Polishing behaviors of single crystalline ceria abrasives on silicon dioxide and silicon nitride CMP

The effects of single crystalline ceria (CeO₂) abrasives in chemical mechanical polishing (CMP) slurries were investigated for silicon dioxide (SiO₂) and silicon nitride (Si₃N₄) CMP process. The size of ceria abrasives was controlled by varying hydrothermal reaction conditions. Polishing removal rate was measured with four slurries, with different mean primary particle size of 62, 116, 163 and 232 nm. The polishing results showed that the single crystalline ceria abrasives were not easily broken-down by mechanical force during CMP process. It was found that the removal rate of oxide and nitride film strongly depend upon abrasive size, whereas the surface uniformity deteriorates as abrasive size increases. The observed polishing results confirmed that there exists an optimum abrasive size (163 nm) for maximum removal selectivity between oxide and nitride films. The polishing behavior of the single crystalline ceria abrasives was discussed in terms of morphological properties of the abrasive particle.     

Platinum chemical mechanical polishing (CMP) characteristics for high density ferroelectric memory applications

The key component of ferroelectric random access memory (FeRAM) is a capacitor including a ferroelectric thin film and electrode materials. Platinum is one of the suitable metals which meet requirements such as low resistivity, high thermal stability, and good oxygen resistance. Generally, the ferroelectric and the electrode materials were patterned by a plasma etching process. The application possibility of chemical mechanical polishing (CMP) processes to the patterning of ferroelectric thin film instead of plasma etching was investigated in our previous study for improvement of an angled sidewall which prevents the densification of FeRAM. In this study, the characteristics of platinum CMP for FeRAM applications were also investigated by an approach as bottom electrode materials of ferroelectric material in CMP patterning. The removal rate was increased from 24.81 nm/min by the only alumina slurry (0.0 wt% of H₂O₂ oxidizer) to 113.59 nm/min at 10.0 wt% of H₂O₂ oxidizer. Electrochemical study of platinum and alumina slurry with various concentrations of H₂O₂ was performed in order to investigate the change of the removal rate. The decreased particle size in the alumina slurry with an addition of 10.0 wt% H₂O₂ oxidizer made the improved surface roughness of the platinum thin films. Micro-scratches were observed in all polished samples.     

A study on the chemical mechanical polishing of oxide film using a zirconia (ZrO2)-mixed abrasive slurry (MAS)

We have studied the chemical mechanical polishing (CMP) characteristics of mixed abrasive slurry (MAS) retreated by adding of zirconium oxide (ZrO₂) abrasives within 1:10 diluted silica slurry. These mixed abrasives in the MAS are evaluated with respect to their particle size distribution, surface morphology, and CMP performance such as removal rate and non-uniformity. As an experimental result, the comparable slurry characteristics when compared to the original silica slurry were obtained from the viewpoint of high removal rate and low non-uniformity for excellent CMP performance. Therefore, our proposed ZrO₂-MAS can be useful to save on the high cost of slurry consumption since we used a 1:10 diluted silica slurry.     

Surface acoustic wave characteristics of AlN thin films grown on a polycrystalline 3C-SiC buffer layer

In this study, AlN thin films were deposited on a polycrystalline (poly) 3C-SiC buffer layer for surface acoustic wave (SAW) applications using a pulsed reactive magnetron sputtering system. AFM, XRD and FT-IR were used to analyze structural properties and the morphology of the AlN/3C-SiC thin film. Suitability of the film in SAW applications was investigated by comparing the SAW characteristics of an interdigital transducer (IDT)/AlN/3C-SiC structure with the IDT/AlN/Si structure at 160 MHz in the temperature range 30-150 °C. These experimental results showed that AlN films on the poly (1 1 1) preferred 3C-SiC have dominant c-axis orientation. Furthermore, the film showed improved temperature stability for the SAW device, TCF = −18 ppm/°C. The change in resonance frequency according to temperature was nearly linear. The insertion loss decrease was about 0.033 dB/°C. However, some defects existed in the film, which caused a slight reduction in SAW velocity.     

