Modeling of Cu gettering in p- and n-type silicon and in poly-silicon

Based on experimental findings we set up calculations of numerical modeling of gettering efficiencies for Cu in various silicon wafers. Gettering efficiencies for Cu were measured by applying a reproducible spin-on contamination in the 10¹² atoms/cm² range, followed by a thermal treatment to redistribute the metallic impurity. Subsequently, the wafers were analyzed by a novel wet chemical layer-by-layer etching technique in combination with inductively coupled plasma mass spectrometry. We investigated p/p+ and n/n+ epitaxial wafers with different doping levels and different substrate-doping species. We have also investigated gettering efficiencies of phosphorus-diffused p- and n-type wafers. Heavilyboron doped silicon exhibited a gettering efficiency of ∼100%, while gettering by n+ silicon occurred for doping levels >3×10¹⁹ atoms/cm³ only. In another set of experiments we investigated the dependence of the gettering efficiency of p-type wafers with poly-silicon back sides for different cooling rates and Cu spiking levels. A strong dependence on both parameters was found. Cu gettering in p/p+ epitaxial wafers was modeled by calculating the increased solubility of Cu in p+ silicon compared to non-doped silicon taking into account the Fermi-level effect, which stabilizes donors in p+ silicon, and the pairing reaction between Cu and B. Calculated gettering efficiencies were in very good agreement with experimental results. Gettering in n+ silicon was similarly modeled in terms of pairing reactions and the Fermi-level effect. But, for n-type silicon, many experimental uncertainties existed; thus, we applied our expressions to solubility data of Hall and Racette to obtain the unknown parameters. The empirical calculations were in good agreement even with results on n/n+ wafers. For phosphorus-diffused wafers we had to consider an excess vacancy concentration of 1.2–5.5 times the equilibrium concentration to explain the experimental findings by the model. Gettering by poly-silicon back sides was simulated by solving the time-dependent diffusion equation with boundary conditions that take into account different surface reaction rates of silicon point defects. Using this advanced model, the experimentally measured gettering efficiencies were reproduced within the uncertainty of the measurement. Received: 3 September 2001 / Accepted: 4 September 2001 / Published online: 20 December 2001     

Comparison of different gettering techniques for Cu–p+ versus polysilicon and oxygen precipitates

We performed measurements of gettering efficiencies for Cu in silicon wafers with competing gettering sites. Epitaxial wafers (p/p+) boron-doped with a polysilicon back side allowed us to compare p+ gettering with polysilicon gettering. We further measured metal distributions in p+/p- epitaxial test wafers, with the p- substrate wafers pretreated for oxygen precipitation to compare p+ gettering with oxygen precipitate gettering. Our test started with a reproducible spin-on contamination in the 10¹² atoms/cm² range, followed by thermal treatment in order to redistribute the metallic impurity. Wafers were then analyzed by a novel wet chemical layer-by-layer etching technique in combination with inductively coupled plasma mass spectrometry. This led to “stratigraphical” concentration profiles of the impurity, with typical detection limits of 5–10×10¹² atoms/cm³. Twenty-five percent of the total Cu contamination in the p/p+/poly wafer was found in the p+ layer, whilst 75% was gettered by the polysilicon. Obviously, polysilicon exhibits a stronger gettering than p+ silicon, but due to the large distance from the front surface, polysilicon was less effective in reducing impurities from the front side of a wafer compared with p+ gettering. An epitaxial layer p+ on top of p- substrates with oxygen precipitates gettered 50% of the total Cu; while the other 50% of the Cu was measured in the p- substrate wafer with oxygen precipitates. Without oxygen precipitates, 100% of the spiked Cu contamination was detected inside the p+ layer. Gettering by oxygen precipitates thus occurs in the same temperature range as that where p+ silicon begins to getter Cu. Received: 3 September 2001 / Accepted: 17 October 2001 / Published online: 27 March 2002     

Studies of interface structures of W films grown on patterned and bare Si(100) by TEM

