occurring after precursor and plasma exposure. CO₂ and H₂O peaks intensify during the SR period, consistent with ligand combustion, while HNSi₂Me₃⁺ appears following LiHMDS exposure, reflecting gas-phase fragmentation of unreacted precursor. The bottom panel tracks chamber pressure, showing correlation between dose timing and ion evolution. These measurements collectively map the dynamic release of volatile by-products during an ALD half-cycle..

| Time (s) | LiHMDS (A) | O₂* (A) | SR (A) |
|----------|------------|---------|--------|
| 0        | 1.5E-12    | 1.5E-12 | 1.5E-12 |
| 5        | 1.6E-12    | 1.5E-12 | 1.5E-12 |
| 10       | 1.8E-12    | 1.5E-12 | 2.0E-12 |
| 15       | 2.2E-12    | 2.5E-12 | 3.0E-12 |
| 20       | 1.8E-12    | 3.5E-12 | 2.8E-12 |
| 25       | 1.5E-12    | 2.2E-12 | 1.7E-12 |

Answer: Yes

Answer: Around 7 seconds, during the LiHMDS exposure phase.

Answer: H₂O⁺ (m/z = 18), CO₂⁺ (m/z = 44), HNSi₂Me₃⁺ (m/z = 146)

Answer: The sharp rise in CO₂⁺ and H₂O⁺ signals during the SR step indicates that combustion of organic ligands is occurring due to interaction with reactive oxygen species. These by-products are signatures of oxidative ligand removal, suggesting that the SR step is essential for fully eliminating unreacted LiHMDS residues. Understanding the timing and completeness of these signals helps in optimising precursor dosing and plasma timing to ensure efficient surface cleaning and minimal carbon incorporation in the final film , a key control parameter in ALD processes targeting high-purity oxides or nitrides


Figure 6. Time-resolved QMS data of selected  $m / z$  values during the LiHMDS  $+\mathrm{O}_2^*$ $+\mathrm{H}_2^*$  process. The standard ALD recipe (SR) at the start and end of the deposition, corresponding to the slow and fast growth regimes respectively, are compared to the recipes with only LiHMDS, only  $\mathrm{O}_2^*$ $+\mathrm{H}_2^*$  only LiHMDS  $+\mathrm{H}_2^*$  and only LiHMDS  $+\mathrm{O}_2^*$ .

The figure presents ion current versus time data across several subplots, each tracking a different species (e.g., H₂O⁺, SiH₃⁺, CO₂⁺, HNSi₂Me₃⁺) detected by mass spectrometry at their respective m/z values. Different reactant conditions, such as LiHMDS alone, and combinations with O₂* and H₂*,  are compared to observe how plasma and precursor combinations influence gaseous by-product formation. For example, the H₂O⁺ signal peaks during exposure to O₂*, indicating oxidative ligand removal, while HNSi₂Me₃⁺ signals provide evidence of volatile organosilicon fragments. The pressure trace at the bottom confirms timing of reagent pulses and surface reactions (SR), validating the synchrony of signal changes with process steps

| Time (s) | LiHMDS (m/z=18) | O₂* (m/z=30) | H₂* (m/z=44) | H₂O (m/z=146) |
|----------|------------------|--------------|--------------|----------------|
| 0        | 1E-10            | 1E-11        | 1E-12        | 1E-12          |
| 10       | 1.2E-10          | 1.1E-11      | 1.3E-12      | 1.2E-12        |
| 20       | 1.5E-10          | 1.4E-11      | 1.6E-12      | 1.8E-12        |
| 30       | 1.3E-10          | 1.3E-11      | 1.4E-12      | 1.5E-12        |
| 40       | 1.1E-10          | 1.2E-11      | 1.2E-12      | 1.3E-12        |

Answer: Yes

Answer: Around 20 seconds.

Answer: SiH₃⁺ (m/z = 30), CO₂⁺ (m/z = 44), and HNSi₂Me₃⁺ (m/z = 146)

Answer: The ion current trends suggest that ligand combustion and surface reactions are being actively driven during the LiHMDS + O₂* + H₂* exposure. The sharp rise in H₂O⁺ indicates oxidative ligand breakdown, possibly of methyl or HMDS groups. Concurrent increases in CO₂⁺ and HNSi₂Me₃⁺ imply that both organic and silicon-containing fragments are released as volatile by-products. The sequential timing and magnitude of these signals can guide optimization of ALD cycle parameters, such as plasma duration and purge steps,  to ensure complete removal of precursor residues and maximise film purity. This is particularly important when designing ALD processes for sensitive electronics, where residual ligands can impair dielectric or conductive properties.


Figure 7. Time-resolved QMS data of selected  $m / z$  values during the  $\mathrm{LiHMDS} + \mathrm{H}_2^* +\mathrm{O}_2^*$  process. The standard ALD recipe (SR) at the start and end of the deposition, corresponding to the slow and fast growth regimes respectively, are compared to the recipes with only LiHMDS, only  $\mathrm{O}_2^* +\mathrm{H}_2^*$ , only  $\mathrm{LiHMDS} + \mathrm{H}_2^*$  and only  $\mathrm{LiHMDS} + \mathrm{O}_2^*$ .

This figure presents time-resolved quadrupole mass spectrometry (QMS) data tracking the evolution of several ion fragments (e.g., CH₃⁺, H₂O⁺, SiH₂⁺, CO₂⁺, HNSi₂Me₅⁺) under sequential exposure to LiHMDS, hydrogen plasma (H₂*), oxygen plasma (O₂*), and combined steps in an ALD process. Notably, the CH₃⁺ and HNSi₂Me₅⁺ signals are elevated during LiHMDS dosing, consistent with precursor fragmentation. H₂O⁺ and CO₂⁺ peaks emerge during SR phases involving oxidants, suggesting combustion of ligands. The pressure trace shows dosing windows for each reactant and aligns with corresponding ion signal surges. Together, these data elucidate the chemical pathways of ligand decomposition and by-product release across plasma-activated ALD cycles

