Tetrakis Ethylmethylamido Hafnium Research Articles

Investigation of tetrakis(ethylmethylamido)hafnium adsorption mechanism in initial growth of atomic layer deposited-HfO2 thin films on H-/OH-terminated Si (100) surfaces

The continuous scaling down of dynamic random access memory devices has necessitated a comprehensive understanding of the initial growth mechanism in atomic layer deposition. In this study, HfO2 was deposited using tetrakis(ethylmethylamido)hafnium (TEMAHf)-H2O on H-/OH-terminated Si (100) surfaces. By analyzing the Hf-O peak in the FTIR spectra and medium-energy ion scattering measurements, it was determined that a monolayer was formed on the H-Si surface at a rate (10 cycles) lower than that for the OH-Si surface (4 cycles). The ligand variations during each cycle, as determined by FTIR measurements, enabled the suggestion of the initial precursor adsorption mechanism. An analysis of the infrared spectra and secondary ion mass spectrometry depth profiles revealed surface-dependent differences in interfacial bonding. This explained the variation in the rate of formation of 1 Ml. Additionally, theoretical investigations using density functional theory calculations identified the reaction pathway with the lowest energy barrier, thereby validating the experimentally proposed mechanism. This study to elucidate the Si surface and the TEMAHf-H2O reaction mechanism provided insights into the analysis of the initial precursor adsorption mechanism for other types of precursors.

Growth mode evolution of hafnium oxide by atomic layer deposition

HfO2 thin films were deposited using tetrakis-ethylmethylamido hafnium and H2O as precursors on silicon by atomic layer deposition (ALD). The morphology and microstructures at different ALD cycles were characterized by atomic force microscopy and high-resolution transmission electron microscopy. Based on the height–height correlation function and power spectral density function, quantitative analysis of surface morphologies was performed. Three characteristic dimensions (ξ1, ξ2, and ξ3) corresponding to three surface structures, islands, local and global fluctuations, were identified. The evolution of ALD growth mode at range of the three critical scales was investigated, respectively. It suggests the transformation of growth mode from quasi two-dimensional layer-by-layer to three-dimensional island for global fluctuations.

Quantum Cascade Laser-Based Measurement of Metal Alkylamide Density during Atomic Layer Deposition

An in situ gas-phase diagnostic for the metal alkylamide compound tetrakis(ethylmethylamido) hafnium (TEMAH), Hf[N(C(2)H(5))(CH(3))](4), was demonstrated. This diagnostic is based on direct absorption measurement of TEMAH vapor using an external cavity quantum cascade laser emitting at 979 cm(-1), coinciding with the most intense TEMAH absorption in the mid-infrared spectral region, and employing 50 kHz amplitude modulation with synchronous detection. Measurements were performed in a single-pass configuration in a research-grade atomic layer deposition (ALD) chamber. To examine the detection limit of this technique for use as a TEMAH delivery monitor, this technique was demonstrated in the absence of any other deposition reactants or products, and to examine the selectivity of this technique in the presence of deposition products that potentially interfere with detection of TEMAH vapor, it was demonstrated during ALD of hafnium oxide using TEMAH and water. This technique successfully detected TEMAH at molecular densities present during simulated industrial ALD conditions. During hafnium oxide ALD using TEMAH and water, absorbance from gas-phase reaction products did not interfere with TEMAH measurements while absorption by reaction products deposited on the optical windows did interfere, although interfering absorption by deposited reaction products corresponded to only ≈4% of the total derived TEMAH density. With short measurement times and appropriate signal averaging, estimated TEMAH minimum detectable densities as low as ≈2 × 10(12) molecules/cm(3) could be obtained. While this technique was demonstrated specifically for TEMAH delivery and hafnium oxide ALD using TEMAH and water, it should be readily applicable to other metal alkylamide compounds and associated metal oxide and nitride deposition chemistries, assuming similar metal alkylamide molar absorptivity and molecular density in the measurement chamber.

<I>In Situ</I> Gas Phase Measurements During Metal Alkylamide Atomic Layer Deposition

Metal alkylamide compounds, such as tetrakis(ethylmethylamido) hafnium (TEMAH), represent a technologically important class of metalorganic precursors for the deposition of metal oxides and metal nitrides via atomic layer deposition (ALD) or chemical vapor deposition. The development of in situ diagnostics for processes involving these compounds could be beneficial in, e.g., developing deposition recipes and validating equipment-scale simulations. This report describes the performance of the combination of two techniques for the simultaneous, rapid measurement of the three major gas phase species during hafnium oxide thermal ALD using TEMAH and water: TEMAH, water, and methylethyl amine (MEA), the only major reaction by-product. For measurement of TEMAH and MEA, direct absorption methods based on a broadband infrared source with different mid-IR bandpass filters and utilizing amplitude modulation and synchronous detection were developed. For the measurement of water, wavelength modulation spectroscopy utilizing a near-IR distributed feedback diode laser was used. Despite the relatively simple reactor geometry employed here (a flow tube), differences were easily observed in the time-dependent species distributions in 300 mL/min of a helium carrier gas and in 1000 mL/min of a nitrogen carrier gas. The degree of TEMAH entrainment was lower in 300 mL/min of helium compared to that in 1000 mL/min of nitrogen. The capability to obtain detailed time-dependent species concentrations during ALD could potentially allow for the selection of carrier gas composition and flow rates that would minimize parasitic wall reactions. However, when nitrogen was employed at the higher flow rates, various flow effects were observed that, if detrimental to a deposition process, would effectively limit the upper range of useful flow rates.

