RESUMEN
Atomic layer deposition (ALD) has attracted much attention, particularly for applications in nanoelectronics because of its atomic-level controllability and high-quality products. In this study, we developed a plasma-enhanced atomic layer deposition (PEALD) process to fabricate a homogeneous indium aluminum oxide (IAO) semiconductor film. Trimethylaluminum (TMA) and dimethylaluminum isopropoxide (DMAI) were used as Al precursors, which yielded different compositions. Density functional theory (DFT) calculations on the surface reactions between indium and aluminum precursors showed that while highly reactive TMA would etch In, DMAI with lower reactivity would allow indium to persist in the films, resulting in a more controlled doping of Al. The In/Al composition ratio could be further precisely controlled by adjusting the indium precursor dose time to sub-saturation. IAO based on DMAI was applied to fabricate thin-film transistors (TFTs), showing that Al can be a carrier suppressor of indium oxide. TFTs with PEALD IAO containing 3.8 atomic % Al showed a turn-on voltage of -0.4 ± 0.3 V, a subthreshold slope of 0.09 V/decade, and a field effect mobility of 18.9 cm2/(V s).
RESUMEN
Surface fluorination and volatilization using hydrogen fluoride and trimethyaluminum (TMA) is a useful approach to the thermal atomic layer etching of Al2O3. We have previously shown that significant enhancement of the TMA etching effect occurs when performed in the presence of lithium fluoride chamber-conditioning films. Now, we extend this enhanced approach to other alkali halide compounds including NaCl, KBr, and CsI. These materials are shown to have varying capacities for the efficient removal of AlF3 and ultimately lead to larger effective Al2O3 etch rates at a given substrate temperature. The most effective compounds allow for continuous etching of Al2O3 at substrate temperatures lower than 150 °C, which can be a valuable route for processing temperature-sensitive substrates and for improving the selectivity of the etch over other materials. The strong interaction between TMA and alkali halide materials also results in material-selective thin-film deposition at these reduced substrate temperatures. We discuss possible mechanisms of this etching enhancement and prospects for extending this approach to other material systems. The consequences of using TMA as an ALD and ALE precursor are discussed in the context of interface engineering for alkali-containing substrates such as lithium battery materials.
RESUMEN
Polyphthalaldehyde is a self-developing resist material for electron beam and thermal scanning probe lithography (t-SPL). Removing the resist in situ (during the lithography process itself) simplifies processing and enables direct pattern inspection, however, at the price of a low etch resistance of the resist. To convert the material into a etch resistant hard mask, we study the selective cyclic infiltration of trimethyl-aluminum (TMA)/water into polyphthalaldehyde. It is found that TMA diffuses homogeneously through the resist, leading to material expansion and formation of aluminum oxide concurrent to the exposure to water and the degradation of the polyphthalaldehyde polymer. The plasma etch resistance of the infiltrated resist is significantly improved, as well as its stability. Using a silicon substrate coated with 13 nm silicon nitride and 7 nm cross-linked polystyrene, high resolution polyphthalaldehyde patterning is performed using t-SPL. After TMA/H2O infiltration, it is demonstrated that pattern transfer into silicon can be achieved with good fidelity for structures as small as 10 nm, enabling >10× amplification and low surface roughness. The presented results demonstrate a simplified use of polyphthalaldehyde resist, targeting feature scales at nanometer range, and suggest that trimethyl-aluminum infiltration can be applied to other resist-based lithography techniques.
RESUMEN
Thermal atomic layer etching (ALE) is an emerging technique that involves the sequential removal of monolayers of a film by alternating self-limiting reactions, some of which generate volatile products. Although traditional ALE processes rely on the use of plasma, several thermal ALE processes have recently been developed using hydrogen fluoride (HF) with precursors such as trimethylaluminum (TMA) or tin acetylacetonate. While HF is currently the most effective reagent for ALE, its potential hazards and corrosive nature have motivated searches for alternative chemicals. Herein, we investigate the feasibility of using fluoroform (CHF3) with TMA for the thermal ALE of SiO2 and Al2O3 surfaces and compare it to the established TMA/HF process. A fundamental mechanistic understanding is derived by combining in situ Fourier transform infrared spectroscopy, ex situ X-ray photoemission spectroscopy, ex situ low-energy ion scattering, and ex situ spectroscopic ellipsometry. Specifically, we determine the role of TMA, the dependence of the etch rate on precursor gas pressure, and the formation of a residual fluoride layer. Although CHF3 reacts with TMA-treated oxide surfaces, etching is hindered by the concurrent deposition of a fluorine-containing layer, which makes it unfavorable for etching. Moreover, since fluorine contamination can be deleterious to device performance and its presence in thin films is an inherent problem for established ALE processes using HF, we present a novel method to remove the residual fluorine accumulated during the ALE process by exposure to water vapor. XPS analysis herein reveals that an Al2O3 film etched using TMA/HF at 325 °C contains 25.4 at. % fluorine in the surface region. In situ exposure of this film to water vapor at 325 °C results in â¼90% removal of the fluorine. This simple approach for fluorine removal can easily be applied to ALE-treated films to mitigate contamination and retain surface stoichiometry.