| Time (s) | LiHMDS (A) | LiHMDS+H₂* (A) | H₂*+O₂* (A) | LiHMDS+O₂* (A) | SR end (A) |
|----------|-------------|----------------|-------------|----------------|------------|
| 0        | 9.5E-11     | 9.5E-11        | 9.5E-11     | 9.5E-11        | 9.5E-11    |
| 5        | 1.1E-10     | 1.1E-10        | 1.1E-10     | 1.1E-10        | 1.1E-10    |
| 10       | 1.0E-10     | 1.0E-10        | 1.0E-10     | 1.0E-10        | 1.0E-10    |
| 15       | 9.0E-11     | 9.0E-11        | 9.2E-11     | 9.0E-11        | 9.0E-11    |
| 20       | 1.2E-10     | 1.1E-10        | 1.3E-10     | 1.2E-10        | 1.2E-10    |
| 25       | 8.5E-11     | 9.0E-11        | 1.1E-10     | 9.5E-11        | 9.0E-11    |
| 30       | 6.5E-11     | 7.5E-11        | 9.0E-11     | 7.0E-11        | 7.0E-11    |
| 35       | 5.0E-11     | 6.0E-11        | 8.0E-11     | 6.0E-11        | 6.0E-11    |
| 40       | 3.5E-11     | 4.0E-11        | 6.5E-11     | 4.5E-11        | 4.5E-11    |

| Time (s) | Pressure (mTorr) |
|----------|------------------|
| 0        | 0                |
| 5        | 50               |
| 10       | 120              |
| 15       | 50               |
| 20       | 0                |
| 25       | 50               |
| 30       | 100              |
| 35       | 50               |
| 40       | 0                |

Answer: The rise in CO₂⁺ during the SR period following O₂* exposure suggests effective combustion of organic ligands from the LiHMDS precursor, implying that oxidative plasma plays a key role in removing residual carbonaceous species. Meanwhile, HNSi₂Me₅⁺ signals peaking during the LiHMDS step indicate gas-phase fragmentation rather than surface retention. The differing behaviors underscore the sequential decomposition of ligands and highlight the importance of synchronizing plasma exposure to ensure full ligand removal.

Answer: Yes

Answer: About 120 mTorr.

Answer: H₂O⁺ (m/z=18), CO₂⁺ (m/z=44), and CH₃⁺ (m/z=15)


Fig. 12 a Normalized values of  $S_{ID} / I_{ID}^{2}$  plotted at various values of  $(V_{GS} - V_{th})$ ; b Hooge's coefficient  $(a_{\parallel})$  plotted with respect to  $(V_{GS} - V_{th})$  for the conventional HEMT and the  $\mathrm{Ga}_{2}\mathrm{O}_{3}$  MOS-HEMT

Multiple line chart displaying the relationship between frequency and Sid/ID for Ni/Au and MOS at V_GS=0.4.

Multiple line chart displaying the relationship between frequency and Sid/ID for Ni/Au and MOS at V_GS=0.6.

Multiple line chart displaying the relationship between frequency and Sid/ID for Ni/Au and MOS at V_GS=0.8.

Multiple line chart displaying the relationship between frequency and Sid/ID for Ni/Au and MOS at V_GS=01.

Scatter plot showing the relationship between VGS-Vth and Hooge's Parameter (αH) for Ni/Au-HEMT and Ga2O3 MOS-HEMT.

| Frequency (Hz) | Ni/Au | MOS |
| --- | --- | --- |
| 10^2 | 10^-10 | 9*10^-10 |
| 10^4 | 10^-12 | 10^-11 |

| Frequency (Hz) | Ni/Au | MOS |
| --- | --- | --- |
| 10^2 | 9*10^-10 | 9*10^-11 |
| 10^4 | 10^-13 | 9^-13 |

| Frequency (Hz) | Ni/Au | MOS |
| --- | --- | --- |
| 10^2 | 10^-11 | 10^-11 |
| 10^4 | 4-10^-13 | 9*10^-12 |

| VGS-Vth (V) | Ni/Au-HEMT  | Ga2O3 MOS-HEMT  |
| --- | --- | --- |
| 0.2 | 8*10^-1 | 7*10^-2 |
| 0.4 | 10^-2 | 9*10^-2 |
| 0.6 | 9*10^-1 | 3*10^-3 |
| 0.8 | 4*10^-2 | 10^-3 |

Answer: As the frequency increases, the S_iD/I_d ratio decreases for both the Ni/Au and the MOS curves.

Answer: The Ni/Au sample.

Answer: 100 Hz.

Answer: The S_iD/I_d ratio decreases when the difference increases from 0.4 to 1.

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


Fig. 3 a Growth rate of the  $\mathrm{Ga}_{2}\mathrm{O}_{3}$  thin films plotted with respect to the TEG pulse time and plasma time. b Film thickness plotted with respect to the number of applied ALD cycles

The figure shows the growth rate vs plasma time and the growth rate vs TEG pulse time. The growth rate of a material increases with increasing TEG pulse time and plasma time up to a certain point and then plateaus.

The figure shows the thickness as a function of the number of ALD cycles. The thickness of a material increases linearly with the number of ALD cycles.

| TEG pulse time | Growth rate | Plasma time | Growth rate |
| --- | --- | --- | --- |
| 0.00 | 0.015 | 0 | 0.016 |
| 0.05 | 0.06 | 5 | 0.06 |
| 0.10 | 0.06 | 10 | 0.06 |
| 0.20 | 0.06 | 20 | 0.06 |

| ALD cycle (number) | Thickness (nm) |
| --- | --- |
| 0 | 0 |
| 100 | 7 |
| 200 | 13 |
| 300 | 17 |
| 400 | 25 |
| 600 | 35 |
| 700 | - |

Answer: TEG and O2 plasma.

Answer: After 5 s of plasma exposure.

Answer: The film thickness increases with the number of ALD cycles, in accordance with the ALD process.

Answer: Yes


Figure 2. Elemental depth profiles of the samples with increasing number of  $\mathrm{LiO}^{\prime}\mathrm{Bu} - \mathrm{H}_{2}\mathrm{O}$  cycles.

The depth profile shows oxygen and manganese dominating the near-surface region of the MnO₂ film. Both elements remain fairly constant through most of the film thickness. Silicon rises sharply beyond ~1500 ×10¹⁵ at/cm², marking the substrate interface. No lithium is detected in this pristine sample.

After 10 LiO′Bu–H₂O cycles, a small lithium signal appears near the surface. Oxygen and manganese profiles remain similar to pristine MnO₂. Lithium does not penetrate deeply and drops to zero before the Si interface. This suggests early-stage, surface-limited lithiation.

