Plasma etching of high-k and metal gate materials

Etching characteristics of high-k dielectric materials (HfO₂) and metal electrode materials (Pt, TaN) have been studied in high-density chlorine-containing plasmas at pressures around 10 mTorr. The etching of HfO₂ was performed in BCl₃ without rf biasing, giving an etch rate of about 5 nm/min with a high selectivity of >10 over Si and SiO₂. The etching of Pt and TaN was performed in Ar/O₂ with high rf biasing and in Ar/Cl₂ with low rf biasing, respectively, giving a Pt etch rate of about several tens nm/min and a TaN etch rate of about 200 nm/min with a high selectivity of >8 over HfO₂ and SiO₂. The etched profiles were outwardly tapered for Pt, owing to the redeposition of etch or sputter products on feature sidewalls, while the TaN profiles were almost anisotropic, probably owing to the ion-enhanced etching that occurred.     

Effect of additive gases on the selective etching of ZrOx film using inductively coupled BCl3-based plasmas

In this study, the effect of BCl₃/C₄F₈ gas mixture on the ZrO_x etch rates and the etch selectivities of ZrO_x/Si were investigated and its etch mechanism was studied. The increase of C₄F₈ in BCl₃/C₄F₈ decreased the silicon etch rate significantly and finally deposition instead of etching occurred by mixing C₄F₈ more than 3%. In the case of ZrO_x, the etch rate remained similar until 4% of C₄F₈ was mixed, however, the further increase of C₄F₈ percentage finally decreased the ZrO_x etch rate and deposition instead of etching occurred by mixing more than 6%. Therefore, by mixing 3-4% of C₄F₈ to BCl₃, infinite etch selectivity of ZrO_x/Si could be obtained while maintaining the similar ZrO_x etch rate. The differences in the etch behaviors of ZrO_x and Si were related to the different thickness of C-F polymer formed on the surfaces. The thickness of the C-F polymer on the ZrO_x surface was smaller due to the removal of carbon incident on the surface by forming CO_x with oxygen in ZrO_x. Using 12 mTorr BCl₃/C₄F₈ (4%), 700 W of rf power, and − 80 V of dc bias voltage, the ZrO_x etch rate of about 535 Å/min could be obtained with infinite etch selectivity to Si.     

Influence of high temperature processing of sol-gel derived barium titanate thin films deposited on platinum and strontium ruthenate coated silicon wafers

Thin films of barium titanate (BTO) of 200 nm thickness, derived from an alkoxide-carboxylate sol-gel process, were deposited on Pt/Ti and SrRuO₃/ZrO₂-8%Y₂O₃ coated Si wafers. Films with a dense columnar microstructure were obtained by repeated deposition of thin amorphous layers from low-concentrated sols, and crystallization at 800 °C. This method added 10 nm thickness to the crystalline BTO film in each deposition step. The harsh processing conditions had a negative impact on the platinized silicon wafers, where Pt-Si silicides were formed. This led to diffusion of Si into BTO and interfacial silicate formation. The interfacial silicate layer was the cause of deteriorated dielectric and ferroelectric properties of the BTO layer. Use of SrRuO₃/ZrO₂-8%Y₂O₃/Si substrates solved the problem. No diffusion of Si was observed, and BTO films with good dielectric and ferroelectric properties were obtained.     

High aspect ratio via etch development for Cu nails in 3-D-stacked ICs

In this study the etch development of high aspect ratio vias in Si for the fabrication of Cu nails is described. To enable subsequent metallisation, these vias need to meet strict requirements with respect to uniformity, slope, sidewall roughness and undercut. For aspect ratios up to 5 a SiO₂ hard mask based SF6/O₂ etch approach is used. For aspect ratios up to 10, a resist based passivation polymer type etch approach with C4F8/SF6 was used to successfully pattern vias in Si. Typical problems of this process and optimization to overcome the issues are described.     