+ Si(100) and bare Si(100) wafers by low pressure chemical vapour deposition (LPCVD) at 230–280 °C. The films were investigated by transmission electron microscopy (TEM). The cross-sectional TEM samples of W/Si(100) exhibited a fine scale interface roughness, which was attributed to the surface preparation. Irregular W plug structures were observed depending on the predeposition procedures. It was observed that an insufficient deposition of W films on the contact surface leads to the presence of aluminium around and underneath the plugs. This was observed by energy dispersive X-ray spectrometry (EDX). A study, using conventional electron diffraction, confirmed that no silicides formed at the interfaces of W-bare Si(l00) wafers. Received: 16 December 1996/Accepted: 6 May 1997     

Low-threshold field electron emission of Si micro-tip arrays produced by laser ablation

Low-threshold field electron emission (FEE) is reported for periodic arrays of micro-tips produced by laser ablation of Si wafers. The best samples show emission at threshold fields as low as 4–5 V/μm for n-type Si substrates and of 1–2 V/μm for p-doped Si substrates, as measured with a flat-screen technique. Auger electron spectroscopy and X-ray electron spectroscopy reveal island-like deviation of the SiO₂ stoichiometry on the tip surfaces, with lateral dimensions of less than 100 nm. Microscopic studies using a special field-emission STM show that the emission originates from well-conducting regions of sub-micron size. The experimental data suggest FEE from the tip arrays by a geometric field enhancement of both the individual micro-tip and the narrow conducting channels in the tip body. Received: 3 May 2002 / Accepted: 1 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +7-095/135-82-34, E-mail: shafeev@kapella.gpi.ru     

Structural and electrical characteristics of zirconium oxide layers derived by photo-assisted sol–gel processing

This paper reports the photo-assisted formation of ZrO₂ layers derived by sol–gel processing at low temperatures using intense radiation from ultraviolet (UV) excimer lamps. Excellent layer properties can be readily obtained for these sol–gel layers after 5-min exposure to the UV irradiation at around 300 °C. Analyses of the as-deposited sol–gel layers by UV/VIS spectrophotometry show that the organic species contained in the layers have been removed to a large extent after 5-min irradiation. This is further confirmed by X-ray photoelectron spectroscopy analyses of the same irradiated layers, which indicate the formation of ZrO₂ with little carbon contamination contributed by the organic species and less oxidation of Si at the interface. Electrical measurements of these layers are also reported. Received: 31 July 2001 / Accepted: 6 September 2001 / Published online: 17 October 2001     

KrF excimer laser dry and steam cleaning of silicon surfaces with metallic particulate contaminants

KrF excimer laser-assisted dry and steam cleaning of single-crystal silicon wafers contaminated with three different types of metallic particles was studied. The laser fluence used was 0.3 J/cm². In the dry process, for samples cleaned with 100 laser pulses the cleaning efficiency was 91, 71 and 59% for Au, Cu and W particles, respectively, whilst in steam cleaning the efficiency is about 100% after 5 laser pulses, independently of the type of contaminant. The effects of laser irradiation on the Si surface are investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Laser processing at 0.3 J/cm² does not deteriorate the Si-wafer surface, either in dry or steam cleaning. However, the measured XPS intensity coming from the metallic component is greater on the cleaned surfaces than in the initial condition. Quantification of the XPS results, assuming a stratified overlayer model for the detected species and accounting for the presence of the metallic particles on the surface, showed that the obtained results can be explained by the formation of a fractional metallic monolayer on the cleaned surfaces, due to partial vaporisation of small particles initially present on the sample surface. This contamination of the substrate could be considered excessive for some applications and it shows that the process requires careful optimisation for the required efficiency to be achieved without degradation of the substrate. Received: 14 January 2001 / Accepted: 19 February 2001 / Published online: 20 June 2001     

Ni reactions with surfaces: dependence of gettering efficiencies for Ni on crystal-growth conditions, back-side-gettering techniques, oxygen precipitates and thermal treatments