With 50 cycles, lithium concentration increases and extends further into the film. The Li profile is still higher near the surface but now reaches deeper compared to 10 cycles. Mn and O remain stable within the film region. The MnO₂ framework appears preserved.

At 100 cycles, lithium is clearly incorporated throughout most of the MnO₂ layer. The Li profile becomes flatter inside the film before dropping near the Si interface. Oxygen and manganese concentrations remain relatively unchanged. This indicates a transition toward bulk lithiation.

The lithium signal strengthens further and becomes more uniform across the film thickness. Only a slight decrease is seen near the interface region. Mn and O profiles still show no major disruption. Lithiation is no longer confined to the surface.

After 300 cycles, lithium shows a high and nearly constant concentration throughout the film. The Li profile closely tracks the MnO₂ layer thickness. Oxygen and manganese remain stable until the Si interface. This panel reflects fully developed bulk lithiation.

| Depth (×10^15 at/cm^2) | O (at.%) | Mn (at.%) | Si (at.%) | Li (at.%) |
|---|---|---|---|---|
| 0    | ~0  | ~0  | ~0   | ~0  |
| 200  | ~60 | ~38 | ~0   | ~0  |
| 500  | ~62 | ~36 | ~0   | ~0  |
| 1000 | ~62 | ~34 | ~0   | ~0  |
| 1400 | ~55 | ~25 | ~10  | ~0  |
| 1600 | ~10 | ~5  | ~80  | ~0  |
| 2000 | ~0  | ~0  | ~98  | ~0  |
| 2500 | ~0  | ~0  | ~100 | ~0  |

| Depth (×10^15 at/cm^2) | O (at.%) | Mn (at.%) | Si (at.%) | Li (at.%) |
|---|---|---|---|---|
| 0    | ~0  | ~0  | ~0   | ~0  |
| 200  | ~60 | ~38 | ~0   | ~1  |
| 500  | ~60 | ~36 | ~0   | ~1  |
| 1000 | ~58 | ~33 | ~0   | ~1  |
| 1400 | ~40 | ~18 | ~20  | ~0  |
| 1600 | ~5  | ~2  | ~90  | ~0  |
| 2000 | ~0  | ~0  | ~98  | ~0  |
| 2500 | ~0  | ~0  | ~100 | ~0  |

| Depth (×10^15 at/cm^2) | O (at.%) | Mn (at.%) | Si (at.%) | Li (at.%) |
|---|---|---|---|---|
| 0    | ~0  | ~0  | ~0   | ~0  |
| 200  | ~60 | ~38 | ~0   | ~3  |
| 500  | ~60 | ~36 | ~0   | ~3  |
| 1000 | ~58 | ~34 | ~0   | ~2  |
| 1400 | ~35 | ~15 | ~25  | ~0  |
| 1600 | ~5  | ~2  | ~92  | ~0  |
| 2000 | ~0  | ~0  | ~98  | ~0  |
| 2500 | ~0  | ~0  | ~100 | ~0  |

| Depth (×10^15 at/cm^2) | O (at.%) | Mn (at.%) | Si (at.%) | Li (at.%) |
|---|---|---|---|---|
| 0    | ~0  | ~0  | ~0   | ~0  |
| 200  | ~58 | ~36 | ~0   | ~5  |
| 500  | ~60 | ~36 | ~0   | ~4  |
| 1000 | ~58 | ~33 | ~0   | ~2  |
| 1300 | ~45 | ~20 | ~10  | ~0  |
| 1500 | ~10 | ~5  | ~80  | ~0  |
| 2000 | ~0  | ~0  | ~98  | ~0  |
| 2500 | ~0  | ~0  | ~100 | ~0  |

| Depth (×10^15 at/cm^2) | O (at.%) | Mn (at.%) | Si (at.%) | Li (at.%) |
|---|---|---|---|---|
| 0    | ~0  | ~0  | ~0   | ~0  |
| 200  | ~55 | ~34 | ~0   | ~10 |
| 500  | ~56 | ~32 | ~0   | ~11 |
| 1000 | ~56 | ~30 | ~0   | ~9  |
| 1400 | ~40 | ~15 | ~15  | ~2  |
| 1600 | ~5  | ~2  | ~92  | ~0  |
| 2000 | ~0  | ~0  | ~98  | ~0  |
| 2500 | ~0  | ~0  | ~100 | ~0  |

| Depth (×10^15 at/cm^2) | O (at.%) | Mn (at.%) | Si (at.%) | Li (at.%) |
|---|---|---|---|---|
| 0    | ~0  | ~0  | ~0   | ~0  |
| 200  | ~52 | ~28 | ~0   | ~15 |
| 500  | ~52 | ~28 | ~0   | ~16 |
| 1000 | ~52 | ~27 | ~0   | ~13 |
| 1400 | ~35 | ~12 | ~20  | ~4  |
| 1600 | ~5  | ~2  | ~92  | ~0  |
| 2000 | ~0  | ~0  | ~98  | ~0  |
| 2500 | ~0  | ~0  | ~100 | ~0  |

Answer: It can be observed that, as the concentration of Li increases, Li can be found deeper in the sample.

Answer: The oxygen concentration remains approximately the same for all the samples and it can be found at depths of 1500-2000 x 10^15 at/cm^2.

Answer: No lithiation in pristine MnO₂, Surface-limited lithiation at low cycle numbers (10c–100c), Homogeneous lithiation throughout the film at high cycle numbers (200c–300c)

Answer: The surface-localized lithium signal suggests that lithium incorporation is favored near the film surface rather than uniformly throughout the bulk. This behavior is consistent with surface-limited incorporation or post-deposition modification effects, rather than bulk diffusion during growth.

Answer: Only the surface of the film is lithiated. The depth profile shows, that lithium concentration peaks near the surface and drops to neglibly low values at approx. 500x10^15 at/cm². On the other hand, the manganese and oxygene signals extend much deeper (approx. 1500 x10^15 at/cm²), indicating that the bulk of the film consists of pure manganese oxide.

Answer: Lithium in the top layer rises from 0.6 at.% (10c) to 3.2 at.% (50c) to 9.6 at.% (100c). After 300 cycles, the film becomes stoichiometric LiMn₂O₄.

Answer: At 50 cycles, lithium penetrates deeper into the MnO₂ film compared to 10 cycles. While the concentration remains highest near the surface, the Li signal now extends further toward the film interior. This reflects a progression from surface-limited to partial bulk lithiation.