Nanocrystallized tetragonal metastable ZrO2 thin films deposited by metal-organic chemical vapor deposition for 3D capacitors

ZrO₂ is a potential candidate for the realization of 3D capacitors on silicon for future Systems-on-Chip. This paper reports on the deposition of ZrO₂ thin films by metal-organic chemical vapor deposition on planar and 3D structures. Physico-chemical as well as electrical properties of the films are investigated. It is shown that the change of phase and microstructure of the film due to annealing at 900 °C under O₂ impacts directly on the electrical performance of the capacitors. Capacitance densities are 2 nF/mm² for planar capacitors and reach 8 nF/mm² for capacitors with pores etched in silicon with a 4:1 aspect ratio.     

Black SiC formation induced by Si overlayer deposition and subsequent plasma etching

Black SiC formation by plasma etching with SF₆/O₂ chemistry is reported. Black SiC was produced by depositing Si overlayer on SiC and then etching the Si/SiC stack sequentially, thus replicating the black Si morphology to SiC. Black SiC is obtained with almost zero reflectance over the wavelengths from 300 nm to 1050 nm. Thicker Si film was advantageous, and it was important to optimize the etch condition considering both the black Si morphology and the flattening effect of SiC.     

Structural, optical and electrical properties of high-k ZrO2 dielectrics on Si prepared by plasma assisted pulsed laser deposition

ZrO₂ films were grown on p-type Si(100) using plasma assisted pulsed laser deposition and the electrical characteristics of the ZrO₂ dielectrics incorporated in metal oxide silicon (MOS) capacitors were studied in combination with their structural and optical properties. The ZrO₂ dielectric layers are of polycrystalline structure with a monoclinic phase and show good interfacial properties without obvious SiO_x interface. The electrical performance of the capacitors exhibits typical MOS-type capacitance-voltage (C-V) and leakage current density-voltage (J-V) characteristics. Thermal annealing of the ZrO₂ dielectrics results in an improvement in C-V and J-V characteristics and a reduction in C-V hysteresis without obvious introduction of leakage paths for the fabricated MOS capacitors. The dielectric constant was calculated to be 15.4 and the leakage current density was measured to be 6.7 × 10^− 6 A/cm² at a gate voltage of + 1.0 V for 900 °C annealed ZrO₂ dielectric layers with an equivalent oxide thickness of 5.2 nm.     

Fabrication of high quality Ge virtual substrates by selective epitaxial growth in shallow trench isolated Si (001) trenches

To further boost the CMOS device performance, Ge has been successfully integrated on shallow trench isolated Si substrates for pMOSFET fabrication. However, the high threading dislocation densities (TDDs) in epitaxial Ge layers on Si cause mobility degradation and increase in junction leakage. In this work, we studied the fabrication of Ge virtual substrates with low TDDs by Ge selective growth and high temperature anneal followed by chemical mechanical polishing (CMP). With this approach, the TDDs in both submicron and wider trenches were simultaneously reduced below 1 × 10⁷ cm^− 2 for 300 nm thick Ge layers. The resulting surface root-mean-square (RMS) roughness is about 0.15 nm. This fabrication scheme provides high quality Ge virtual substrates for pMOSFET devices as well as for III-V selective epitaxial growth in nMOSFET areas. A confined dislocation network was observed at about 50 nm above the Ge/Si interface. This dislocation network was generated as a result of effective threading dislocation glide and annihilation. The separation between the confined threading dislocations was found in the order of 100 nm.     