RESUMEN
Methyltrioxorhenium (ReO3Me) is introduced as the first rhenium atomic layer deposition (ALD) precursor and used to grow rhenium-aluminum oxide thin films in combination with trimethylaluminum (TMA-AlMe3). The growth rate of the smooth Re-Al oxide films, with general stoichiometry RexAlyO3x, has been monitored by in situ quartz crystal microbalance (QCM) and ex situ ellipsometry, and found to be 3.2 Å/cycle. X-ray photoelectron spectroscopy (XPS) revealed the mixed valent composition of the film with Re(III) species being the main component. In addition, ReO3Me has been successfully used to deposit rhenium oxide in NU-1000, a mesoporous zirconium-based metal-organic framework (MOF). The metalated MOF was found to retain porosity and crystallinity and to be catalytically active for ethene hydrogenation.
RESUMEN
The thermal atomic layer etching (ALE) of SiO2 was performed using sequential reactions of trimethylaluminum (TMA) and hydrogen fluoride (HF) at 300 °C. Ex situ X-ray reflectivity (XRR) measurements revealed that the etch rate during SiO2 ALE was dependent on reactant pressure. SiO2 etch rates of 0.027, 0.15, 0.20, and 0.31 Å/cycle were observed at static reactant pressures of 0.1, 0.5, 1.0, and 4.0 Torr, respectively. Ex situ spectroscopic ellipsometry (SE) measurements were in agreement with these etch rates versus reactant pressure. In situ Fourier transform infrared (FTIR) spectroscopy investigations also observed SiO2 etching that was dependent on the static reactant pressures. The FTIR studies showed that the TMA and HF reactions displayed self-limiting behavior at the various reactant pressures. In addition, the FTIR spectra revealed that an Al2O3/aluminosilicate intermediate was present after the TMA exposures. The Al2O3/aluminosilicate intermediate is consistent with a "conversion-etch" mechanism where SiO2 is converted by TMA to Al2O3, aluminosilicates, and reduced silicon species following a family of reactions represented by 3SiO2 + 4Al(CH3)3 â 2Al2O3 + 3Si(CH3)4. Ex situ X-ray photoelectron spectroscopy (XPS) studies confirmed the reduction of silicon species after TMA exposures. Following the conversion reactions, HF can fluorinate the Al2O3 and aluminosilicates to species such as AlF3 and SiOxFy. Subsequently, TMA can remove the AlF3 and SiOxFy species by ligand-exchange transmetalation reactions and then convert additional SiO2 to Al2O3. The pressure-dependent conversion reaction of SiO2 to Al2O3 and aluminosilicates by TMA is critical for thermal SiO2 ALE. The "conversion-etch" mechanism may also provide pathways for additional materials to be etched using thermal ALE.
RESUMEN
Atomic layer deposition (ALD) of alumina using trimethylaluminum (TMA) has technological importance in microelectronics. This process has demonstrated a high potential in applications of protective coatings on Cu surfaces for control of diffusion of Cu in Cu2S films in photovoltaic devices and sintering of Cu-based nanoparticles in liquid phase hydrogenation reactions. With this motivation in mind, the reaction between TMA and oxygen was investigated on Cu(111) and Cu2O/Cu(111) surfaces. TMA did not adsorb on the Cu(111) surface, a result consistent with density functional theory (DFT) calculations predicting that TMA adsorption and decomposition are thermodynamically unfavorable on pure Cu(111). On the other hand, TMA readily adsorbed on the Cu2O/Cu(111) surface at 473 K resulting in the reduction of some surface Cu(1+) to metallic copper (Cu(0)) and the formation of a copper aluminate, most likely CuAlO2. The reaction is limited by the amount of surface oxygen. After the first TMA half-cycle on Cu2O/Cu(111), two-dimensional (2D) islands of the aluminate were observed on the surface by scanning tunneling microscopy (STM). According to DFT calculations, TMA decomposed completely on Cu2O/Cu(111). High-resolution electron energy loss spectroscopy (HREELS) was used to distinguish between tetrahedrally (Altet) and octahedrally (Aloct) coordinated Al(3+) in surface adlayers. TMA dosing produced an aluminum oxide film, which contained more octahedrally coordinated Al(3+) (Altet/Aloct HREELS peak area ratio ≈ 0.3) than did dosing O2 (Altet/Aloct HREELS peak area ratio ≈ 0.5). After the first ALD cycle, TMA reacted with both Cu2O and aluminum oxide surfaces in the absence of hydroxyl groups until film closure by the fourth ALD cycle. Then, TMA continued to react with surface Al-O, forming stoichiometric Al2O3. O2 half-cycles at 623 K were more effective for carbon removal than O2 half-cycles at 473 K or water half-cycles at 623 K. The growth rate was approximately 3-4 Å/cycle for TMA+O2 ALD (O2 half-cycles at 623 K). No preferential growth of Al2O3 on the steps of Cu(111) was observed. According to STM, Al2O3 grows homogeneously on Cu(111) terraces.
RESUMEN
Interface-formation processes in atomic layer deposition (ALD) of Al2O3 on InGaAs surfaces were investigated using on-line Auger electron spectroscopy. Al2O3 ALD was carried out by repeating a cycle of Al(CH3)3 (trimethylaluminum, TMA) adsorption and oxidation by H2O. The first two ALD cycles increased the Al KLL signal, whereas they did not increase the O KLL signal. Al2O3 bulk-film growth started from the third cycle. These observations indicated that the Al2O3/InGaAs interface was formed by reduction of the surface oxides with TMA. In order to investigate the effect of surface-oxide reduction on metal-insulator-semiconductor (MIS) properties, capacitors and field-effect transistors (FETs) were fabricated by changing the TMA dosage during the interface formation stage. The frequency dispersion of the capacitance-voltage characteristics was reduced by employing a high TMA dosage. The high TMA dosage, however, induced fixed negative charges at the MIS interface and degraded channel mobility.