Plasma-assisted atomic layer deposition : an in situ diagnostic study

The method of atomic layer deposition (ALD) is considered one of the primary candidates for the uniform and conformal deposition of ultrathin films vital for the continuous miniaturization in the semiconductor industry and related high-technology markets. By the virtue of two selflimiting surface reactions, the ALD technique yields an ultimate control of film growth in the sense that a submonolayer of material is deposited per so-called ALD cycle. With established materials being at the verge of industrial implementation, efforts are continuously undertaken to optimize and develop new ALD configurations and processes. So far, the main emphasis within the field of ALD has been on the materials characterization of the films by means of ex situ analysis. The research described in this thesis aims at the development of the relatively new configuration of plasma-assisted ALD and at in situ diagnostics studies of the (plasmaassisted) ALD processes. In plasma-assisted ALD, a plasma is used to activate the reactants in the gas phase in order to supply additional reactivity to the ALD chemistry. Plasma-assisted ALD is researched to provide benefits in the development of new ALD processes and materials. In particular, the opportunities to improve and tune the film properties, and to deposit films at reduced substrate temperatures have been addressed in this thesis. This work has been accompanied by studies using various in situ diagnostics, from which fundamental insight into the reaction mechanisms governing the ALD processes can be obtained. Moreover, in situ techniques provide the opportunity to monitor, optimize, and control the ALD process. In this work the use of in situ spectroscopic ellipsometry, transmission infrared spectroscopy, mass spectrometry, and optical emission spectroscopy has been demonstrated in studies of the plasma-assisted ALD processes of metal nitrides and metal oxides. The results of the film characterization obtained by these techniques have been corroborated and complemented by extensive ex situ analysis. In particular, the combination of in situ spectroscopic ellipsometry and the layer-by-layer ALD growth has been explored comprehensively. The merits of this in situ technique during ALD have been demonstrated by addressing various aspects relevant to ALD processes and materials. A large part of the work has concentrated on the plasma-assisted ALD process of the metal nitrides TiN and TaN. The merits of plasma-assisted ALD were observed in the deposition TiN films with excellent conductivity and low impurity content, even at low deposition temperatures. Furthermore, it was shown that by variation of the plasma condition in the ALD process of TaN, the film properties could be tailored from conductive, cubic TaNx;x??1 to semiconductive, amorphous Ta3N5. These aspects were clearly demonstrated by in situ spectroscopic ellipsometry, where the transition in TaNx phase could be distinguished by monitoring the energy dispersion in the optical constants. For the conductive films, the light absorption by free conduction electrons could be probed and that enabled extraction of the electrical film properties from the ellipsometry data. The latter was valuable to demonstrate electron-impurity scattering and finite size effects in TiN films. Furthermore, fundamental insight into the reaction mechanisms of plasma-assisted ALD process of TaN was obtained by detection of the volatile reaction by-products by mass spectrometry and optical emission spectroscopy. The possibilities for plasma-assisted ALD to improve the material properties and to deposit at reduced temperatures have been demonstrated for the process of Al2O3. The Al2O3 films were deposited at substrate temperatures down to room temperature and these films yielded good moisture permeation barrier properties as relevant for encapsulation purposes. The fundamental reaction mechanisms of this plasma-assisted ALD process were elucidated by transmission infrared spectroscopy in order to understand and further improve the film properties obtained at these reduced deposition temperatures. It was established that the surface chemistry is ruled by –CH3 and –OH surface groups created by the Al(CH3)3 precursor adsorption and the combustionlike reactions during the O2 plasma step, respectively. Moreover, infrared spectroscopy provided insight into the influence of deposition temperature on the material properties. It was shown that by prolonging the plasma exposure, i.e., by supplying more plasma reactivity to the ALD process, the surface chemistry at low temperatures was enhanced and the impurity content in the Al2O3 was reduced. In conclusion, the knowledge gained through the in situ diagnostic studies in this work is relevant to further develop the ALD technique. The insight obtained into the reaction mechanisms and the material properties of the ALD films in this work are particularly useful to further exploit the possibilities and opportunities of the plasma-assisted ALD technique in the synthesis of novel (complex) materials