We have performed measurements on the gettering efficiencies for Ni in different silicon wafers. Gettering efficiencies were measured of wafers grown by different crystal-growth techniques, such as Czochralski-grown (CZ) and floating zone (FZ), as well as wafers containing crystal-originated particles (COPs) of different size and density. Lightly boron doped CZ wafers covered with an epitaxial layer were also evaluated. In another set of experiments, we compared different back-side-gettering techniques, like poly-silicon, stacking faults and He-implanted back sides and the dependence of back-side gettering on cooling rate and contamination level. Internal surfaces of oxygen precipitates were also investigated. The gettering test started with a reproducible spin-on contamination in the range around 10¹² atoms/cm² and was followed by a thermal treatment to redistribute the Ni impurity in the wafer. Subsequently, wafers were analyzed for their surface and bulk contamination by a novel layer-by-layer etching, stratigraphical technique in combination with inductively coupled plasma mass spectrometry. No detectable gettering effect of COPs was found. FZ wafers differed remarkably in their gettering behavior from CZ wafers, obviously due to differences in aggregated self-point defects. Most remarkably, the deposition process of an epitaxial layer changed the gettering behavior of p/p- wafers. Comparing the gettering efficiencies of different back sides, an extraordinarily high gettering efficiency of He-implanted voids can be anticipated, which was higher than the gettering efficiency of poly-silicon and stacking faults. High cooling rates at the end of the drive-in cycle and low contamination levels lowered the gettering efficiencies of back-side-gettering techniques, suggesting a diffusion-limited gettering process. Based on the dependence of the gettering efficiencies on different drive-in cycles, a surface reaction as a mechanistic initiation of the drive-in must be assumed. Oxygen precipitates exhibited a high gettering effect for Ni contamination. All experimental results are interpreted by available active surfaces in the gettering phases. Received: 30 May 2001 / Accepted: 16 June 2001 / Published online: 30 August 2001     

Ion-beam-assisted MBE growth of semi-spherical SiGe/Si nano-structures

Semi-spherical SiGe/Si nano-structures of a new type are presented. Epitaxial islands of 30–40 nm in base diameter and 11 nm in height and having a density of about 6×10¹⁰ cm^-2 were produced on (001) Si by molecular beam epitaxial growth of Si/Si_0.5Ge_0.5 layers with in situ implantation of 1-keV As⁺ ions. It was found by cross-section transmission electron microscopy that the islands have a complicated inner structure and consist of a micro-twin nucleus and semi-spherical nano-layers of various SiGe compositions. The nature of the surface patterning is interpreted by stress relaxation through implantation-induced defects. Received: 12 July 2001 / Accepted: 4 September 2001 / Published online: 2 October 2001     

The linkage between macroscopic gettering mechanisms and electronic configuration of 3d-elements in p/p+ epitaxial silicon wafers

We have measured the gettering efficiencies for Cr, Mn, Fe, Co, Ni and Cu in p/p+ epitaxial wafers. The gettering test started with a reproducible spin-on contamination on the front side of the wafers in the 10¹²–10¹⁴ atoms/cm² range, followed by thermal treatment to redistribute the metallic impurities in the wafer. The gettering efficiencies were measured by a novel wet chemical stratigraphic etching technique in combination with inductively-coupled plasma mass spectrometry. The residual bulk metal contamination was also measured by this method. This procedure led to global distributions of the 3d elements on the wafer’s front side, in the bulk of the wafer and on the wafer’s back side. Recovery rates were found to be 34%, 2.3%, 100%, 85%, 100% and 100% for Cr, Mn, Fe, Co, Ni and Cu, respectively. An impurity segregation effect in the wafer bulk was measured for Cu (100%) and Cr (34%), while no detectable segregation-induced gettering mechanisms were detected for the other elements in the applied concentration range. The segregation-induced gettering mechanisms were interpreted from the electronic structure of the metallic impurities. For segregation gettering by increased solubility in p+ silicon, the metallic species must form donors. Only Cu⁺ (3d ¹⁰) and Cr⁺ (3d ⁵) can form singly positively charged species that exhibit a spherical electronic distribution. It is well known from spinell structures that 3d ¹⁰ and, to a smaller extent 3d ⁵, are stable configurations in tetrahedral structures like the silicon lattice. Thus, we link the segregation-induced gettering mechanism in p/p+ epitaxial wafer to the electronic configuration of the 3d elements. Received: 19 January 2001 / Accepted: 31 January 2001 / Published online: 20 June 2001     