Answer: It can be observed that, as the concentration of Li increases, Li can be found deeper in the sample.

Answer: The oxygen concentration remains approximately the same for all the samples and it can be found at depths of 1500-2000 x 10^15 at/cm^2.

Answer: The 300cLi-MnO2.

Answer: It is relatively homogeneous, reaching a concentration of around15 at%. Furthermore, it can be found throughout the bulk of the material.

Answer: At low cycle numbers (10-50), lithium penetrates only the surface region. At 100 cycles, Li reaches ~50% of the film depth. Above 100 cycles (200-300), lithium distributes throughout the entire film thickness, enabling stoichiometric LiMn₂O₄ formation.

Answer:
-Enables uniform electrochemical activity
-Reduces concentration gradients
-Improves cycling stability
-Enhances charge transport consistency

Answer: The lithium is not evely distributed. Deeper in the film there is less lithium, this could be due to a nucleation delay.

Answer: It can be observed that, as the concentration of Li increases, Li can be found deeper in the sample.

Answer: The oxygen concentration remains approximately the same for all the samples and it can be found at depths of 1500-2000 x 10^15 at/cm^2.

Answer: It is relatively homogeneous, reaching a concentration of around15 at%. Furthermore, it can be found throughout the bulk of the material.

Answer: Approximately 1500 x10^15 at/cm².

Answer: Yes

Answer: It can be observed that, as the concentration of Li increases, Li can be found deeper in the sample.

Answer: The oxygen concentration remains approximately the same for all the samples and it can be found at depths of 1500-2000 x 10^15 at/cm^2.

Answer: Homogeneous lithium distribution ensures uniform conversion of MnO₂ into stoichiometric LiMn₂O₄, which is essential for stable electrochemical performance and reproducible material properties.

Answer: Oxygen.

Answer: In the samples 200cLi−MnO2 and 300cLi−MnO2, lithium is observed to penetrate throughout the whole film thickness.

Answer: Partial lithiation creates a layered structure with only the surface enriched in Li. Full lithiation produces a uniform bulk composition. This homogeneity improves mechanical and electrochemical stability.

Answer: Depth profiles show very low impurity levels. High purity minimizes side reactions, improves cycling stability, and is essential for achieving high performance and long life in battery cathodes.

Answer: At x ≈ 0.5 in LiₓMn₂O₄ (~100 cycles), the crystal structure transforms from tetragonal β-MnO₂ to cubic spinel. The spinel structure has 3D Li⁺ diffusion pathways, enabling lithium to migrate throughout the film rather than being confined to surface channels.

Answer: The deposition is performed on a silicon wafer, based on the high silicon contant deeper in the sample. It is likely that the starting surface is thermal silicon oxide.

Answer: Yes

Answer: Lithium.

Answer: The depth profiles reveal that lithium is distributed only in the top part of the film in the samples 10cLi−MnO2, 50cLi−MnO2, and 100cLi−MnO2, that is, when the average composition of the material is LixMn2O4, x ≤ 0.5. In the lithiated top parts of the films in these samples, the lithium concentrations were 0.6, 3.2, and 9.6 at. %, respectively.

Answer: A weak lithium signal appears near the surface but does not penetrate deeply.

Answer: It can be observed that, as the concentration of Li increases, Li can be found deeper in the sample.

Answer: The oxygen concentration remains approximately the same for all the samples and it can be found at depths of 1500-2000 x 10^15 at/cm^2.

Answer: There is no lithium incorporation for 10 cycles of lithium deposition, this indicates that there is a delay.

Answer: It can be observed that, as the concentration of Li increases, Li can be found deeper in the sample.

Answer: The oxygen concentration remains approximately the same for all the samples and it can be found at depths of 1500-2000 x 10^15 at/cm^2.

Answer: Increasing the number of LiOtBu–H₂O cycles progressively enhances lithium incorporation into the MnO₂ films. At low cycle numbers, lithium is confined to the near-surface region, while higher cycle numbers enable lithium to penetrate deeper into the film. At 200 and 300 cycles, lithium is distributed throughout the entire film thickness, indicating complete and homogeneous gas-phase lithiation.

Answer: Across all samples, oxygen and manganese show relatively stable concentration profiles through most of the film thickness, while lithium is more concentrated near the surface and decreases with depth. Silicon concentration increases toward the interface region, indicating proximity to the substrate. The overall depth-dependent trends are similar between samples, with differences primarily in the relative prominence of the lithium signal.

Answer: No

Answer: ~1:2.

Answer: 33:66.

Answer: 300 cycles.

Answer: 0.6, 3.2 and 9.6 at.% Li, respectively.

Answer: The depth profiles show that at low cycle numbers (10-100 cycles), lithium remains confined to the upper layers of the MnO2 film. This results in compositions of LixMn2O4 with x < 0.5, where the lithium concentrations in the surface region are 0.6-9.6 at.%, depending on cycle count. At higher cycle numbers, specifically 200 and 300 cycles, lithium penetrates through the entire film, indicating complete lithiation.

Answer:
The depth profiles correspond to the following samples
a. MnO2
b. 10cLi-MnO2
c. 50cLi-MnO2
d. 100cLi-MnO2
e. 200cLi-MnO2
f. 300cLi-MnO2

Answer: Lithium is initially confined to the surface region after 10–100 cycles. It gradually penetrates deeper, achieving full, homogeneous distribution throughout the entire film after 200–300 cycles.

Answer: The Si signal marks the interface between the MnO₂/LiₓMn₂O₄ film and the Si(100) substrate.

Answer: Time-of-flight elastic recoil detection analysis (TOF-ERDA) using ⁷⁹Br⁷⁺ ions from a 5 MV tandem accelerator.

Answer: Oxygen and manganese dominate the near-surface region.

Answer: The data suggests that the ratio of Mn:O is not 1:2. This means that the film is a mixture of MnO2 and Mn2O3.


Fig. 2. Thickness profile of selected  $\mathrm{HfO_2}$  films grown from  $\mathrm{Hf[N(CH_3) - }$ $(\mathrm{C}_2\mathrm{H}_5)]_4$  and  $\mathrm{H}_2\mathrm{O}$  on borosilicate glass substrates. Growth temperatures and numbers of growth cycles applied are indicated by labels. Thicknesses are measured at variable distance from the leading edge of the substrate, which is the edge closest to the precursor inlet.

