(Color online) Ball-and-stick representation of atomic geometries optimized using DFT precursor fragments M(NR1R2)2 adsorbed onto a hydroxylated MO2 surface where (a) x = 3, (b) x = 2, and (c) x = 1; colour code for M = grey, O = red, C = dark grey, N = dark blue, H = white.
Saturation curve of the TEMAZ precursor: ZrO2 thickness and standard deviation in dependence of the TEMAZ pulse time for 47 reaction cycles and a 3 s O3 pulse time at TD = 265 °C.
TEM micrograph of a hole with an aspect ratio of 1:20 showing ∼81% step coverage of 103 cycles ZrO2 at TD = 265 °C.
(Color online) Linear growth of ZrO2 thin films: ZrO2 thickness and standard deviation as function of reaction cycles at different deposition temperatures TD.
(Color online) ALD temperature window of new the ZrO2 process indicating the amorphous GPC (a-GPC) and crystalline GPC (c-GPC) at different deposition temperatures TD.
(Color online) X-ray diffraction pattern of the ZrO2 film thickness series at a deposition temperature of 270 °C.
(Color online) Surface roughness measured as rms-value by AFM plotted against the number of ALD reaction cycles for deposition temperatures of 270 and 275 °C.
(Color online) XPS spectrum of the Zr3d peak doublet of ZrO2 deposited on SiO2/Si-substrate at a TD of 270 °C.
(Color online) Angle-resolved XPS spectra of Zr3d peak doublets of as-deposited and annealed ZrO2 on a TiN-substrate at detection angles of 80°, 40°, and 20° to the surface normal (TD = 265 °C).
(Color online) EOT vs film thickness of as-deposited and annealed ZrO2 deposited at TD = 270 °C.
(Color online) Leakage current density vs bias of MIM capacitors with 10 nm TiN bottom and top electrode and 7.9 and 9.0 nm ZrO2 thin films, respectively (TD = 265 °C). The electrical parameters qϕFN and ε∞ are indicated for both capacitors and both polarities.
(Color online) Time-dependent saturation curve of sheet resistivity indicating the TiO2 formation on a 10 nm TiN thin film after an HF-dip.
(Color online) XPS spectra of the Ti2p peak doublet of an oxidized TiN surface compared to a TiN surface cleaned by an HF-dip fitted with three components TiO2, TiON, and TiN at a detection angle of 0°.
(Color online) Quantitative XPS analysis showing the chemical composition of the Ti2p peak doublet after an HF-dip with different queue times and O3 pulse time variations in the following deposition of the new ZrO2 process (TD = 265 °C).
(Color online) ToF-SIMS depth profile of a ZrO2/TiN film stack manufactured with HF-dip (5 min queue time) and 3 s O3 pulse time compared to the interface without O3 pulse in the first 10 cycles of the ALD (TD = 265 °C).
(Color online) XPS spectra of Ti2p peak doublet after the deposition and annealing of 5 nm ZrO2 thin films (TD = 265 °C) at a detection angle of 40°.
(Color online) Leakage current density as function of the electric field of MIM capacitors with standard integration of 7.9 nm ZrO2 and with optimized interface below a 8.4 nm ZrO2 film (TD = 265 °C). The electrical parameters qϕFN and ε∞ are indicated for the optimized integration route and both polarities.
Estimation of surface coverage of ligands at end of the metal precursor pulse. The diameter of the adsorbate is measured from DFT-optimized geometries and is used to calculate the area of hard discs, which are assumed to cover the surface in a perfect hexagonal array.
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