Reaction mechanisms of atomic layer deposition of TaNx from Ta(NMe2)5 precursor and H2-based plasmas

The reaction mechanisms of plasma-assisted atomic layer deposition (ALD) of TaNx using Ta(NMe2)5 were studied using quadrupole mass spectrometry (QMS). The fact that molecule dissociation and formation in the plasma have to be considered for such ALD processes was illustrated by the observation of 4% NH3 in a H2-N2 (1:1) plasma. Using QMS measurements the reaction products during growth of conductive TaNx using a H2 plasma were determined. During the Ta(NMe2)5 exposure the reaction product HNMe2 was detected. The amount of adsorbed Ta(NMe2)5 and the amount of HNMe2 released were found to depend on the number of surface groups generated during the plasma step. At the beginning of the plasma exposure step the molecules HNMe2, CH4, HCN, and C2H2 were measured. After an extended period of plasma exposure, the reaction products CH4 and C2H2 were still present in the plasma. This change in the composition of the reaction products can be explained by an interplay of aspects including the plasma-surface interaction, the ALD surface reactions, and the reactions of products within the plasma. The species formed in the plasma (e.g., CHx radicals) can re-deposit on the surface and influence to a large extent the TaNx material composition and propertie

New ultrahigh vacuum setup and advanced diagnostic techniques for studying a-Si:H film growth by radical beams

A new ultrahigh vacuum setup is presented which is designed for studying the surface science aspects of a-Si:H film growth using various advanced optical diagnostic techniques. The setup is equipped with plasma and radical sources which produce well-defined radicals beams such that the a-Si:H deposition process can be mimicked. In this paper the initial experiments with respect to deposition of a-Si:H using a hot wire source and etching of a-Si:H by atomic hydrogen are presented. These processes are monitored by real time spectroscopic ellipsometry and the etch yield of Si by atomic hydrogen is quantified to be 0.005±0.002 Si atoms per incoming H atom

In situ spectroscopic ellipsometry for atomic layer deposition

The application of in situ spectroscopic ellipsometry during thin film synthesis by atomic layer deposition (ALD) is examined for results obtained on Al2O3, TaN2, and TiN films with thicknesses ranging from 0.1 to 100 nm. By analyzing the film thickness and the energy dispersion of the optical constants of the films, the layer-by-layer growth and material properties of the ALD films can be studied in detail. The growth rate per cycle and the nucleation behavior of the films can be addressed by monitoring the thickness as a function of the number of cycles. It is shown that from the energy dispersion relation, insight into the conductive properties of metallic films can be derived. Moreover, the shape of the dispersion relation can be used to discriminate between different material compositions