Novel Hf and La Formamidinates for ALD Application

AbstractHfO2 is a promising dielectric for alternative high-k gate dielectrics and DRAM capacitor applications because of its high dielectric constant, excellent thermal stability and compatibility with Si processing. Particularly atomic layer deposition (ALD) is suitable as a deposition tool for gate dielectrics as well as capacitor dielectrics due to its excellent conformity and precise thickness control. In order to achieve ideal ALD performance, it is critical to have appropriate precursors. In order to achieve ideal ALD performance, it is critical to use appropriate enabling precursors. So far, Tetrakisethylmethylamidohafnium (TEMAHf) has been considered as one of the most promising precursors due to its good physical properties. However, this precursor has relatively low thermal stability, which has often become a drawback to ALD process for HfO2. To circumvent the decomposition issues of TEMAHf during ALD deposition, often low process temperatures have been used that lead to less dense films and high level of carbon contamination. In order to overcome these challenges, the novel hafnium formamidinate (Hf-FAMD) precursor is developed as an alternate Hf source at Dow Electronic Materials. Following our success with formamidinate platform in previously reported novel lanthanum formamidinate (La-FAMD) source, this new precursor also exhibits high thermal stability and high reactivity towards water and ozone. In this work, we report, for the first time, comparative studies with TEMAHf and novel Hf-FAMD source, e.g. Hf-FAMD exhibits acceptable vapor pressure (> 0.1 Torr at 100 °C) similar to that of TEMAHf, and higher thermal stability than TEMAHf, thus leading to high quality ALD films. We also present the crystal structure of La-FAMD, elucidated by X-Ray Crystallography, and physical properties of novel Hf-FAMD relevant to ALD.

Atomic Layer Deposition of Metal Oxide Films on GaAs (100) surfaces

AbstractAtomic Layer Deposition is used to deposit HfO2 and TiO2 films on GaAs (100) native oxides and etched surfaces. For the deposition of HfO2 films two different but similar ALD chemistries are used: i) tetrakis dimethyl amido hafnium (TDMAHf) and H2O at 275°C and ii) tetrakis ethylmethyl amido hafnium (TEMAHf) and H2O at 250°C. TiO2 films are deposited from tetrakis dimethyl amido titanium (TDMATi) and H2O at 200°C. Rutherford Back Scattering shows linear film growth for all processes. The film/substrate interface is examined using x-ray Photoelectron Spectroscopy and confirms the presence of an “interfacial cleaning” mechanism.

High-Quality HfO[sub 2] Formation using Zr Reduced High-Purity TEMAH

HfO 2 films have been grown by an atomic layer deposition method using a high-purity tetrakis(ethylmethylamido)hafnium (TEMAH). TEMAH, which has been used as a source material for HfO 2 film formation, is likely to include zirconium (Zr) or titanium (Ti) atoms as impurities in the manufacturing process, and further purification was difficult. We succeeded in synthesizing a high-purity TEMAH with a reduced Zr concentration of impurities. The electrical properties of HfO 2 films were investigated, and the breakdown voltage and leakage current were improved by decreasing Zr impurities.

Preparation of HfO2 Thin Films Using Flashing Spray CVD Method

The authors proposed the novel evaporation supply method, flashing spray chemical vapor deposition (FS-CVD). In the experiment, tetrakisethylmethylamidohafnium (TEMAH) was used as the precursor and n-pentane was used as the low boiling point organic solvent. The critical consolute temperature of TEMAH and n-pentane mixed material solution was 276K. The vapor pressure of the mixed material solution was ten times higher than that of TEMAH by formation of two-phase region. HfO2 film was deposited on Si wafer by using TEMAH and n-pentane with FS-CVD. As the result, the uniformity of HfO2 film was +/-5% and film thickness was 133.6nm. The uniformity of HfO2 film of refractive index was +/-5% and refractive index was 1.63. It is found that the precursor was evaporated by flash boiling and HfO2 film was deposited by decomposition.

In-situ Infrared Absorption Monitoring of Atomic Layer Deposition of Metal Oxides on Functionalized Si and Ge Surfaces

AbstractThe nature of the interface between Si and Ge substrates and high-k dielectrics often controls the performance of MOSFET devices. Precleaning and/or chemical functionalization of the surfaces can dramatically affect the formation of an interfacial layer. We have used in-situ IR spectroscopy to probe the relevant interfaces during ALD growth for a variety of surface treatments, including H- and Cl-termination, and nitridation. This paper focuses on understanding of the mechanisms for interfacial SiO2 (or GeOx) formation during HfO2 growth using tetrakis-ethylmethylamidohafnium (TEMAH) as the metal precursor and water or ozone as the oxygen precursor. We find that impurities arising from incomplete ligand elimination during growth (e.g. OH for H2O processing and CO- and NO-containing species for O3 processing) are incorporated into the HfO2 film during growth. Upon annealing, most of these species react, but can also migrate to the interface. Nitridation of Si and Ge surfaces will in general prevent SiO2 or GeOx formation but can also affect the growth rate.

Vapour pressure measurement of low volatility precursors

The introduction of new chemicals into semiconductor production processes is an expensive, time consuming exercise. A key parameter required to ensure equipment set up is well suited to the source from the outset of trials is reliable precursor volatility data. In this paper we present details of a newly commissioned vapour pressure (VP) measurement system and latest vapour pressure values for the technologically interesting Hf and Ta precursors pentakis(dimethylamido)tantalum (PDMAT) and tetrakis(ethylmethylamido)hafnium (TEMAH). Calibration data is also presented to illustrate the accuracy of the equipment.