Texture optimization process of ZnO:Al thin films using NH4Cl aqueous solution for applications as antireflective coating in thin film solar cells

ZnO:Al thin films varying the thickness from 80 to 110 nm were deposited on polished float zone < 100 > Si wafers by radio frequency magnetron sputtering at 100 °C. To texturize these surfaces with the aim of being used as antireflective coating, a wet etching process based on NH₄Cl was applied. Taking into account that the layer thickness was small, the control of the etch parameters such as etchant concentration and etching time was evaluated as a function of the textured film properties. An appropriate control of the etching rate to adjust the final thickness to the 80 nm required for the application was realized. Using NH₄Cl concentrations of 10 wt.% and short times of up to 25 s, an increase of the film roughness up to a factor of 5.6 of the as-deposited films was achieved. These optimized textured films showed weighted reflectance values below 15% and considerable better electrical properties than the as-deposited 80 nm-thick ZnO:Al films.     

Low-temperature epitaxy of silicon by electron beam evaporation

In this paper we report on homoepitaxial growth of thin Si films at substrate temperatures T_s = 500-650 °C under non-ultra-high vacuum conditions by using electron beam evaporation. Si films were grown at high deposition rates on monocrystalline Si wafers with (100), (110) and (111) orientations. The ultra-violet visible reflectance spectra of the films show a dependence on T_s and on the substrate orientation. To determine the structural quality of the films in more detail Secco etch experiments were carried out. No etch pits were found on the films grown on (100) oriented wafers. However, on films grown on (110) and (111) oriented wafers different types of etch pits could be detected. Films were also grown on polycrystalline silicon (poly-Si) seed layers prepared by an Aluminum-Induced Crystallisation (AIC) process on glass substrates. Electron Backscattering Diffraction (EBSD) shows that the film growth proceeds epitaxially on the grains of the seed layer. But a considerably higher density of extended defects is revealed by Secco etch experiments.     

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.     

High resolution Rutherford Backscattering Spectrometry investigations of ZrO2 layer growth in the initial stage on native silicon oxide and titanium nitride

High Resolution Rutherford Backscattering Spectrometry (HR-RBS) with a depth resolution of about 0.3 nm near the surface was used to analyse the interface between ultrathin high-k ZrO₂-layers and the substrate. In order to improve the quality of the analysis, a method was developed that takes local thickness variations, obtained by atomic force microscopy, into account during simulation of the HR-RBS spectra. The initial stages of atomic layer deposition (ALD) growth processes on Si(100) covered with native silicon oxide (SiO₂) or with TiN have been studied. In the first case the interface is sharp, except for a small intermediate ZrSiO₄-layer, and no diffusion of Zr-atoms in SiO₂ could be detected. A quite different behaviour could be derived from high resolution spectra for the growth of ZrO₂ on TiN. In addition, measurements of the surface topography of the TiN-layer revealed non-negligible surface roughness. Diffusion of Zr into polycrystalline TiN was demonstrated after correction for surface roughness. This observation indicates that already during the first ALD reaction cycle a small proportion of the deposited Zr-atoms diffuses - probably along grain boundaries - into the TiN-layer up to a depth of 3 nm.     

HfO2 etching mechanism in inductively-coupled Cl2/Ar plasma

Etching characteristics and the mechanism of HfO₂ thin films in Cl₂/Ar inductively-coupled plasma were investigated. The etch rate of HfO₂ was measured as a function of the Cl₂/Ar mixing ratio in the range of 0 to 100% Ar at a fixed gas pressure (6 mTorr), input power (700 W), and bias power (300 W). We found that an increase in the Ar mixing ratio resulted in a monotonic decrease in the HfO₂ etch rate in the range of 10.3 to 0.7 nm/min while the etch rate of the photoresist increased from 152.1 to 375.0 nm/min for 0 to 100% Ar. To examine the etching mechanism of HfO₂ films, we combined plasma diagnostics using Langmuir probes and quadrupole mass spectrometry with global (zero-dimensional) plasma modeling. We found that the HfO₂ etching process was not controlled by ion-surface interaction kinetics and formally corresponds to the reaction rate-limited etch regime.     

