Dry etching of TiN in N2/Cl2/Ar adaptively coupled plasma

We investigated the N₂ additive effect on the etch rates of TiN and SiO₂ and etch profile of TiN in N₂/Cl₂/Ar adaptively coupled plasma (ACP). The mixing ratio of Cl₂ and Ar was fixed at 75 and 25 sccm, respectively. The N₂ flow rate was increased from 0 to 9 sccm under the constant pressure of 10 mTorr. As N₂ flow rate was increased in N₂/Cl₂/Ar plasma, the etch rate of TiN was linearly increased, but that of SiO₂ was increased non-monotonically. The etch profile and the compositional changes of TiN was investigated with field emission-scanning electron microscope (FE-SEM), FE-Auger electron spectroscopy (FE-AES) and x-ray photoelectron spectroscopy (XPS). When 9 sccm N₂ was added into Cl₂/Ar, a steep etch profile and clean surface of TiN was obtained. In addition, the signals of TiN and Ti were disappeared in FE-AES and XPS when N₂ additive flow into Cl₂/Ar was above 6 sccm. From the experimental data, the increase in TiN etch rate was mainly caused by the increase of desorption and evacuation rate of etch by products because of the increased effective pumping speed. The etch mechanism of TiN in N₂/Cl₂/Ar ACP plasma can be concluded as the ion enhanced chemical etch.     

Etching characteristics of Al2O3 thin films in inductively coupled BCl3/Ar plasma

The investigation of Al₂O₃ etch characteristics in the BCl₃/Ar inductively coupled plasma was carried out in terms of effects of input process parameters (gas pressure, input power, bias power) on etch rate and etch selectivity over poly-Si and photoresist. It was found that, with the changes in gas pressure and input power, the Al₂O₃ etch rate follows the behavior of ion current density while the process rate is noticeably contributed by the chemical etch pathway. The influence of input power on the etch threshold may be connected with the concurrence of chemical and physical etch pathways in ion-assisted chemical reaction.     

Basic investigation of HfO2 based metal-insulator-metal diodes

Very fast frequency response of metal-insulator-metal (MIM) diodes extends into the terahertz regime making them attractive as key elements as alternative to photovoltaic solar energy harvesting and ultrahigh speed wireless communication systems. The tunnelling phenomena, which is crucial for achieving high performance in these devices is extremely sensitive to the nanoscale structural and chemical quality of interface regions. Modern chemical deposition techniques like Pulsed Injected Metal-Organic Chemical Vapour Deposition (PICVD), Atomic Layer Deposition (ALD) and Atomic Vapour Deposition (AVD®) will be used for the extremely precise growth of thin HfO₂ films on TiN bottom electrodes. However, different deposition techniques may give unpredictably different results in terms of film density, surface and interface property and consequently in physical properties of the device.In this work, the influence of deposition techniques on the charge transport characteristics of HfO₂ MIM diodes was investigated by Conducting Atomic Force Microscopy (C-AFM) and X-ray Photoelectron Spectroscopy (XPS).     

Combined spectroscopic ellipsometry and attenuated total reflection analyses of Al2O3/HfO2 nanolaminates

The microstructure of thin HfO₂-Al₂O₃ nanolaminate high κ dielectric stacks grown by atomic vapor deposition has been studied by attenuated total reflection spectroscopy (ATR) and 8 eV spectroscopic ellipsometry (SE). The presence of Al₂O₃ below HfO₂ prevents the crystallisation of HfO₂ if an appropriate thickness is used, which depends on the HfO₂ thickness. A thicker Al₂O₃ is required for thicker HfO₂ layers. If crystallisation does occur, we show that the HfO₂ signature in both ATR and 8 eV SE spectra allows the detection of monoclinic crystallites embedded in an amorphous phase.     

The effects of O2/Ar ratio on the structure and properties of hafnium dioxide (HfO2) films

HfO₂ films at various O₂/Ar flow ratios were prepared by reactive dc magnetron sputtering. The effects of O₂/Ar ratio on the structure and properties of HfO₂ films were studied using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and UV-Visible spectroscopy. The results showed that the HfO₂ films were amorphous at different O₂/Ar ratios, and the atomic ratio of O/Hf in the HfO₂ films at high O₂/Ar ratio was nearly to 2:1. The peaks of Hf4f and O1s shifted to higher binding energy with increasing the oxygen flow proportion. The HfO₂ films at high O₂/Ar ratio had high transmissivity at the range of 400-1100 nm.     