The chart shows the thickness of HfO₂ film as a function of distance from the leading edge at various growth temperatures and cycle counts.

| DISTANCE FROM THE LEADING EDGE [mm] | 150 °C, 1000 cycles [nm] | 250 °C, 1500 cycles [nm] | 275 °C, 1500 cycles [nm] | 300 °C, 1500 cycles [nm] | 225 °C, 2500 cycles [nm] |
|---|---|---|---|---|---|
| 5 | 110 | 140 | 160 | 180 | 210 |
| 10 | 110 | 140 | 160 | 180 | 210 |
| 15 | 110 | 140 | 160 | 180 | 210 |
| 20 | 110 | 140 | 150 | 180 | 200 |
| 25 | 100 | 140 | 150 | 170 | 200 |
| 30 | 100 | 130 | 150 | 170 | 200 |
| 35 | 100 | 130 | 150 | 160 | 200 |
| 40 | 100 | 130 | 150 | 160 | 200 |
| 45 | 100 | 130 | 150 | 160 | 200 |

Answer: 150, 225, 250, 275 and 300 °C.

Answer: 1000 cycles for 150 °C, 1500 cycles for 250, 275 and 300 °C, 2500 cycles for 225 °C.

Answer: At 5 mm, the film thickness is about 110 nm and at 45 mm, the film thickness is about 100 nm. The total change in thickness is therefore around 10 nm.

Answer: The samples prepared above 250 °C have a more pronounced difference in thickness compared to the beginning and end of the leading edge. The distance from the leading edge corresponds to how close that part of the film is to the precursor inlet. It is theorised by the authors that above 250 °C, the thermal decomposition of the precursor, which happens at all temperatures, becomes more significant above that temperature. Parts of the film that are closer to the precursor inlet are therefore more likely to be thicker, leading to an additional dependency.


Fig. 7. Concentrations of hydrogen, carbon, and nitrogen residues versus growth temperature. Lines are guides for the eye.

The chart shows the concentration of hydrogen, carbon, and nitrogen at various HfO₂ growth temperatures.

| HfO2 GROWTH TEMPERATURE, °C | at.% H | at.% C | at.% N |
|---|---|---|---|
| 150 | 5 | 0.5 | 0.1 |
| 175 | 3 | 0.8 | 0.2 |
| 200 | 3 | 0.6 | 0.3 |
| 225 | 2.5 | 0.7 | 0.4 |
| 250 | 2 | 0.9 | 0.5 |
| 275 | 2.5 | 1.1 | 0.6 |
| 300 | 2.5 | 1.2 | 0.7 |
| 325 | 5 | 1.5 | 0.8 |

Answer: Between 175 and 300 °C.

Answer: From 275 °C on.

Answer: 250 °C.

Answer: About 2 at.%.


Figure 1. Thermogravimetric analyses and evaporation rates of 1 (black) and 2 (gray) run at  $10^{\circ}\mathrm{C / min}$  ramp rate, with  $10^{\circ}\mathrm{C}$  increments for the stepped isotherm used to determine evaporation rate.

Thermogravimetric analyses and evaporation rates of 1 (black) and 2 (gray) run at 10 °C/min ramp rate, with 10 °C increments for the stepped isotherm used to determine evaporation rate. TGA graph shows how much mass is left as Compound 1 is heated. The black trace indicates that all of the compound vaporized cleanly starting at 91 °C, leaving 0% residue by about 150 °C.

This label shows the evaporation rate (in nmoles/min) of two compounds (1 in black, 2 in gray) as temperature increases (plotted as 1/T in K⁻¹ × 10³). Both lines are straight and sloping upward,the steeper slope for Compound 1 suggests it has a higher activation energy for evaporation than Compound 2, meaning it is more temperature-sensitive.

| temperature (°C) | mass loss (%) |material  |
|---|---|---|
| 50 | 100 | 1 |
| 50 | 100 | 2 |
| 100 | 98 | 1 |
| 100 | 98 | 2 |
| 150 | 92 | 1 |
| 150 | 92 | 2 |
| 200 | 0  | 1 |
| 200 | 20 | 2 |
| 250 | 0  | 1 |
| 250 | 18 | 2 |
| 300 | 0  | 1 |
| 300 | 17 | 2 |
| 350 | 0  | 1 |
| 350 | 15 | 2 |

| temperature (1/K x10^3) | evaporation rate (nmol/min) |material  |
|---|---|---|
| 2.25 | 1200 | 1  |
| 2.25 | 1100 | 2  |
| 2.3  | 1050 | 1  |
| 2.3  | 1030 | 2  |
| 2.35 | 1000 | 1  |
| 2.35 | 800 | 2  |
| 2.41 | 800 | 1  |
| 2.41 | 600 | 2  |
| 2.47 | 600 | 1  |
| 2.47 | 500 | 2  |
| 2.5  | 500 | 1  |
| 2.5  | 300 | 2  |
| 2.52 | 300 | 1  |
| 2.52 | 150 | 2  |
| 2.6 | 150 | 1  |
| 2.6 | 100 | 2  |

Answer: TGA measures how much mass is lost as a sample is subject to increased temperature. Thermogravimetric analysis (TGA) showed the onset of volatility at 91 °C and a residual mass of 0%.

Answer: Compound 1 vaporized completely with 0% residue, while Compound 2 left 7.4% solid residue, meaning it was less cleanly volatile and likely partially decomposed during heating. Since the mass of copper in 2 comprises 15.72% of the total molecular mass, this compound was possibly undergoing volatilization and decomposition over the thermal range of the TGA.

Answer: Because Compound 1’s evaporation rate changes sharply with small temperature changes (steep slope). To keep the vapor supply stable and repeatable for uniform film growth, the precursor temperature must be controlled very accurately (±1 °C or better).

Answer: Plotting against 1/T (inverse Kelvin) gives a straight line when evaporation follows the Arrhenius equation. The slope of the line tells us the activation energy for evaporation – a steeper slope (like Compound 1) means evaporation is more sensitive to temperature changes.


Figure 1. (Color online) Thickness measured by in situ SE as a function of the number of cycles for the  $\mathrm{Pt}$  and  $\mathrm{PtO_2}$  ALD processes. The process conditions are listed in Table I. The starting substrate at 0 cycles was  $\mathrm{Si(100)}$  with  $400 \mathrm{nm} \mathrm{SiO_2}$ . After 150 cycles of remote plasma ALD, the  $\mathrm{Pt}$  film growth is continued by thermal ALD.