Effect of H2O evolving from TEOS based SiO2 film on the EEPROM cell characteristic

In this paper, we investigate the effect of water (H₂O) molecules evolving from silicon dioxide (SiO₂) film deposited by low pressure chemical vapor deposition (LPCVD) at 670 °C on the transistor characteristic of an electrically erasable programmable read only memory (EEPROM) cell. Fourier Transform Infra red (FT-IR) analysis reveals that H₂O is captured during film deposition and diffused to silicon surface during high thermal processing. The diffused H₂O molecules lower threshold voltage (V_t) of cell transistor and, thus, leakage current of the cell transistor is increased. In erased cell, V_t lowering is 0.25 V in which it increases leakage current of cell transistor from 1 to 100 pA. This results in the lowering of high voltage margin of a 512 Kb EEPROM from 2.8 to 2.6 V at 85 °C.     

Repair of plasma-damaged p-SiOCH dielectric films in supercritical CO2

The silylation of plasma-damaged p-SiOCH low-k dielectric films was investigated with trimethychlorosilane (TMCS), hexamethyldisilazane (HMDS) and dimethyldichlorosilane (DMDCS) dissolved in supercritical CO₂ (scCO₂) and the effect of thermal pre-treatment on the repair performance was also studied. The surface hydrophobicity was rapidly recovered by silylation and the order of recovery efficiency was HMDS (85.4°) > DMDCS (83.4°) > TMCS (75.0°). The FTIR analyses revealed that the restoration to the original state was not achieved over various reaction conditions (up to 31 MPa, 85 °C, and 3 h reaction time). After pre-treatment in a vacuum cell at 250 °C, the Si-O-Si peak intensity increased slightly, and the surface hydrophobicity was partially recovered to 54.4° due to the removal of physically adsorbed H₂O molecules as well as some extent of dehydration of neighboring surface silanol groups. The hydrophobicity increased to 84.4° after subsequent treatment with HMDS in scCO₂. From DSIMS, the carbon concentration did not increase in bulk region after silylation of thermally pre-treated low-k films.     

Optimization of slurry components for a copper chemical mechanical polishing at low down pressure using response surface methodology

Copper replaced aluminium and the low-dielectric constant material (low-k dielectrics) served as a better isolator, which has become the inevitable developing trend of IC technology. Due to the low compression resistance of low-k material, the mechanical strength must be reduced in order to ensure the functional integrity, which is a challenge for the traditional chemical-mechanical polishing (CMP) technology. To solve this issue, it is necessary to develop a chemically dominant CMP process at low down pressure. It is generally known that the implementation of optimum slurry composition is one of the important issues. To achieve a high removal rate (RR) and minimal WIWNU (Within-Wafer Non-Uniformity) at a down pressure of 0.63 psi, the response surface methodology (RSM) was applied to optimize slurry composition which contains silica sols, H₂O₂ and FA/O chelating agent. A central composite design, which is the standard design of RSM, was used to evaluate the effects and interactions of three factors. The optimal conditions obtained from the compromise of the two desirable responses, RR and WIWNU, were silica sols concentration of 13.88 vol.%, H₂O₂ concentration of 16.13 ml/L and FA/O chelating agent concentration of 20.22 ml/L, respectively. The RSM was demonstrated as an appropriate approach for the optimization of the slurry components by confirmation experiments.     

Anomalous thermal oxidation of gadolinium thin films deposited on silicon by high pressure sputtering

Thin gadolinium metallic layers were deposited by high-pressure sputtering in pure Ar atmosphere. Subsequently, in situ thermal oxidation was performed at temperatures ranging from 150 to 750 °C. At an oxidation temperature of 500 °C the films show a transition from monoclinic structure to a mixture of monoclinic and cubic. Regrowth of interfacial SiO_x is observed as temperature is increased, up to 1.6 nm for 750 °C. This temperature yields the lowest interface trap density, 4 × 10¹⁰ eV⁻¹ cm⁻², but the effective permittivity of the resulting dielectric is only 7.4. The reason of this low value is found on the oxidation mechanism, which yields a surface with located bumps. These bumps increase the average thickness, thus reducing the capacitance and therefore the calculated permittivity.     

