Crystallization study by transmission electron microscopy of SrTiO3 thin films prepared by plasma-assisted ALD

The crystallization behavior of thin strontium titanate (SrTiO3, STO) films with ~15 nm thickness was studied by Transmission Electron Microscopy (TEM). Amorphous STO films with [Sr]/([Sr]+[Ti]) ratio ranging from 0.50 to 0.63 were deposited at 350°C by plasma-assisted ALD and subsequently treated by rapid thermal annealing in flowing N2 for crystallization. Different temperatures and annealing durations were employed to fully characterize the crystallization process. TEM analysis showed that transrotational crystals were formed and evidenced the influence of the STO composition and of the thermal budget applied on the grain size, crack and void formation. In particular, Sr-rich layers ([Sr]/([Sr]+[Ti] = 0.59) showed a finer crystalline structure which was imputed to a higher nucleation probability at the onset of the crystallization process. Crystallization into the perovskite structure was confirmed for all the film compositions studied. By tuning the STO composition and the thermal budget of the annealing step it was demonstrated that it is possible to control the microstructure of the crystallized film as a further step in optimizing the STO film properties

Low-temperature deposition of TiN by plasma-assisted atomic layer deposition

Titanium nitride (TiN) films were deposited by a plasma-assisted at. layer deposition (PA-ALD) process, based on TiCl4 precursor dosing and remote H2-N2 plasma exposure, at temps. ranging from 100 to 400 DegC. The plasma, the PA-ALD process, and the resulting TiN material properties were extensively investigated. The plasma was studied by optical emission spectroscopy and Langmuir probe, revealing an ion d. of 109 cm-3 and an electron temp. of 3.5 eV just above the substrate. Under floating conditions there is thus a considerable ion flux towards the substrate per ALD cycle with a typical ion energy of .apprx.15 eV. TiN film growth was studied by in situ spectroscopic ellipsometry, revealing self-limiting surface reactions for the complete temp. range. At 100 DegC the growth rate of 0.3 A/cycle was found to be significantly lower than the growth rate of 0.6 A/cycle at 400 DegC. The stoichiometry of the films varied with the plasma exposure time, while the Cl content was mostly affected by the deposition temp. (2.1 atom % at 100 DegC to 0.07 atom % at 400 DegC). Resistivities as low as 71 mW cm were obtained at a temp. of 400 DegC, while at 100 DegC a fair resistivity of 209 mW cm was reached. These results show that PA-ALD with TiCl4 and H2-N2 plasma is well suited for low-temp. deposition of high-quality TiN films. [on SciFinder (R)

Apparatus and method for reactive ion etching

The invention relates to an apparatus for reactive ion etching of a substrate, comprising: a plasma etch zone including an etch gas supply and arranged with a plasma generating structure for igniting a plasma and comprising an electrode structure arranged to accelerate the etch plasma toward a substrate portion to have ions impinge on the surface of the substrate; a passivation zone including a cavity provided with a passivation gas supply; said supply arranged for providing a passivation gas flow from the supply to the cavity; the cavity in use being bounded by the injector head and the substrate surface; and a gas purge structure comprising a gas exhaust arranged between said etch zone and passivation zone; the gas purge structure thus forming a spatial division of the etch and passivation zones

Vanadium oxide monolayer catalysts. 3. A Raman spectroscopic and temperature-programmed reduction study of monolayer and crystal-type vanadia on various supports

Vanadium(V) oxide supported on 7-A1203, GO2, Cr2O3, Si02, Ti02, and Zr02 was studied by X-ray fluorescence, by X-ray diffraction, and especially by the combination of Raman spectroscopy and temperature-programmed reduction (TPR) for qualitative and quantitative structural analysis, respectively. Catalysts were prepared via ion-exchange and wet-impregnation methods. The V contents ranged from - 1 to 40 wt % V. At low surface concentrations only surface vanadate phases of two-dimensional character are observed for all carriers. According to Raman and TPR data the structure of these surface vanadate species is independent of the preparation technique. At medium and high surface concentrations, the webimpregnated samples already contain crystalline V20b At equal surface concentrations the ion-exchanged catalysts contain no V205 crystallites. An exception is Si02 on which also crystalline V206 is formed in both preparation techniques. Monolayer stability toward thermal treatment decreases in the order AZO>3 Ti02> Ce02,w hereas on heating ion-exchanged V/Si02 the crystalline V206 spreads out over the silica surface. The reducibilities of the ion-exchanged catalyats, as measured by TPR, can be used as a measure for the contact interaction between vanadia and the carrier oxides. At temperatures of 500-800 K, this interaction ranges from strong with titania to weak with silica as a carrier