Gettering efficiencies for Cu and Ni as a function of size and density of oxygen precipitates in p/p- silicon epitaxial wafers

We have measured the gettering efficiencies for Cu and Ni in p/p-Si epitaxial wafers. The wafers were pretreated to obtain oxygen precipitates of different sizes and densities in the bulk. Gettering tests started with a reproducible spin-on spiking in the range of 10¹² atoms/cm², followed by thermal treatment to drive-in and redistribute the impurities in the wafer. Subsequently, the wafers were analyzed by a novel stratigraphical layer-by-layer etching technique in combination with inductively coupled plasma mass spectrometry. Gettering efficiencies for Ni did not depend on oxygen precipitate sizes and densities as long as ΔO_i was larger than 0.2×10¹⁷ atoms/cm³ and the bulk micro defect densities were detectable by preferential etching (10⁷ cm^-3). In these cases, gettering efficiencies were 96–99% for Ni, while wafers not containing any measurable BMDs exhibited no detectable gettering. Cu exhibited a more complex behavior because the total Cu contamination was found to be divided into two species, one mobile and the other immobile species. A dependence on BMD size and BMD density of the Cu distributions in the wafers was also detected. Gettering effects were increased with increasing BMD densities and sizes. For BMD densities <10⁹ cm^-3, Cu was not efficiently gettered by oxygen precipitates. Even for BMD densities >10¹⁰ cm^-3, gettering effects due to oxygen precipitates were one order of magnitude lower than in heavily boron-doped silicon. Received: 19 January 2001 / Accepted: 31 January 2001 / Published online: 20 June 2001     

Defects in III–V semiconductor surfaces

This work reports the measurement of the nano-scale physical properties of surface vacancies and the extraction of the types and concentrations of dopant atoms and point defects inside compound semiconductors, primarily by cross-sectional scanning tunneling microscopy on cleavage surfaces of III–V semiconductors. The results provide the basis to determine the physical mechanisms governing the interactions, the formation, the electronic properties, and the compensation effects of surface as well as bulk point defects and dopant atoms. Received: 10 May 2001 / Accepted: 23 July 2001 / Published online: 3 April 2002     

Silicon grain arrays prepared using a pattern crystallization technique of pulsed-excimer laser irradiation

Silicon grain arrays were prepared using a pattern crystallization technique of pulsed KrF excimer laser irradiation. The precursor material was hydrogenated amorphous silicon (a-Si:H) thin films deposited on single crystal Si wafers by plasma-enhanced chemical vapor deposition. It was shown that Si grains with a uniform size and a well-defined periodicity embedded in the a-Si:H matrix were obtained by this simple technique. The grain size was less than 2 μm. Relativly strong photo-luminescence with two peaks at 720 and 750 nm was observed at room temperature. We expect to reduce Si grain sizes by optimizing the growth conditions of a-Si:H thin films and controlling the temperature distribution in the film during laser irradiation. Received: 21 November 2000 / Accepted: 12 December 2000 / Published online: 9 February 2001     

MeV-boron implanted layer, oxygen precipitates and poly-silicon back side combined in one silicon wafer: at what defect will Cu and Ni be gettered?