The etching characteristics of Al2O3 thin films in an inductively coupled plasma

In this study, the etching characteristics of ALD deposited Al₂O₃ thin film in a BCl₃/N₂ plasma were investigated. The experiments were performed by comparing the etch rates and the selectivity of Al₂O₃ over SiO₂ as functions of the input plasma parameters, such as the gas mixing ratio, the DC-bias voltage, the RF power, and the process pressure. The maximum etch rate was obtained at 155.8 nm/min under a 15 mTorr process pressure, 700 W of RF power, and a BCl₃ (6 sccm)/N₂ (14 sccm) plasma. The highest etch selectivity was 1.9. We used X-ray photoelectron spectroscopy (XPS) to investigate the chemical reactions on the etched surface. Auger electron spectroscopy (AES) was used for the elemental analysis of the etched surfaces.     

Hysteresis-free HfO2 film grown by atomic layer deposition at low temperature

Hysteresis-free hafnium oxide films were fabricated by atomic layer deposition at 90 °C without any post-deposition annealing, and their structures and properties were compared with films deposited at 150 °C and 250 °C. The refractivity, bandgap, dielectric constant and leakage current density all increase with deposition temperature, while the growth rate and breakdown field decrease. All films are amorphous with roughly the same composition. Although the thin films deposited at the above-mentioned temperatures all show negligible hysteresis, only the 90 °C-deposited films remain hysteresis-free when the film thickness increases. The 90 °C-deposited films remain hysteresis-free after annealing at 300 °C. The hysteresis in films deposited at high temperatures increases with deposition temperature. Evidences show such hysteresis originates in the HfO₂ film instead of the interface. Based on a careful structure analysis, middle-range order is suggested to influence the trap density in the films. HfO₂ films deposited at low temperature with negligible hysteresis and excellent electrical properties have great potential for the fabrication and integration of devices based on non-silicon channel materials and in applications as tunneling and blocking layers in memory devices.     

Inductively coupled plasma reactive ion etching of titanium thin films using a Cl2/Ar gas

Inductively coupled plasma reactive ion etching of titanium thin films patterned with a photoresist using Cl₂/Ar gas was examined. The etch rates of the titanium thin films increased with increasing the Cl₂ concentration but the etch profiles varied. In addition, the effects of the coil rf power, dc-bias voltage and gas pressure on the etch rate and etch profile were investigated. The etch rate increased with increasing coil rf power, dc-bias voltage and gas pressure. The degree of anisotropy in the etched titanium films improved with increasing coil rf power and dc-bias voltage and decreasing gas pressure. X-ray photoelectron spectroscopy revealed the formation of titanium compounds during etching, indicating that Ti films etching proceeds by a reactive ion etching mechanism.     

Etching characteristics and mechanism of Ga-doped ZnO thin films in inductively-coupled HBr/X (X = Ar, He, N2, O2) plasmas

We investigated the etch characteristics and mechanisms of Ga-doped ZnO (Ga-ZnO) thin films in HBr/X (X = Ar, He, N₂, O₂) inductively-coupled plasmas. The etch rates of Ga-ZnO thin films were measured as a function of the additive gas fraction in the range of 0-100% for Ar, He, N₂, and O₂ at a fixed gas pressure (6 mTorr), input power (700 W), bias power (200 W), and total gas flow rate (40 sccm). The plasma chemistry was analyzed using a combination of the global (zero-dimensional) plasma model and Langmuir probe diagnostics. By comparing the behavior of the etch rate and fluxes of plasma active species, we found that the Ga-ZnO etch process was not limited by ion-surface interaction kinetics and appeared in the reaction rate-limited etch regime. In the HBr/O₂ plasma, the etch kinetics were probably influenced by oxidation of the etched surface.     

Structural and electrical properties of HfO2/Dy2O3 gate stacks on Ge substrates

In the present work we report on the structural and electrical properties of metal-oxide-semiconductor (MOS) devices with HfO₂/Dy₂O₃ gate stack dielectrics, deposited by molecular beam deposition on p-type germanium (Ge) substrates. Structural characterization by means of high-resolution Transmission Electron Microscopy (TEM) and X-ray diffraction measurements demonstrate the nanocrystalline nature of the films. Moreover, the interpretation of the X-ray reflectivity measurements reveals the spontaneous growth of an ultrathin germanium oxide interfacial layer which was also confirmed by TEM. Subsequent electrical characterization measurements on Pt/HfO₂/Dy₂O₃/p-Ge MOS diodes show that a combination of a thin Dy₂O₃ buffer layer with a thicker HfO₂ on top can give very good results, such as equivalent oxide thickness values as low as 1.9 nm, low density of interfacial defects (2-5 × 10¹² eV^− 1 cm^− 2) and leakage currents with typical current density values around 15 nA/cm² at V_g = V_FB − 1V.     