Research Update: Atmospheric pressure spatial atomic layer deposition of ZnO thin films: Reactors, doping, and devices

Atmospheric pressure spatial atomic layer deposition (AP-SALD) has recently emerged as an appealing technique for rapidly producing high quality oxides. Here, we focus on the use of AP-SALD to deposit functional ZnO thin films, particularly on the reactors used, the film properties, and the dopants that have been studied. We highlight how these films are advantageous for the performance of solar cells, organometal halide perovskite light emitting diodes, and thin-film transistors. Future AP-SALD technology will enable the commercial processing of thin films over large areas on a sheet-to-sheet and roll-to-roll basis, with new reactor designs emerging for flexible plastic and paper electronics.The authors acknowledge the support of the Rutherford Foundation of New Zealand and the Cambridge Commonwealth, European and International Trusts, and the ERC Advanced Investigator Grant, Novox, ERC-2009-adG247276. DMR acknowledges Marie Curie Actions (FP7/2007-2013, Grant Agreement Nos. 219332 and 631111), and the Ramon y Cajal 2011 programme from the Spanish MICINN and the European Social Fund, and the Comissionat per a Universitats I Recerca (CUR) del DIUE de la Generalitat de Catalunya, Spain.This is the final published version of the article. It was originally published in APL Materials (Hoye RLZ, Muñoz-Rojas D, Nelson SF, Illiberi A, Poodt P, Roozeboom F, MacManus-Driscoll JL, APL Materials, 2015, 3, 040701, doi:10.1063/1.4916525). The final version is available at http://dx.doi.org/10.1063/1.491652

Thermal and Remote Plasma ALD of Ru from CpRu(CO)2Et and O2

Ruthenium (Ru) is regarded as an electrode candidate on ultrahigh-k SrTiO3 dielectric films for future high-density trench capacitors. To achieve conformal film growth, atomic layer deposition (ALD) of Ru is investigated. To this end, the use of an oxidizing reactant is desired to avoid electronic degradation of the interface properties of SrTiO3 as found when using a NH3 plasma for Ru ALD or when using thermal ALD TiN as electrode. Thermal ALD of Ru using O2 gas, however, generally results in a pronounced nucleation delay and high surface roughness. The current work aims at developing ALD of Ru using an O2 plasma in order to improve the film nucleation and to try to obtain smoother films. Using the novel CpRu(CO)2Et precursor and O2, both thermal and remote plasma ALD of Ru were studied in the same reactor at wafers up to 200 mm. Unlike thermal ALD, the Ru film growth by remote plasma ALD does not rely on the dissociative chemisorption of O2 on the Ru surface and good film nucleation is expected by providing O radicals from the gas phase. In situ spectroscopic ellipsometry, x-ray reflectometry and diffractometry, and electrical measurements clearly show this benefit of the O2 plasma. The Ru films almost immediately nucleate for the plasma-based process, whereas the thermal process showed a nucleation delay of approximately 100 cycles. Once the film growth has started, the growth per cycle (1 Å/cycle), the electrical properties (20 µOcm for >5 nm films), and the polycrystalline structure are similar for both ALD processes. However, despite the drastically improved nucleation, the remote plasma ALD Ru films show higher roughness values than the thermal ALD Ru films (roughness of 13 nm and 8 nm for 20 nm thick films, respectively). To elucidate this unexpected phenomenon, the film nucleation and surface reactions were examined. Mass spectrometry provided insight into the reaction products (CO, CO2 and H2O mainly) and, therefore, into the surface chemistry ruling both ALD processes. Optical emission spectroscopy delivered information on the species created during plasma exposure. A reaction mechanism will be proposed for these oxygen-based ALD Ru processes that accounts not only for the differences in nucleation, but also relates to the roughness development of the Ru films