We have measured the gettering efficiencies for Cu and Ni of various silicon wafers, such as MeV-boron-implanted p- polished wafers treated with two different implantation doses of 3×10¹³ atoms/cm² B and 1×10¹⁵ atoms/cm² B, respectively. A third kind of wafer was covered with a poly-silicon back side and thermally pretreated before the gettering test to form oxygen precipitates in the bulk. The gettering test started with a reproducible spin-on spiking on the front side of the wafers in the range around 10¹² atoms/cm², followed by a thermal treatment to redistribute the metallic impurities in the wafer. Then the gettering efficiencies were measured by a novel wet chemical layer-by-layer etching technique in combination with inductively coupled plasma mass spectrometry. This led to “stratigraphical concentration profiles” of the metallic impurities in the wafer with typical detection limits of (5–10)×10¹² atoms/cm³. The concentration profiles were compared with concentration profiles found after testing the gettering efficiency of p/p+ epitaxial wafers. Almost 100% of the total intentional Cu spiking was recovered in the boron buried layer for both implantation doses. On the front surface and in the region between the front surface and the buried layer a Cu concentration ∼20 times higher than on/in p/p+ epitaxial wafers/layers was measured for the implanted specimen. The lower implantation dose led to higher Cu-concentration levels on the front surface compared to the higher implantation dose. The wafer containing a MeV-boron-implanted layer as well as oxygen precipitates and a poly-silicon back side exhibited a Cu distribution of 30/∼0/70%, respectively. Thus, the gettering by poly-silicon exceeded both the gettering effects by the buried layer and by the oxygen precipitates. Ni gettering in MeV-boron-implanted wafers exhibited other characteristics. The gettering efficiency of the buried layer was 65%, while the remaining Ni contamination was equally distributed between the front-side region and the wafer back side. A wafer containing a buried layer obtained by a 1×10¹⁵ atoms/cm³ B dose and oxygen precipitates exhibited 17% of the total Ni contamination in the boron layer, while ∼80% of the total Ni contamination was gettered by oxygen precipitates. In the case of buried layer/oxygen precipitates/poly-silicon back side the distribution was found to be 13/37/45%, thus exhibiting equal gettering strengths for oxygen precipitates and the poly-silicon back side for Ni contamination. The results were discussed in terms of segregation and relaxation-induced gettering mechanisms including different reaction rates. Received: 30 May 2001 / Accepted: 16 June 2001 / Published online: 30 August 2001     

Luminescence properties of thin films prepared by laser ablation of Nd-doped potassium gadolinium tungstate

Optically active thin films on Si substrates have been produced by laser ablation of a Nd-doped potassium gadolinium tungstate (Nd:KGW) single crystal. Films grown at low oxygen pressures (<0.6 mbar) are potassium-deficient and appear to be mainly disordered. They show a poor photoluminescence (PL) performance that improves upon annealing in air at temperatures in the range 700–1000 °C. Films grown at high oxygen pressure (1 mbar) show instead good stoichiometry and the presence of a dominant textured gadolinium-tungstate phase compared to KGW. These films have low absorption, a refractive index close to that of bulk KGW and good PL performance, the emission lifetimes being longer (τ>150 μs) under certain conditions than those measured in the single-crystal material. Received: 25 July 2001 / Accepted: 26 July 2001 / Published online: 17 October 2001     

Analyses of HF/NH4F buffer-treated Si(111) surfaces using XPS,REM and SIMS

The effect of different cleaning procedures on Si(111) wafers has been studied. A three-step cleaning process was used. The first two steps (thermal oxidation followed by RCA cleaning) were common to all samples. The final step involved rinsing in one of a set of HF/NH4F buffer solutions with a wide range ofpH values. Three different surface techniques were used for characterizing the chemical condition and morphology of the treated surfaces: XPS (X-ray Photoemission Spectroscopy), REM (Reflection Electron Microscopy) and SIMS (Secondary-Ion Mass Spectroscopy). It has been found that thepH value of an HF solution does significantly affect the etching rate and morphology of the Si(111) surface: For the same type of solution, the smaller thepH value, the higher the etching rate. Basic solutions withpH values larger than eight have a much weaker etching effect on the surface, which is contradictory to some previous reports. The most effective solutions for the etching of the Si(111) surface are the solutions of HF buffered by NH₄F, with thepH in the range of 2–6. REM images indicate that the surface morphology after etching in the HF solution is strongly affected by the length of the etching time: Overetching will roughen the surface. The SIMS data show that water rinsing in air during the cleaning process does speed up oxidation, but it is necessary to use water to clean off the residuals from the HF solutions.     