The chart shows the thickness of materials deposited using different ALD methods (Remote plasma ALD Pt, Remote plasma ALD PtO₂, and Thermal ALD Pt) as a function of the number of cycles. Thermal Pt ALD shows no growth unless  applied after a Pt seed layer has been formed by remote plasma ALD. The remote plasma processes show near-linear thickness increase after a short initial nucleation period.

| Sample ID | Deposition mode and Material |  Number of cycles | Thickness (nm) |
|---|---|---|---|
| A | Thermal ALD Pt | 0 | 0 |
| A | Thermal ALD Pt | 50 | 0.05 |
| A | Thermal ALD Pt | 100 | 0.05 |
| A | Thermal ALD Pt | 150 | 0.05 |
| A | Thermal ALD Pt | 200 | 0.05 |
| A | Thermal ALD Pt | 250 | 0.06 |
| B | Remote plasma ALD PtO2| 0 | 0 |
| B | Remote plasma ALD PtO2| 20 | 0.08 |
| B | Remote plasma ALD PtO2| 30 | 0.37 |
| B | Remote plasma ALD PtO2| 40 | 0.77 |
| B | Remote plasma ALD PtO2| 50 | 1.47 |
| B | Remote plasma ALD PtO2| 60 | 2.47 |
| B | Remote plasma ALD PtO2| 130 | 4.92 |
| B | Remote plasma ALD PtO2| 200 | 7.76 |
| B | Remote plasma ALD PtO2| 250 | 9.98 |
| C | Remote plasma ALD Pt| 0 | 0 |
| C | Remote plasma ALD Pt| 20 | 0.52 |
| C | Remote plasma ALD Pt| 40 | 1.43 |
| C | Remote plasma ALD Pt| 60 | 2.99 |
| C | Remote plasma ALD Pt| 100 | 5.07 |
| C | Remote plasma ALD Pt| 150 | 7.23 |
| C | Thermal ALD Pt| 160 | 7.45 |
| C | Thermal ALD Pt| 200 | 8.97 |
| C | Thermal ALD Pt| 250 | 10.89 |

Answer: After approximately 50 cycles.

Answer: In the plot, thermal ALD Pt on the initial surface stays essentially at zero thickness over the full cycle range, indicating little to no growth. After 150 cycles of remote plasma ALD Pt, the process is switched to thermal ALD on the same sample and the thickness then increases steadily. This contrast shows that thermal ALD Pt growth proceeds when a Pt surface (seed layer) is present, but not on the starting  surface.

Answer: Remote plasma ALD Pt.

Answer: After roughly 50 cycles.


Fig. 11. Chemical compositions of TiN ALD films measured using XPS techniques. (a) Composition vs. deposition temperature using the short reactant exposure pulse sequence. (b) Composition vs. TDMAT exposure at  $180^{\circ}\mathrm{C}$ .

As deposition temperature increases, oxygen content decreases markedly while nitrogen content increases, whereas titanium remains nearly constant, indicating improved Ti–N formation at higher temperatures. Carbon remains low and only weakly temperature dependent.

Increasing TDMAT exposure at 180 °C raises oxygen content and reduces nitrogen content, while titanium stays stable, suggesting that excess precursor exposure promotes oxygen incorporation rather than additional nitridation. Overall, deposition temperature appears to be the dominant parameter governing TiN film stoichiometry.

| Deposition Temperature (°C) | O (at.%) | Ti (at.%) | N (at.%) | C (at.%) |
|---|---|---|---|---|
| ~60 | ~56 | ~31 | ~9 | ~3 |
| ~120 | ~44 | ~32 | ~19 | ~5 |
| ~180 | ~39 | ~32 | ~23 | ~5 |
| ~240 | ~37 | ~33 | ~28 | ~6 |

| TDMAT Exposure (s) | O (at.%) | Ti (at.%) | N (at.%) | C (at.%) |
|---|---|---|---|---|
| 0 | ~40 | ~32 | ~23 | ~5 |
| ~20 | ~45 | ~31 | ~18 | ~6 |
| ~100  | ~46 | ~31 | ~17 | ~7 |

Answer: Extended precursor exposure increases surface residence time of reactive species, which can promote unintended oxygen uptake. Rather than enhancing nitridation, excess exposure appears to favor impurity incorporation. This suggests saturation of Ti sites occurs early in the exposure window.

Answer: Oxygen content saturates after short TDMAT exposures and remains high at longer exposure times.

Answer: The opposing oxygen and nitrogen trends indicate competitive incorporation during growth. As temperature increases, nitrogen more effectively replaces oxygen within the film, promoting Ti–N bonding. This reflects a shift toward a more stoichiometric TiN phase.

Answer: Higher deposition temperatures are most favorable due to lower oxygen and higher nitrogen content.


Fig. 12. QCM mass ratios predicted for TiN ALD vs. the number of dimethylamine molecules produced during the TDMAT reaction,  $x$ , and the number of dimethylamino ligands incorporated per Ti atom,  $y$ .

This figure presents predicted QCM mass ratios for TiN ALD as a function of the number of dimethylamine molecules produced during the TDMAT reaction (x). Each curve corresponds to a different number of dimethylamino ligands retained per Ti atom (y). For all values of y, the QCM mass ratio increases monotonically with x. At a fixed x, higher ligand retention shifts the curves upward, indicating larger net mass uptake. The model therefore highlights the coupled influence of byproduct formation and incomplete ligand removal on QCM signals.

| y (ligand per Ti) | x (approx. range) | QCM mass ratio R (approx.) |
|----------------------|-----------------------|--------------------------------------|
| 0.0 | ~2.7–3.0 | ~0.60–0.70 |
| 0.5 | ~2.1–2.9 | ~0.70–0.90 |
| 1.0 | ~1.6–2.7 | ~0.65–1.00 |
| 1.5 | ~1.3–2.4 | ~0.75–1.10 |
| 2.0 | ~1.0–2.0 | ~0.85–1.15 |

Answer: Increased production of dimethylamine byproducts during the TDMAT reaction.

Answer: It increases the QCM mass ratio.

Answer: Retaining more dimethylamino ligands increases the mass remaining on the surface after reaction. This added mass contribution raises the predicted QCM mass ratio for any given amount of dimethylamine production.