Ni-Al-O diffusion barrier layer for high-κ metal-oxide-semiconductor capacitor

Using amorphous Ni-Al-O (a-Ni-Al-O) thin film as the intermediate layer, poly-crystalline Er₂O₃ thin film was grown on a-Ni-Al-O/Si (p-type) via laser molecular beam epitaxy, forming the Er₂O₃/Ni-Al-O gate stack. It was found that the mean dielectric constant of the Er₂O₃/Ni-Al-O gate stack with an equivalent oxide thickness of 1.5 nm is about 17-23, the interfacial states density is about 3.16 × 10¹² cm⁻² and the stack gate leakage current density is as small as 4.1 × 10^− 6 A/cm². Furthermore, The insertion of the Ni-Al-O thin film between the Er₂O₃ gate dielectric and p-Si substrate prevents the oxygen from being out-diffused, which significantly improved the stability of gate stack, showing that the Er₂O₃/Ni-Al-O gate stack thin film could be used as an ideal gate oxide layer for the future Metal Oxide Semiconductor Field Effect Transistors.     

Structure and optical properties of Zr1−xSixN thin films on sapphire

A series of zirconium silicon nitride (Zr_1−xSi_xN) thin films were grown on r-plane sapphire substrates using reactive RF magnetron co-sputtering of Zr and Si targets in a N₂/Ar plasma. X-ray diffraction pole figure analysis, X-ray reflectivity, X-ray photoelectron spectroscopy (XPS), optical microscopy, and optical absorption spectroscopy were used to characterize the film stoichiometries and structures after growth at 200 °C and post-deposition annealing up to 1000 °C in ultra-high vacuum. The atomically clean r-plane sapphire substrates induce high quality (100) heteroepitaxy of ZrN films rather than the (111) orientation observed on steel and silicon substrates, but the addition of Si yields amorphous films at the 200 °C growth temperature. After the annealing treatment, films with Si content x < 0.15 have compressive stress and crystallize into a polycrystalline structure with (100) fiber texture. For x > 0.15, the films are amorphous and remain so even after ultra-high vacuum annealing at 1000 °C. XPS spectra indicate that the bonding changes from covalent to more ionic in character as Si―N bonds form instead of Zr―N bonds. X-ray reflectivity, atomic force microscopy (AFM) and optical microscopy data reveal that after post-deposition annealing the 100 nm thick films have an average roughness < 2 nm, except for Si content near x = 0.15 corresponding to where the film becomes amorphous rather than being polycrystalline. At this stoichiometry, evidence was found for regions of film delamination and hillock formation, which is presumably driven by strain at the interface between the film and sapphire substrate. UV-visible absorption spectra also were found to depend on the film stoichiometry. For the amorphous Si-rich films (x > 0.15), the optical band gap increases with Si content, whereas for Zr-rich films (x < 0.15), there is no band gap and the films are highly conductive.     

Interfacial layer growth of ZrO2 films on silicon

In this work, the interfacial layer growth for both as-deposited and annealed ZrO₂ thin films on silicon is analyzed in detail by the high-resolution cross-sectional transmission electron microscope and spectroscopic ellipsometry. For as-deposited ZrO₂/SiO₂/Si, the thickness of a SiO₂-like layer at the silicon interface was found to depend on the oxygen partial pressure during deposition. At oxygen partial pressure ratio of above 50% the interfacial silicon oxide thickness increased through oxygen diffusion through the ZrO₂ film and silicon consumption at the interface. At oxygen partial pressure ratio in the range 7-50%, the visible growth of interfacial silicon oxide layer was not present. The interfacial layer for ZrO₂/Si with optimal partial pressure (15%) during annealing at 600 °C was found to be the two-layer structure composed of the ZrSi_xO_y overlayer and the SiO_x downlayer. The formation of the interfacial layer is well accounted for diffusion mechanisms involving Si indiffusion and grain-boundary diffusion.     

