Anita Brady-Boyd

2,2′,7,7′-Tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (Spiro-OMeTAD) is widely used as a hole-transporting material in perovskite solar cells (PSCs); however, its intrinsic thermal stability remains insufficiently understood. Here, the thermal stability and high-temperature behaviour of pristine Spiro-OMeTAD films prepared by solution processing and vacuum deposition are systematically investigated using real-time and standard x-ray photoelectron spectroscopy, with annealing temperatures up to 500 °C under ultra-high vacuum. Spiro-OMeTAD films deposited on different substrates exhibit similar chemical environments and photoemission characteristics, demonstrating that the surface chemistry is largely insensitive to deposition method and substrate. Pristine Spiro-OMeTAD remains chemically stable up to 300 °C. Above an onset temperature of approximately 350 °C, partial decomposition of surface molecules occurs, characterised by progressive detachment of the terminating methoxy groups. In contrast, the spirobifluorene and phenylamine backbones retain structural integrity up to 500 °C, without evidence of evaporation or fragmentation, even for vacuum-deposited films. The loss of methoxy groups leads to a modification of the valence band structure, with the valence band maximum shifting towards higher binding energy and the ionisation potential increasing accordingly. These results define intrinsic thermal limits for pristine Spiro-OMeTAD and indicate that, provided other functional layers permit, processing temperatures up to 300 °C may be accessible, whereas exposure above 350 °C is expected to compromise interfacial electronic properties in PSCs.

Perfluorododecyl iodide (I-PFC12) is of interest for area-selective deposition (ASD) applications as it exhibits intriguing properties such as ultralow surface energy, the ability to modify silicon’s band gap, low surface friction, and suitability for micro-contact patterning. Traditional photolithography is struggling to reach the required critical dimensions. This study investigates the potential of using I-PFC12 as a way to produce contrast between the growth area and non-growth areas of a surface subsequent to extreme ultraviolet (EUV) exposure. Once exposed to EUV, the I-PFC12 molecule should degrade with the help of the photocatalytic substrate, allowing for the subsequent selective deposition of the hard mask. The stability of a vapor-deposited I-PFC12 self-assembled monolayer (SAM) was examined when exposed to ambient light for extended periods of time by using X-ray photoelectron spectroscopy (XPS). Two substrates, SiO₂ and TiO₂, are investigated to ascertain the suitability of using TiO₂ as a photocatalytic active substrate. Following one month of exposure to light, the atomic concentrations showed a more substantial fluorine loss of 10.2% on the TiO₂ in comparison to a 6.2% loss on the SiO₂ substrate. This more pronounced defluorination seen on the TiO₂ is attributed to its photocatalytic nature. Interestingly, different routes to degradation were observed for each substrate. Reference samples preserved in dark conditions with no light exposure for up to three months show little degradation on the SiO₂ substrate, while no change is observed on the TiO₂ substrate. The results reveal that the I-PFC12 SAM is an ideal candidate for resistless EUV lithography.

This study describes the utilization of near edge X‐ray absorption fine structure (NEXAFS) to investigate the hole transporting material (HTM) 2,2ʹ,7,7ʹ‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐ 9,9ʹ‐spirobifluorene (Spiro‐OMeTAD) and its most common dopants, lithium bis‐(trifluoromethylsulfonyl) imide (LiTFSI), 4‐tert‐butylpiridine (tBP), and 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4‐TCNQ). By changing the angle of the sample with respect to the beam, the orientation of the molecules on the surface can be observed. The data suggest that it is difficult to determine any orientational preference for Spiro‐OMeTAD deposited on a surface due to the 3D propeller‐like geometry of this molecule. Both doped and undoped samples show thermal stability beyond the glass transition temperature of the molecules. Significant changes to the Spiro‐OMeTAD spectra are observed with the addition of the dopants, in particular the C K‐edge. Differences are also observed in the valence band spectra when dopants are added. It is also demonstrated how the doping combination of LiFTSI with tBP and, F4‐TCNQ act as p‐type dopants by altering the position of the HOMO levels. The F4‐TCNQ induces a larger change in the HOMO levels when compared to the LiTFSI and tBP. These results are important to increase the understanding of Spiro‐OMeTAD and the effect dopants have on this material for next generation solar cells.

The rush for better-performing electronics, and manufacturing processes that heavily rely on "top-down" patterning techniques, is making the integration of "self-aligned" fabrication methods, such as area-selective deposition (ASD), a critical objective for continued device scaling. The fully self-aligned via (FSAV) scheme is broadly proposed as a "killer application" to determine whether ASD can shift from an R&D process to high-volume manufacturing. Nevertheless, the lack of a suitable low-κ deposition process has prevented the realization of FSAV by dielectric-on-dielectric ASD. This is primarily due to the high temperature and/or strong oxidizers employed during low-κ dielectric deposition and their unsuitability in the presence of organic masks, such as self-assembled monolayers (SAMs), used to prevent material nucleation during ASD. In this work, AlO_x and Al-silicate atomic layer deposition (ALD) processes are studied to provide suitable materials for ASD-enabled FSAV. Dimethylaluminum isopropoxide and H₂O are utilized to deposit the metal oxide, whereas Al-silicate is grown by adding 2,2-dimethoxy-1,6-diaza-2-silacyclooctane (DMDAcO) pulses to the AlO_x ALD cycle. The selectivity of such processes is demonstrated on 50 nm Cu/SiO₂ structures, using octadecanethiol-derived SAMs to inhibit material nucleation on the metal lines. Scanning and transmission electron microscopies are employed to assess the quality of the ASD processes and investigate the mechanisms behind defect generation on a nongrowth surface. X-ray photoelectron spectroscopy measurements show the high purity of the AlO_x film, whereas DMDAcO-ligand incorporation into the Al-silicate matrix is observed. Planar capacitor structures are used to assess the electrical properties of both ASD films, revealing that the silicate film exhibits a relatively low κ-value (5.3 ± 0.2), with a high acceleration field factor (32.4 ± 1.4) and a dielectric breakdown voltage of 6.0 ± 0.3 V at 100 °C.

HfO2 is investigated for its suitability to act as an oxygen and moisture barrier to prevent Cu oxidation in redistribution layers (RDLs) in 3D packaging technologies. HfO2 barriers of varying thicknesses were deposited via atomic layer deposition (ALD) on Cu surfaces and then stressed by (i) high temperature stress and (ii) humidity and thermal stress for 1000 h to ascertain the optimal thickness to prevent oxidation of the Cu. The thickness of the ALD HfO2 film was monitored by ellipsometry, while the extent of Cu oxidation was monitored by focus ion beam prepared SEM cross sections. It is found that & SIM;9 nm of HfO2 is sufficient to prevent Cu oxidation.