Answer: Yes


Fig. 3. Integrated absorbance of  $\mathrm{C - H}$  and  $\mathrm{N - H}$  stretching vibrations vs. TDMAT and  $\mathrm{NH}_3$  exposures at  $152^{\circ}\mathrm{C}$ . (a) Third TDMAT exposure in ABAB... sequence. (b) Fourth  $\mathrm{NH}_3$  exposure in ABAB... sequence.

This figure tracks surface functional group evolution during an ABAB… ALD sequence using integrated IR absorbances of C–H and N–H stretching modes at 152 °C. In panel (a), increasing TDMAT exposure causes the N–H signal to rapidly decrease toward zero while the C–H signal rises and approaches saturation, indicating that TDMAT consumption of NHx*-terminated sites is accompanied by accumulation of methyl-containing ligands on the surface.

In this figure, increasing NH₃ exposure produces the opposite behavior: N–H absorbance increases and saturates while C–H absorbance decreases and levels off, consistent with NH₃-driven ligand removal and surface re-termination by NHx* species. Together, the two panels demonstrate complementary half-reactions and self-limiting surface chemistry characteristic of ALD cycling.

| TDMAT Exposure (Torr·min) | C–H (integrated absorbance) | N–H (integrated absorbance) |
|---|---|---|
| 0   | ~0.23 | ~1.00 |
| 3   | ~0.78 | ~0.25 |
| 6   | ~0.88 | ~0.15 |
| 10  | ~0.90 | ~0.10 |
| 15  | ~0.94 | ~0.06 |
| 20  | ~0.95 | ~0.04 |
| 25  | ~0.98 | ~0.02 |
| 35  | ~1.00 | ~0.01 |

| NH₃ Exposure (Torr·min) | C–H (integrated absorbance) | N–H (integrated absorbance) |
|---|---|---|
| 0     | ~1.00 | ~0.00 |
| 500   | ~0.45 | ~0.78 |
| 1000  | ~0.38 | ~0.95 |
| 1500  | ~0.36 | ~0.95 |
| 2000  | ~0.34 | ~0.85 |
| 3000  | ~0.34 | ~0.95 |
| 3500  | ~0.33 | ~0.98 |

Answer: It implies that NH₃ effectively removes methyl-derived ligands and re-terminates the surface with NHx* species. This regeneration of reactive sites is essential for sustaining cyclic ALD growth.

Answer: Residual C–H indicates carbon-containing fragments remain on the surface, which can incorporate into the growing film as impurities. Carbon contamination can increase resistivity and degrade barrier performance, so effective NH₃ exposure is critical for high-quality TiN films.

Answer: The N–H absorbance decreases most rapidly during the initial TDMAT exposure.

Answer: Saturation of the C–H signal implies that available reactive surface sites have been fully occupied by methyl-containing ligands. Additional precursor exposure does not increase adsorption, indicating complete surface coverage. This confirms self-limiting precursor chemisorption.


Fig. 8. QCM mass ratio,  $R = (m_0 + m_1) / m_0$ , measured during TiN ALD using long, medium and short reactant pulse sequences at deposition temperatures of  $60 - 240^{\circ}\mathrm{C}$ .

This plot shows the QCM mass ratio as a function of deposition temperature for three reactant pulse sequences. The short-pulse sequence remains lowest across the full temperature range (≈0.60 → 0.93), indicating a smaller relative contribution from the NH₃ half-cycle. The medium-pulse sequence starts high at 50 °C, dips near 90 °C, and then increases steadily to ~1.16 at 240 °C. The long-pulse sequence stays near ~0.85–0.95 up to 150 °C and then rises above unity at higher temperatures, reflecting a growing contribution from the second half-reaction.

| Pulse sequence | Deposition Temperature (°C) | QCM Mass Ratio R |
|---|---|---|
| Long (100-10-20-30) | 50  | ~0.88 |
| Long (100-10-20-30) | 90  | ~0.84 |
| Long (100-10-20-30) | 120 | ~0.84 |
| Long (100-10-20-30) | 150 | ~0.92 |
| Long (100-10-20-30) | 180 | ~1.02 |
| Long (100-10-20-30) | 210 | ~1.07 |
| Long (100-10-20-30) | 240 | ~1.11 |
| Medium (20-10-6-10) | 50  | ~1.06 |
| Medium (20-10-6-10) | 90  | ~0.86 |
| Medium (20-10-6-10) | 120 | ~0.88 |
| Medium (20-10-6-10) | 150 | ~0.98 |
| Medium (20-10-6-10) | 180 | ~1.08 |
| Medium (20-10-6-10) | 210 | ~1.14 |
| Medium (20-10-6-10) | 240 | ~1.16 |
| Short (1-0.5-1-5)   | 50  | ~0.60 |
| Short (1-0.5-1-5)   | 90  | ~0.66 |
| Short (1-0.5-1-5)   | 120 | ~0.67 |
| Short (1-0.5-1-5)   | 150 | ~0.70 |
| Short (1-0.5-1-5)   | 180 | ~0.78 |
| Short (1-0.5-1-5)   | 210 | ~0.80 |
| Short (1-0.5-1-5)   | 240 | ~0.93 |

Answer: Medium (20-10-6-10), R ≈ 1.16.

Answer: 180 °C (R ≈ 1.20)

Answer: An increasing R indicates that the net mass change after a full cycle grows relative to the precursor-only mass gain. This suggests that the NH₃ half-cycle contributes more strongly at higher temperatures, likely due to more complete ligand removal or enhanced reaction progress.

Answer: Yes


Fig. 9. Resistivities of TiN ALD films measured using the four-point probe for long, medium and short reactant pulse sequences at deposition temperatures of  $60 - 240^{\circ}\mathrm{C}$ .

This figure shows the electrical resistivity of TiN ALD films as a function of deposition temperature. For all pulse lengths, resistivity decreases sharply with increasing temperature. Short pulse sequences consistently yield the lowest resistivity at high temperature. Medium pulses show intermediate behavior, while long pulses retain substantially higher resistivity, especially at lower temperatures. The results indicate that both deposition temperature and pulse timing strongly influence TiN film electrical quality.

| Pulse sequence | Deposition temperature (°C) | Resistivity (µΩ·cm) |
|---|---|---|
| Short  | 60  | ~2.5×10⁷ |
| Short  | 120 | ~5×10⁶ |
| Short  | 180 | ~5×10⁴ |
| Short  | 240 | ~1.5×10⁴ |
| Medium | 120 | ~2×10⁷ |
| Medium | 180 | ~3×10⁵ |
| Medium | 240 | ~2×10⁴ |
| Long   | 180 | ~1×10⁷ |
| Long   | 240 | ~3×10⁵ |

Answer: The short pulse sequence.