Dry etching process of GaAs in capacitively coupled BCl3-based plasmas

Dry etching of GaAs was investigated in BCl₃, BCl₃/N₂ and BCl₃/Ar discharges with a mechanical pump-based capacitively coupled plasma system. Etched GaAs samples were characterized using scanning electron microscopy and surface profilometry. Optical emission spectroscopy was used to monitor the BCl₃-based plasma during etching. Pure BCl₃ plasma was found to be suitable for GaAs etching at > 100 mTorr while producing a clean and smooth surface and vertical sidewall. Adding N₂ or Ar to the BCl₃ helped increase the etch rates of GaAs. For example, the GaAs etch rate was doubled with 20% N₂ composition in the BCl₃/N₂ plasma compared to the pure BCl₃ discharge at 150 W CCP power and 150 mTorr chamber pressure. The GaAs etch rate was ∼ 0.21 µm/min in the 20 sccm BCl₃ plasma. The BCl₃/Ar plasma also increased etch rates of GaAs with 20% of Ar in the discharge. However, the surface morphology of GaAs was strongly roughened with high percentage (> 30%) of N₂ and Ar in the BCl₃/N₂ and BCl₃/Ar plasma, respectively. Optical emission spectra showed that there was a broad BCl₃-related molecular peak at 450-700 nm wavelength in the pure BCl₃ plasma. When more than 50% N₂ was added to the BCl₃ plasma, an atomic N peak (367.05 nm) and molecular N₂ peaks (550-800 nm) were detected. Etch selectivity of GaAs to photoresist decreased with the increase of % N₂ and Ar in the BCl₃-based plasma.     

Tensile strain engineering of Si thin films using porous Si substrates

Highly tensile strained (up to 2.2%) thin monocrystalline silicon (mc-Si) films were fabricated by a simple and low-cost method based on the in-plane expansion of meso-porous silicon (PS) substrates upon low temperature oxidation. To control the film thickness below 100 nm, an original “two wafer” technique was employed during the porosification process. This method enables the fabrication of a 60 nm thick mc-Si films on 250 μm thick meso-porous silicon substrates over areas as large as 2 in. with a surface roughness and cleanliness comparable to that of standard Si wafers. Crack-free 60 nm thick Si films can be strained up to 1.2% by controlled low temperature oxidation of the PS substrate. Structural and strain analysis of the PS/mc-Si structures performed by transmission electron microscopy and micro-Raman scattering spectroscopy are reported.     

Gas phase particle formation and elimination on Si (100) in low temperature reduced pressure chemical vapor deposition silicon-based epitaxial layers

Gas phase particle formation and elimination in silicon epitaxial layers grown on Si (100) substrates using reduced pressure chemical vapor deposition at low temperatures (< 600 °C) are investigated. High-order silane precursors (Si_nH_2n + 2; n = 3, n > 3) are useful for high growth rate epitaxy at low temperature. However, particulates are observed on the surface of the epitaxial layers grown with high-order silanes. These particulates are attributed to gas phase particles. As atomically smooth epitaxial films are desired, the elimination of gas phase particles is required. Cyclical deposition and etch process and/or low pressure deposition enables atomically smooth SiCP epitaxial films with a high-order silane.     

Thermal treatment effects on interfacial layer formation between ZrO2 thin films and Si substrates

This paper describes the growth condition of stoichiometric ZrO₂ thin films on Si substrates and the interfacial structure of ZrO₂ and Si substrates. The ZrO₂ thin films were prepared by rf-magnetron sputtering from Zr target with mixed gas of O₂ and Ar at room temperature followed by post-annealing in O₂ ambient. The stoichiometric ZrO₂ thin films with smooth surface were grown at high oxygen partial pressure. The thick Zr-free SiO₂ layer was formed with both Zr silicide and Zr silicate at the interface between ZrO₂ and Si substrate during the post-annealing process due to rapid diffusion of oxygen atoms through the ZrO₂ thin films. After post annealing at 650-750 °C, the multi-interfacial layer shows small leakage current of less than 10⁻⁸ A/cm² that is corresponding to the high-temperature processed thermal oxidized SiO₂.