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

Dielectric material options for integrated capacitors

Future MIM capacitor generations will require significantly increased specific capacitances by utilization of high-k dielectric materials. In order to achieve high capacitance per chip area, these dielectrics have to be deposited in three-dimensional capacitor structures by ALD or AVD (atomic vapor deposition) process techniques. In this study eight dielectric materials, which can be deposited by these techniques and exhibit the potential to reach k-values of over 50 were identified, prepared and characterized as single films and stacked film systems. To primarily focus on a material comparison, preliminary processes were used for film deposition on planar test devices. Measuring leakage current density versus the dielectric constant k shows that at low voltages (=1 V) dielectrics with k-values up to 100 satisfy the typical leakage current density specification o

A New Route to the Deposition of Al2O3 by MOCVD

Thin films of aluminium oxide, Al2O3, have been deposited by atmospheric pressure MOCVD using trimethylaluminium (Me3Al) and iso-propanol (Pr'OH) as precursors. The films were deposited over the temperature range 400-600°C and had growth rates of up to 67 Å min-1. Analysis by Auger electron spectroscopy showed that films deposited at 400°C were high purity with carbon contamination < 0.5 at %

Plasma-enhanced ALD of TiO2 using a novel cyclopentadienyl alkylamido precursor [Ti(CPMe)(NMe2)3] and O2 plasma

Titanium oxide thin films of both amorphous and anatase morphologies have been deposited using remote plasma ALD over a wide temperature range (100-350 °C), using a novel heteroleptic alkylamido precursor Ti(CpMe)(NMe2)3. A high growth per cycle (GPC) of 0.07-0.08 nm (50 % higher than the GPC obtained with most other organometallic precursors). Films obtained were stoichiometric and of high compositional purity

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

Wavelength-dispersive x-ray microanalysis as a novel method for studying magnesium doping in gallium nitride epitaxial films

Magnesium doping is critically important in GaN device technology, since it provides the only viable method of producing layers with p-type conductivity. Electron probe microanalysis with wavelength dispersive x-ray spectrometry (WDX-EPMA) was used to measure magnesium atom concentrations in doped GaN films grown by metal organic vapour phase epitaxy (MOVPE). Our study compared the behaviour of a widely used magnesium source in MOVPE, bis(cyclopentadienyl) magnesium, when vaporized as a solid and as a proprietary two-phase source, Solution Cp2Mg™. The WDX-EPMA technique was capable of measuring [Mg] values in GaN layers at practically useful concentrations of 1019 cm−3 upwards. Excellent agreement in [Mg] values was obtained between [Mg] values measured by WDX-EPMA and the more widely used technique of secondary ion mass spectrometry (SIMS). A set of 12 GaN:Mg samples was studied by WDX-EPMA to investigate the dependence of [Mg] on the flow rate of the magnesium source into the MOVPE reactor, with other conditions held constant, including a growth set-point temperature of 1130 °C. These measurements suggested a solid solubility limit at ~1020 cm−3, consistent with previous studies. Up to a value of about half the saturation limit, [Mg] values were proportional to the magnesium source flow, and indicated magnesium atom incorporation from the gas phase with ~11% of the efficiency of gallium atoms. No systematic differences were seen between the behaviour of solid magnesocene and Solution Cp2Mg™. A more limited study of the temperature dependence of magnesium incorporation showed a reduction in incorporation of ~40% as the growth temperature was reduced from 1130 to 1090 °C, consistent with kinetic control. Selected GaN:Mg samples were studied by Hall measurements and high-resolution x-ray diffraction. This work showed no systematic structural degradation of GaN:Mg close to the magnesium solubility limit. Our most conductive sample had a hole concentration of 4.4 × 1017 cm−3, consistent with the expected generation of acceptors from only a small fraction of the magnesium atoms. We also discuss the relative capabilities of SIMS and WDX-EPMA in the context of analysing GaN:Mg samples. SIMS offers superior depth profiling capability and detection limits, whilst WDX-EPMA offers superior spatial resolution, non-destructive analysis, plus simultaneous imaging and cathodoluminescence spectroscopy

Wavelength-dispersive x-ray microanalysis as a novel method for studying magnesium doping in gallium nitride epitaxial films

Magnesium doping is critically important in GaN device technology, since it provides the only viable method of producing layers with p-type conductivity. Electron probe microanalysis with wavelength dispersive x-ray spectrometry (WDX-EPMA) was used to measure magnesium atom concentrations in doped GaN films grown by metal organic vapour phase epitaxy (MOVPE). Our study compared the behaviour of a widely used magnesium source in MOVPE, bis(cyclopentadienyl) magnesium, when vaporized as a solid and as a proprietary two-phase source, Solution Cp2Mg™. The WDX-EPMA technique was capable of measuring [Mg] values in GaN layers at practically useful concentrations of 1019 cm−3 upwards. Excellent agreement in [Mg] values was obtained between [Mg] values measured by WDX-EPMA and the more widely used technique of secondary ion mass spectrometry (SIMS). A set of 12 GaN:Mg samples was studied by WDX-EPMA to investigate the dependence of [Mg] on the flow rate of the magnesium source into the MOVPE reactor, with other conditions held constant, including a growth set-point temperature of 1130 °C. These measurements suggested a solid solubility limit at ~1020 cm−3, consistent with previous studies. Up to a value of about half the saturation limit, [Mg] values were proportional to the magnesium source flow, and indicated magnesium atom incorporation from the gas phase with ~11% of the efficiency of gallium atoms. No systematic differences were seen between the behaviour of solid magnesocene and Solution Cp2Mg™. A more limited study of the temperature dependence of magnesium incorporation showed a reduction in incorporation of ~40% as the growth temperature was reduced from 1130 to 1090 °C, consistent with kinetic control. Selected GaN:Mg samples were studied by Hall measurements and high-resolution x-ray diffraction. This work showed no systematic structural degradation of GaN:Mg close to the magnesium solubility limit. Our most conductive sample had a hole concentration of 4.4 × 1017 cm−3, consistent with the expected generation of acceptors from only a small fraction of the magnesium atoms. We also discuss the relative capabilities of SIMS and WDX-EPMA in the context of analysing GaN:Mg samples. SIMS offers superior depth profiling capability and detection limits, whilst WDX-EPMA offers superior spatial resolution, non-destructive analysis, plus simultaneous imaging and cathodoluminescence spectroscopy