Evolution of SiO2/Ge/HfO2(Ge) multilayer structure during high temperature annealing

Use of germanium as a storage medium combined with a high-k dielectric tunneling oxide is of interest for non-volatile memory applications. The device structure consists of a thin HfO₂ tunneling oxide with a Ge layer either in the form of continuous layer or discrete nanocrystals and relatively thicker SiO₂ layer functioning as a control oxide. In this work, we studied interface properties and formation kinetics in SiO₂/Ge/HfO₂(Ge) multilayer structure during deposition and annealing. This material structure was fabricated by magnetron sputtering and studied by depth profiling with XPS and by Raman spectroscopy. It was observed that Ge atoms penetrate into HfO₂ layer during the deposition and segregate out with annealing. This is related to the low solubility of Ge in HfO₂ which is observed in other oxides as well. Therefore, Ge out diffusion might be an advantage in forming well controlled floating gate on top of HfO₂. In addition we observed the Ge oxidation at the interfaces, where HfSiO_x formation is also detected.     

GaN etch rate and surface roughness evolution in Cl2/Ar based inductively coupled plasma etching

Cl₂/Ar based inductively coupled plasma (ICP) etching of GaN is investigated using photoresist mask in a consequential restricted domain of pressure < 1.2 Pa and radio frequency (RF) sample power < 100 W, for selective mesa etching. The etch characteristics and root-mean-square (rms) surface roughness are studied as a function of process parameters viz. process pressure, Cl₂ percentage in total flow rate ratio, and RF sample power at a constant ICP power, to achieve moderate GaN etch rate with anisotropic profiles and smooth surface morphology. The etch rate and resultant surface roughness of etched surface increased with pressure mainly due to dominant reactant limited etch regime. The etch rate and surface roughness show strong dependence on RF sample power with the former increasing and the later decreasing with the applied RF sample power up to 80 W. The process etch yield variation with applied RF sample power is also reported. The studied etch parameters result in highly anisotropic mesa structures with Ga rich etched surface.     

Rare-earth substituted HfO2 thin films grown by metalorganic chemical vapor deposition

Thin films of HfGdO_x and HfDyO_x were deposited by metalorganic chemical vapor deposition (MOCVD) utilizing guanidinate precursors for Hf, Gd and Dy. The close match in the thermal properties of the precursors enabled the MOCVD of rare-earth (RE) substituted HfO₂ over a wide temperature window. Film deposition was carried out in the temperature range 300-700 °C in the presence of oxygen on Si(100) substrates. HfGdO_x films were analyzed in detail for their structure, composition and morphology using X-ray diffraction, Rutherford backscattering spectrometry, proton induced X-ray emission, X-ray photoelectron spectroscopy and scanning electron microscopy. The electrical properties of HfGdO_x in terms of capacitance-voltage and current-voltage characteristics of metal-insulator-semiconductor device structures were evaluated.     

The dry etching property of TiO2 thin films using metal-insulator-metal capacitor in inductively coupled plasma system

In this work, we investigated the etching characteristics of TiO₂ thin films and the selectivity of TiO₂ to SiO₂ in a BCl₃/Ar inductively coupled plasma (ICP) system. The maximum etch rate of 84.68 nm/min was obtained for TiO₂ thin films at a gas mixture ratio of BCl₃/Ar (25:75%). In addition, etch rates were measured as a function of etching parameters, such as the RF power, DC-bias voltage and process pressure. Using the X-ray photoelectron spectroscopy analysis the accumulation of chemical reaction on the etched surface was investigated. Based on these data, the ion-assisted physical sputtering was proposed as the main etch mechanism for the BCl₃-containing plasmas.     

Influence of plasma heating of wafer substrates on SiO2 deposition rate in a TEOS/O2 high-density plasma CVD system

The influence of plasma heating of the Si and glass wafer substrates on silicon dioxide (SiO₂) deposition rates by a tetraethylorthosilicate/O₂ supermagnetron (high-density) plasma CVD were investigated. With a fixed RF power of 100 W supplied to both upper and lower electrodes, the SiO₂ deposition rate on the Si wafer substrate decreased with increasing wafer-stage temperature, showing a negative activation energy for the deposition rate. When Si and glass wafers were attached to the electrode using adherent thermal conductors, the film thickness increased almost linearly with regard to the deposition time, and both deposition rates became almost the same (about 310 Å/min). When both wafers were simply laid on the electrode without an adhesive bond and hence with poor thermal contact, the film thickness increased nonlinearly with deposition time, showing a gradual decrease in deposition rate with time, being as low as 80 and 150 Å/min, respectively for Si and glass wafers, for a deposition time of 15 min. The difference between the two deposition rates on Si and glass wafers in the case of poor thermal contact to the lower electrode is thought to be caused by plasma heating and related mainly to differences in optical absorption characteristics of the two wafer substrates. Variations in measured thickness distributions across the substrate surface were attributed to an antisymmetric plasma density distribution in the direction perpendicular to the magnetic field lines caused by E×B electron drift.     