Answer: It decreases by several orders of magnitude.

Answer: Shorter pulses limit excessive precursor exposure and reduce residual ligand incorporation in the growing film. At higher temperatures, this favors cleaner surface reactions, improved film densification, and better grain connectivity. These structural improvements reduce electron scattering and lead to lower resistivity compared with longer pulse sequences.

Answer: No


Fig. 10 Absorption coefficient  $(\alpha)$  as a function of the photon energy  $(E)$  of the ALD ZnO:B films deposited at  $150^{\circ}C$  on glass substrates.

The figure shows the absorption coefficient  of ZnO:B as a function of photon energy E, with various doping levels (DF) indicated by different colors, it also highlights the shift in the absorption edge with increasing doping.

| DF | \(\alpha\) \((10^{3} \text{ cm}^{-1})\) @ 1.2 eV | n \((10^{20} \text{ cm}^{-3})\) |
| --- | --- | --- |
| intrinsic ZnO | 0.41 | 0.13 |
| 0.014 | 0.79 | 1.22 |
| 0.016 | 0.96 | 1.79 |
| 0.018 | 1.50 | 2.25 |
| 0.027 | 1.90 | 2.25 |
| 0.034 | 2.60 | 3.10 |
| 0.053 | 2.66 | 2.70 |
| 0.063 | 2.18 | 1.85 |
| 0.075 | 1.59 | 1.34 |
| 0.094 | 1.39 | 1.08 |

Answer: No. From SE data.

Answer:
Clearly in the NIR region, the absorption decreases with increasing DF up to 0.034 whereas it increases again for
higher DF values.

Answer: The absorption increase in NIR region with increase in doping can be attributed to the free-carrier absorption in the films as described by the Drude model

Answer:
The carrier concentration is highest at the following DF,
1. At DF 0.034 = 3.1
2. At DF 0.053 = 2.7
further increase of DF does not increase the concentration and hence this is attributed to FCA


Fig. 9 Transmittance of selected ZnO:B samples  $(\mathrm{DF} = 0.000 - 0.063)$  deposited at  $150^{\circ}C$  and with thicknesses of  $45\pm 5$  nm.

The chart shows the transmittance of ZnO:B at different wavelengths for various doping fractions. The transmittance increases with increasing wavelength, reaching nearly 100% above 1000 nm.

| Wavelength (nm) | Intrinsic ZnO (%) | DF = 0.016 (%) | DF = 0.018 (%) | DF = 0.034 (%) | DF = 0.063 (%) |
|-----------------|--------------------|-----------------|-----------------|-----------------|-----------------|
| 300             | 40                | 38              | 36              | 34              | 32              |
| 400             | 85                | 82              | 80              | 78              | 75              |
| 600             | 92                | 90              | 89              | 87              | 85              |
| 1000            | 94                | 93              | 92              | 91              | 90              |
| 1500            | 95                | 94              | 93              | 92              | 91              |
| 2000            | 95                | 94              | 93              | 92              | 91              |
| 2400            | 95                | 94              | 93              | 92              | 91              |

Answer: The transmittance values were over 90% in the major part of the visible region

Answer: A decrease in transmittance was observed in the NIR region with increasing doping fraction until DF = 0.034. For higher DF values, the transmittance in the NIR increased again. This behaviour can be attributed to free-carrier absorption.

Answer: A blue shift was observed in the ultraviolet absorption edge with increasing doping concentration from intrinsic ZnO to doped ZnO:B films with a DF of 0.063. This is due to the increase of the optical band gap.

Answer: Yes


Figure 5. The imaginary part of the dielectric function  $(\epsilon_{2})$  of the  $\mathrm{Co}_3\mathrm{O}_4$ ,  $\mathrm{Li}_2\mathrm{CO}_3$  and  $\mathrm{LiCoO_2}$  films as determined by in situ spectroscopic ellipsometry.

The imaginary part of the dielectric function, epsilon2, is plotted versus photon energy for Co3O4, LiCoO2, and Li2CO3, as determined by in situ spectroscopic ellipsometry. Co3O4 shows the largest epsilon2 values, LiCoO2 is much lower, and Li2CO3 remains near zero across most of the range, indicating very weak contribution compared with the other films.

| Photon energy (eV) | Co3O4 (epsilon_2) | LiCoO2 (epsilon_2) | Li2CO3 (epsilon_2) |
|---|---|---|---|
| 1.25 | 1.2 | 0.15 | 0.00 |
| 1.50 | 2.5 | 0.18 | 0.00 |
| 1.65 | 5.5 | 0.20 | 0.00 |
| 2.00 | 4.1 | 0.25 | 0.00 |
| 2.40 | 4.8 | 0.35 | 0.00 |
| 2.75 | 6.0 | 0.50 | 0.00 |
| 3.10 | 5.2 | 0.70 | 0.00 |
| 3.40 | 4.6 | 0.60 | 0.01 |
| 3.70 | 4.5 | 0.60 | 0.01 |
| 4.00 | 4.7 | 0.75 | 0.02 |
| 4.25 | 4.9 | 0.90 | 0.03 |
| 4.75 | 5.6 | 1.25 | 0.05 |
| 5.00 | 5.8 | 1.20 | 0.06 |
| 5.40 | 6.0 | 1.15 | 0.08 |
| 5.80 | 5.8 | 1.05 | 0.10 |
| 6.00 | 5.4 | 1.00 | 0.12 |
| 6.50 | 4.6 | 0.80 | 0.05 |

Answer: These reference spectra help distinguish which phases contribute to the optical response measured during growth. The paper notes a clear difference between the three films and uses this comparison to interpret the LiCoO2 signal. In particular, the discussion indicates that Li2CO3 contributes very little to the LiCoO2 epsilon2 spectrum under these conditions.

Answer: Co3O4

Answer: The x axis is photon energy (eV) and the y axis is the dielectric function epsilon2. Epsilon2 is the imaginary part of the dielectric function and is directly related to optical absorption in the material. Larger epsilon2 values generally indicate stronger absorption at those photon energies.

Answer:
Co3O4

LiCoO2

Li2CO3
Smallest epsilon2 curve: Li2CO3