OLED Encapsulation by Room Temperature Plasma-Assisted ALD Al2O3 Films

Organic light emitting diodes (OLEDs, both small molecule and polymer LEDs) require excellent gas and moisture permeation barrier layers to increase their lifetime. The quality of the barrier layer is ultimately controlled by the presence of defects in the layer. Although a barrier layer may be intrinsically excellent (water vapor transmission rate, WVTR = 10-6 g·m-2·day-1) the protected device may fail in the presence of defects that lead to preferential diffusion pathways for H2O (e.g., defects caused by particles from the environment and/or production process). The state-of-the-art barrier coatings are micrometer-thick multi-layer structure, in which organic interlayers are alternated with inorganic barrier layers with the purpose of decoupling the above-mentioned defects. Recently, atomic layer deposition (ALD) has been successfully tested for the deposition of very thin (<50 nm) single layer permeation barriers on pristine polymer substrates [1,2], showing the potential of this highly uniform and conformal deposition technique in the field of moisture permeation barriers. In this contribution the encapsulation of OLEDs by plasma-assisted ALD of thin (20-40 nm) Al2O3 layers is addressed. The layers are synthesized at room temperature by sequentially exposing the substrate to Al(CH3)3 vapor and a remote inductively coupled O2 plasma in Oxford Instruments FlexALTM and OpALTM reactors. The intrinsic quality of the deposited ALD layers was determined by monitoring the oxidation of a Ca film encapsulated by the Al2O3 film: WVTR values as low as 2·10-6 g·m-2·day-1 have been measured. The potential of ALD layers in encapsulating OLEDs, and therefore in successfully covering the defects present on the device, has been investigated by means of electroluminescence measurements of polymer-LEDs (effective emitting area of 5.8 cm2). The black spot density and area growth were followed as a function of the time under standard conditions of 20°C and 50% relative humidity. Within a 500 h test ALD-encapsulated OLEDs show approximately half the black spot density compared to devices encapsulated by plasma deposited a-SiNx:H (300 nm thick). The black spot density is further reduced by combining the a-SiNx:H and ALD Al2O3 layers. These results point towards a very promising application of ALD Al2O3 layers in the field of OLED encapsulation and will be interpreted in terms of possible mechanisms related to film growth in multi-layer structures

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

Atomic layer deposition of Ru from CpRu(CO2)Et using O2 gas and O2 plasma

The metalorganic precursor cyclopentadienylethyl(dicarbonyl)ruthenium (CpRu(CO)2Et) was used to develop an atomic layer deposition (ALD) process for ruthenium. O2 gas and O2 plasma were employed as reactants. For both processes, thermal and plasma-assisted ALD, a relatively high growth-per-cycle of - 1 Å was obtained. The Ru films were dense and polycrystalline, regardless of the reactant, yielding a resistivity of - 16 µO¿cm. The O2 plasma not only enhanced the Ru nucleation on the TiN substrates but also led to an increased roughness compared to thermal ALD

Late Neogene chronology: New perspectives in high-resolution stratigraphy

We present an integrated geochronology for late Neogene time (Pliocene, Pleistocene, and Holocene Epochs) based on an analysis of data from stable isotopes, magnetostratigraphy, radiochronology, and calcareous plankton biostratigraphy. Discrepancies between recently formulated astronomical chronologies and magnetochronologies for the past 6 m.y. have been resolved on the basis of new, high-precision Ar/Ar ages in the younger part of this interval, the so-called Brunhes, Matuyama, and Gauss Epochs (= Chrons C1n-C2An; 0-3.58 Ma), and revised analysis of sea floor anomalies in the Pacific Ocean in the older part, the so-called Gilbert Epoch (= Chron C2Ar-C3r; 3.58-5.89 Ma). The magneto- and astrochronologies are now concordant back to the Chron C3r/C3An boundary at 5.89 Ma. The Neogene (Miocene, Pliocene, Pleistocene, and Holocene) and Paleogene are treated here as period/system subdivisions of the Cenozoic Era/Erathem, replacements for the antiquated terms Tertiary and Quaternary. The boundary between the Miocene and Pliocene Series (Messinian/Zanclean Stages), whose global stratotype section and point (GSSP) is currently proposed to be in Sicily, is located within the reversed interval just below the Thvera (C3n.4n) Magnetic Polarity Subchronozone with an estimated age of 5.32 Ma. The Pliocene/Pleistocene boundary, whose GSSP is located at Vrica (Calabria, Italy), is located near the top of the Olduvai (C2n) Magnetic Polarity Subchronozone with an estimated age of 1.81 Ma. The 13 calcareous nannoplankton and 48 planktonic foraminiferal datum events for the Pliocene, and 12 calcareous nannoplankton and 10 planktonic foraminiferal datum events for the Pleistocene, are calibrated to the newly revised late Neogene astronomical/geomagnetic polarity time scale