UHV-compatible magnetic material for atom optics

Magnetic videotape is of great interest for trapping and guiding cold atomic vapors, but was hitherto considered unsuitable for manipulating Bose–Einstein condensates (BEC) because of the presumed evolution of gas under vacuum. We have studied the outgassing in vacuum of the most promising tape, Ampex 398 Betacam SP. We find that after cleaning in ethanol and baking for 200 h at 100 °C the magnetic patterns are undisturbed and the outgassing is remarkably small: 4×10^-10 Torr l s^-1cm^-2, due mostly to hydrogen. This makes the tape exceedingly attractive for manipulation of BEC. Received: 12 February 2001 / Published online: 7 June 2001     

First-principle study of extrinsic defects in CuScO2 and CuYO2

Using first-principles methods, we studied the extrinsic defects doping in transparent conducting oxides CuMO₂ (MSc, Y). We chose Be, Mg, Ca, Si, Ge, Sn as extrinsic defects to substitute for M and Cu atoms. By systematically calculating the impurity formation energy and transition energy level, we find that BeCu is the most prominent extrinsic donor and CaM is the prominent extrinsic acceptor. In addition, we find that Mg atom substituting for Sc is the most prominent extrinsic acceptor in CuScO₂. Our calculation results are expected to be a guide for preparing n-type and p-type materials through extrinsic doping in CuMO₂ (MSc,Y).     

Thermally stimulated currents in semi-insulating GaAs Schottky diodes and their simulation

We report the investigation of the non-irradiated and irradiated-with-pions Schottky diodes made on semi-insulating GaAs. Thermally stimulated currents have been measured experimentally and modeled numerically. To reveal the influence of the single levels, we used the thermal emptying of the traps by fractional heating. Attention is paid to the comparative analysis of the distribution of the parameters of different samples produced and processed by the same technique, contrary to the usual approach of the analysis of a few different samples. The following main conclusions are drawn. First of all, many different levels (from 8 to 12) have been found in the temperature range from 90 K to 300 K in all samples. Their activation energies range from 0.07 up to 0.55 eV, their capture cross-sections are 10^-22–10^-14 cm², and initial occupation is 2×10¹¹–5×10¹⁴ cm^-3. The irradiation with pions does not influence the density of most levels significantly. On the other hand, levels with activation energies of about 0.07–0.11 eV, 0.33–0.36 eV, 0.4–0.42 eV, and 0.48–0.55 eV have been found only in the irradiated samples. Irradiation also increases the inhomogeneity of the crystals, which causes the scattering of the activation energies obtained by fractional heating technique. Received: 13 November 1998 / Accepted: 16 April 1999 / Published online: 4 August 1999     

Sub-gap absorption study of defects in ion-implanted and annealed Si layers

Sub-gap absorption measurements are presented as a tool to characterize the amorphization and recrystallization processes in ion-implanted and annealed Si layers. The gap state density associated with the disorder introduced in the target crystalline lattice has been shown to saturate once the amorphization dose is exceeded. The doping effect due to implantation of impurity species is also reported. The absorption spectra have also been shown to be very sensitive to defects associated with precipitation of the implanted atoms.     

Novel model for the optical function of GaN

In this work we propose an analytical expression for the complex dielectric function which includes both discrete and continuum exciton effects. We have introduced Lorentzian broadening into Elliott’s formula. The introduction of broadening leads to equations for the dielectric function containing only elementary functions. We have applied the proposed model to the dielectric function of wurtzite GaN in the spectral region 1–10 eV. Excellent agreement with the experimental data has been obtained. We show that the Lorentzian-broadened dielectric function decays more slowly than the experimental data for hexagonal GaN at the low-energy side. This indicates that the broadening of the absorption edge in GaN is not purely Lorentzian. The agreement with the experimental data can be improved using adjustable broadening modification. Received: 29 January 2001 / Accepted: 30 May 2001 / Published online: 25 July 2001