Simulation of Si and SiO2 etching in CF4 plasma

The reactive ion etching (RIE) of Si and SiO₂ in CF₄ plasma is considered. The dependences of RIE rates of Si and SiO₂ on pressure have maxima due to the presence of single-atom vacancies. The RIE rates approach the maximum values at different pressures but at the same concentration of SiF and SiOF molecules in the adsorbed layer. Using the obtained results Si/SiO₂ etching selectivity is investigated.     

Self-consistent global model for inductively coupled Cl2 plasma: Comparison with experimental data and application for the etch process analysis

The investigations of the influence of gas pressure and input power on the Cl₂ plasma parameters in the inductively coupled plasma system were carried out. The investigations combined plasma diagnostics by Langmuir probe and plasma modeling using the self-consistent global model with Maxwellian approximation for electron energy distribution function. From the experiments, it was found that an increase of gas pressure in the range of 0.27-3.33 Pa at 400-700 W input power results in decreasing both electron temperature (3.3-2.0 eV) and density (6.6 × 10¹⁰ − 3.0 × 10¹⁰ cm^− 3 for 400 W and 1.2 × 10¹¹ − 6.4 × 10¹⁰ cm^− 3 for 700 W). The model showed an outstanding agreement with the experiments and provided the data on densities and fluxes of active species. These data combined with the model of etch kinetics demonstrated the possibility of different etch rate behaviors depending on the input process parameters as well as on the properties of the etched surface.     

Dry etching characteristics of HfAlO3 thin films in BCl3/Ar plasma using inductively coupled plasma system

In this study, we monitored the HfAlO₃ etch rate and selectivity to SiO₂ as a function of the etch parameters (gas mixing ratio, RF power, DC-bias voltage, and process pressure). A maximum etch rate of 52.6 nm/min was achieved in the 30% BCl₃/(BCl₃ + Ar) plasma. The etch selectivity of HfAlO₃ to SiO₂ reached 1.4. As the RF power and the DC-bias voltage increased, the etch rate of the HfAlO₃ thin film increased. As the process pressure decreased, the etch rate of the HfAlO₃ thin films increased. The chemical state of the etched surfaces was investigated by X-ray Photoelectron Spectroscopy (XPS). According to the results, the etching of HfAlO₃ thin films follows the ion-assisted chemical etching mechanism.     

Effect of the post-deposition annealing on electrical characteristics of MIS structures with HfO2/SiO2 gate dielectric stacks

In this work, we report on effects of post-deposition annealing on electrical characteristics of metal–insulator–semiconductor (MIS) structures with HfO₂/SiO₂ double gate dielectric stacks. Obtained results have shown the deterioration of electro-physical properties of MIS structures, e.g. higher interface traps density in the middle of silicon forbidden band (D_itmb), as well as non-uniform distribution and decrease of breakdown voltage (U_br) values, after annealing above 400 °C. Two potential hypothesis of such behavior were proposed: the formation of interfacial layer between hafnia and silicon dioxide and the increase of crystallinity of HfO₂ due to the high temperature treatment. Furthermore, the analysis of conduction mechanisms in investigated stacks revealed Poole–Frenkel (P–F) tunneling at broad range of electric field intensity.     

The dry etching of a sol-gel deposited ZnO thin film in a high density BCl3/Ar plasma

The etching characteristics of zinc oxide (ZnO) including the etch rate and the selectivity of ZnO in a BCl₃/Ar plasma were investigated. It was found that the ZnO etch rate showed a non-monotonic behavior with an increasing BCl₃ fraction in the BCl₃/Ar plasma, along with the RF power, and gas pressure. At a BCl₃ (80%)/Ar (20%) gas mixture, the maximum ZnO etch rate of 50.3 nm/min and the maximum etch selectivity of 0.75 for ZnO/Si were obtained. Plasma diagnostics done with a quadrupole mass spectrometer delivered the data on the ionic species composition in plasma. Due to the relatively high volatility of the by-products formed during the etching by the BCl₃/Ar plasma, ion bombardment in addition to physical sputtering was required to obtain the high ZnO etch rates. The chemical state of the etched surfaces was investigated with X-ray Photoelectron Spectroscopy (XPS). Inferred from this data, it was suggested that the ZnO etch mechanism was due to ion enhanced chemical etching.