Thermal stability of Ni silicide films on heavily doped n and p Si substrates

Electrical and structural properties of Ni silicide films formed at various temperatures ranged from 200 °C to 950 °C on both heavily doped n⁺ and p⁺ Si substrates were studied. It was found that surface morphology as well as the sheet resistance properties of the Ni silicide films formed on n⁺ and p⁺ Si substrates at the temperatures higher than 600 °C were very different. Agglomerations of Ni silicide films on n⁺ Si substrates begin to occur at around 600 °C while there is no agglomeration observed in Ni silicide films on p⁺ Si substrates up to a forming temperature of 700 °C. It was also found that the phase transition temperature from NiSi phase to NiSi₂ phase depend on substrate types; 900 °C for NiSi film on n⁺ Si substrate and 750 °C for NiSi film on p⁺ Si substrate, respectively. Our results show that the agglomeration is, especially, important factor in the process temperature dependency of the sheet resistance of Ni silicides formed on n⁺ Si substrates.     

Evaluation of a novel unfluorinated copper precursor for chemical vapor deposition

A kinetics of the chemical vapor deposition (CVD) of copper using novel unfluorinated precursor, copper(I)(N(1(dimethylvinylsiloxy)-1-methylethano)-2-imino-4-pentanoate), namely Cu-KI5, was studied. Since its great thermal stability, Cu-KI5 allowed high source temperature to provide high vapor pressure, for example Cu-KI5 has a vapor pressure of 0.2-2.2 Torr at the temperature range of 100-140 °C. Furthermore, copper could be deposited by direct reduction from Cu-KI5 instead of disproportionation. By using formic acid (HCOOH) as a reducing agent, copper films were deposited on ruthenium substrate at temperature range of 150-350 °C. The activation energy was 48.9 kJ/mol in surface reaction limited region (<210 °C) and 1.9 kJ/mol in diffusion limited region (>210 °C) at the total pressure of 5 Torr. Secondary ion mass spectroscopy (SIMS) analysis showed that CVD copper film of high purity (>99.99%) was deposited at 250 °C. The as-deposited copper films grown at 150-300 °C exhibited strong 〈111〉 preferred orientation. The minimum resistivity of the copper film was 1.77 μΩ cm obtained at the deposition temperature of 250 °C. In the surface reaction limited region, kinetic data extracted from experiments enabled 2-D computational simulation to predict copper deposition into trench structures. Simulation results showed excellent step coverage, which was larger than 90% for aspect ratio of 10:1. Cu-KI5 is a promising Cu-CVD precursor for the fabrication of ultra large scale integration (ULSI) or through silicon via (TSV) copper interconnects.     

Solid phase epitaxial growth of Dy-germanide films on Ge(0 0 1) substrates

Dy thin films are grown on Ge(0 0 1) substrates by molecular beam deposition at room temperature. Subsequently, the Dy film is annealed at different temperatures for the growth of a Dy-germanide film. Structural, morphological and electrical properties of the Dy-germanide film are investigated by in situ reflection high-energy electron diffraction, and ex situ X-ray diffraction, atomic force microscopy and resistivity measurements. Reflection high-energy electron diffraction patterns and X-ray diffraction spectra show that the room temperature growth of the Dy film is disordered and there is a transition at a temperature of 300-330 °C from a disordered to an epitaxial growth of a Dy-germanide film by solid phase epitaxy. The high quality Dy₃Ge₅ film crystalline structure is formed and identified as an orthorhombic phase with smooth surface in the annealing temperature range of 330-550 °C. But at a temperature of 600 °C, the smooth surface of the Dy₃Ge₅ film changes to a rough surface with a lot of pits due to the reactions further.     

Properties of low-k SiCOH films prepared by plasma-enhanced chemical vapor deposition using trimethylsilane

The properties of low-k SiCOH film deposited by plasma-enhanced chemical vapor deposition using trimethylsilane are reported here. The deposition process was performed at different temperatures from 200 to 400 °C. The influence of deposition temperature on the films were characterized using Fourier transform infrared spectroscopy (FTIR) to understand its impact on the studied properties. The films were annealed at ∼450 °C in an inert ambient after deposition in all the cases. The deposition rate decreases with increase in deposition temperature. The refractive index of the films increases as a function of deposition temperature. From FTIR spectra, OH-related bonds were not detected in films even when deposited at 200 °C. The Si-CH₃ bonds were detected in all the films and decreased monotonically from 200 to 400 °C. All deposition conditions studied resulted in films with dielectric constant less than 3, the lowest being ∼2.7 when deposited at 200 °C. All films exhibited good thermal stability.     

Yttrium silicide formation and its contact properties on Si(1 0 0)

Yttrium silicide formation and its contact properties on Si(1 0 0) have been studied in this paper. By evaporating a yttrium metal layer onto Si(1 0 0) wafer in conventional vacuum condition and rapid thermal annealing, we found that YSi_2-x begins to form at 350 °C, and is stable to 950 °C. Atomic force microscopy characterization shows the pinholes formation in the formed YSi_2-x film. By current-voltage measurement, the Schottky barrier height (SBH) of YSi_2-x diode on p-type Si(1 0 0) was shown to be between 0.63 and 0.69 eV for annealing temperature from 500 to 900 °C. By low temperature current-voltage measurement, the SBH of YSi_2-x diode on n-type Si(1 0 0) was directly measured and shown to be 0.46, 0.37, 0.32 eV for annealing temperature of 500, 600, and 900 °C, respectively, and possibly even lower for annealing at 700 or 800 °C.     

Achievement of high planarization efficiency in CMP of copper at a reduced down pressure

We report improved planarization efficiency (ratio of step height reduction and removed layer thickness) in chemical-mechanical planarization (CMP) of copper lines at a down pressure of 2 psi. The CMP slurry used to achieve these results contains fumed silica particles (abrasive), β-alanine (surface complexing agent) and H₂O₂ (oxidizer), combined with dissolution inhibiting ammonium dodecyl sulfate (ADS) and/or low concentrations (≤1 mM) of benzotriazole (BTAH) at a solution pH of 4.0. When only ADS or BTAH is used, Cu dissolution rate is reduced, but at the cost of somewhat low planarization efficiency. Combination of ADS (typically 3 mM) and BTAH (≤1 mM) in the slurry significantly improves both the surface polish rates and the planarization efficiency. The processed surface (examined by optical profilometry) is noticeably defect-free for this particular system. The mechanisms of surface dissolution and passivation are discussed, and contact angle data are used to elucidate the surface passivating nature of the inhibitor films. The results presented here are relevant for further developments in the area of low pressure CMP of Cu lines overlying fragile low-k dielectrics in the new interconnect structures.     

Impact of the CMP process on the electrical properties of ultra low k porous SiOCH

The impact of chemical mechanical polishing (CMP) on SiOCH films (thickness = 300 nm) for the 32-45 nm node Cu-interconnect process is investigated by low-frequency dielectric spectroscopy and thermally stimulated depolarization current (TSDC). After CMP process, the dielectric permittivity is degraded of about 25% in the whole range of the investigated frequency (10⁻¹ Hz-100 kHz). In a same way, the dielectric losses tan δ increase at the lowest frequencies. An annealing (300 °C during 20 min) carried out after CMP induces a reduction of the dielectric permittivity without however reaching the value of initial as-deposited material. In agreement with other published papers focusing on the damage caused by the CMP, OH bonding and water adsorption due to surfactants explain the degradation of these dielectric properties. The identification of OH bonds and an increase in the intensity of CH_x in the 2800-3050 cm⁻¹ range after CMP seems to confirm this point. The moderate temperature of annealing, used to restore layers and to avoid the degradation of copper lines, suppresses the physisorbed water but not the chemisorbed water. TSDC measurements confirm that dipolar relaxation, due to water in the material, result in a peak of relaxation at a temperature around 175 °C.     

Texture and strain in narrow copper damascene interconnect lines: An X-ray diffraction analysis

The behaviour of submicron damascene copper lines raises a number of fundamental issues such as grain growth in narrow trenches, thermomechanical properties of copper in these confined geometries, etc. This experimental study is aimed at evaluating the influence of annealing, polishing and line width on the room temperature strain and texture of narrow copper damascene lines. X-ray diffraction has been performed on arrays of lines with widths ranging between 3 μm and 0.09 μm. Two annealing conditions (150 °C and 400 °C) have been used either prior or after Chemical Mechanical Polishing (CMP). A clear influence of the Cu overburden on the in-line microstructure is evidenced. X-ray diffraction analysis shows that strains in line longitudinal direction are higher in those annealed at 400 °C and decrease with the width of the lines.Effect of CMP on structure and relationship between both texture and strain and temperature of thermal treatments is discussed in light of these observations.     

Properties of ZnO/Cu/ZnO multilayer films deposited by simultaneous RF and DC magnetron sputtering at different substrate temperatures

ZnO/Cu/ZnO transparent conductive multilayer films are prepared by simultaneous RF sputtering of ZnO and DC sputtering of Cu. The properties of the multilayer films are studied at different substrate temperatures. Sheet resistance of the multilayer film decreased initially with increase of substrate temperature and increased further with increase of substrate temperature beyond 100 °C. However, transmittance of the multilayer film increased with increase of substrate temperature. Good transparent conductive film of sheet resistance 9.3 Ω/sq and transmittance of 85% was found at a substrate temperature of 100 °C. The performance of the multilayer film was evaluated using a figure of merit. The observed property of the multilayer film is suitable for the application of transparent conductive electrodes.     

An investigation of ultra low-k dielectrics with high thermal stability for integration in memory devices

For the PMD in a next generation memory device, two kinds of newly developed ultra low-k MSQ materials (k < 2.0) are shown to have good thermal stability, up to 600 °C, while the investigated HSQ (k = 2.9) material degraded at temperatures >500 °C. The thermal stability of the low-k MSQ is correlated with the amount of Si-X (X = H or CH₃), the ratio of Si-X to Si-O, and the structure of the Si-O bonds. With PE-SiO₂ and PE-SiN capping on HSQ, the k-value of  < 3.0 can be maintained up to 800 °C due to Si-H remaining in the film. Similarly, PE-SiC and PE-SiO₂ capping increases the k-value degradation onset temperature of the MSQ materials by 50 °C.     

Ultrathin insulating silica layers prepared from adsorbed TEOS, H2O and NH3 as a catalyst

Homogeneous ultrathin silica films were deposited without need of any expensive equipment and high-temperature processes (t?200 °C). Repeated adsorption of tetraethoxysilane (TEOS) multimolecular layers and their subsequent reaction with H₂O/NH₃ mixed vapours at atmospheric pressure and room temperature were used. By preparing the Al/SiO₂/N-Si MOS structure conditions were attained for electrical characterisation of the thin oxide layer by capacitance (C-V) and current (I-V) measurements. These measurements confirmed acceptable insulating properties of the oxide, the maximum breakdown field intensity being E_bd=5.4 MV/cm. The total defect charge of the MOS structure was positive, affected by a high trap density at the Si-SiO₂ interface.     

Effects of annealing schedule on orientations of Bi3.2Nd0.8Ti3O12 ferroelectric films prepared by metalorganic solution deposition

Fatigue-free Bi_3.2Nd_0.8Ti₃O₁₂ ferroelectric thin films were successfully prepared on p-Si(1 1 1) substrate using metalorganic solution deposition process. The orientation and formation of thin film under different annealing schedules were studied using XRD and AFM. XRD analysis indicated that (2 0 0)-oriented films with degree of orientation of I₍₂₀₀₎/I₍₁₁₇₎ = 2.097 and 0.466 were obtained by preannealing the film at 400 °C for 10 min followed by rapid thermal annealing at 700 °C for 3 min, 10 min and 20 min, respectively, (0 0 8)-oriented film with degree of orientation of I₍₀₀₈₎/I₍₁₁₇₎ = 1.706 were obtained by rapid thermal annealing the film at 700 °C for 3 min without preannealing, and (0 0 8)-oriented film with degree of orientation of I₍₀₀₈₎/I₍₁₁₇₎ = 0.719 were obtained by preheating the film from room temperature to 700 °C at 20 °C/min followed by annealing for 10 min. The a-axis and c-axis orientation decreased as increase in annealing time due to effects of (1 1 1)-oriented substrate. AFM analysis further indicated that preannealing at 400 °C for 10 min followed by rapid thermal annealing at 700 °C for 3 min resulted in formation of platelike crystallite parallel to substrate surface, however rapid thermal annealing at 700 °C for 3 min without preannealing resulted in columnar crystallite perpendicular to substrate surface.