Float Zone Silicon Research Articles

Dry etch damage in n-type crystalline silicon wafers assessed by deep-level transient spectroscopy and minority carrier lifetime

This paper compares the electrically active damage in dry-etched n-type float-zone silicon, using NF3/Ar or H2-plasma exposure and assessed by deep-level transient spectroscopy (DLTS) and recombination lifetime analysis. It is shown that the NF3/Ar-plasma damage consists of at least four different types of electron traps in the upper half of the band gap, which can be associated with vacancy- and vacancy-impurity-related complexes. In the case of H2-plasma damage, it is believed that the accumulation of point defects results in a gradual disordering of the near-surface layer. These defect levels also act as recombination centers, judged by the fact that they degrade the minority carrier lifetime. It is finally shown that lifetime measurements are more sensitive to the etching-induced damage than DLTS.

An effect of residual gas component on detected secondary ions during TOF‐SIMS depth profiling and a method to estimate contained component

With regard to Secondary Ion Mass Spectroscopy (SIMS) measurement of atmospheric gas elements, a problem occurs that the detected signal includes background components caused by residual gas along with contained components. Relating to this issue, an available method to quantify the contained components by separating the background ones had been established for Dynamic SIMS. Time‐of‐Flight SIMS with sputtering ion gun has also applied for depth profiling as well as Dynamic SIMS. However, few studies have attempted to investigate the secondary ion behavior of the atmospheric gas elements for depth profiling by Time‐of‐flight SIMS, especially for low concentration levels. In this study, experimental examinations of the secondary ions of the atmospheric gas elements, such as oxygen, hydrogen, and carbon in the silicon substrate, has been conducted in various analytical conditions of TOF‐SIMS depth profiling mode. Under the analytical conditions of our study, it has been proved that the background intensity of these elements was correlated to the sputtering rate. For the analysis of Floating Zone Silicon substrate, the oxygen intensity of the background component was proportional to the inverse number of the sputtering rate. Based on these facts, the total detected intensity of the atmospheric gas elements was able to be separated into the contained components and background ones by changing the sputtering rate during TOF‐SIMS measurement. An experimental result has shown that the contained oxygen concentration in the Czochralsk Silicon substrate estimated by the “TOF‐SIMS Raster Change Method” has successfully agreed with the result by the Dynamic SIMS.

Infrared defect dynamics—Nitrogen-vacancy complexes in float zone grown silicon introduced by electron irradiation

The interaction of nitrogen and intrinsic point defects, vacancy (V) and self-interstitial (I), was examined by infrared absorption spectroscopy on the electron irradiated and post-annealed nitrogen doped float zone (FZ) silicon crystal. Various absorption lines were observed, at 551 cm−1 in as-grown samples, at 726 and 778 cm−1 in as-irradiated samples (Ir group), at 689 cm−1 after post-annealing at 400 °C and above (400 °C group), at 762 and 951 cm−1 after annealing at 600 °C (600 °C group), and at 714 cm−1 up to 800 °C (800 °C group). By irradiation, a part of N2 was changed into the Ir group. VN2 is the candidate for the origin of the Ir group. By the post annealing at 400 and 600 °C, a part of N2 and the Ir group were changed into the 400 °C group, to less extent at 600 °C. V2N2 is the candidate for the origin of the 400 °C group. By annealing at 600 °C, most of the Ir group turned into 400 °C and 600 °C groups. By annealing at 800 °C, N2 recovered almost completely, and most other complexes were not observed. Recently, lifetime degradation has been observed in the nitrogen doped FZ Si annealed at between 450 and 800 °C. The N-V interaction in the same temperature range revealed here will help to understand the lifetime degradation mechanism. The behavior of the 689 cm−1 line corresponded well to the lifetime degradation.

Three-dimensional modelling of thermal stress in floating zone silicon crystal growth

During the growth of large diameter silicon single crystals with the industrial floating zone method, undesirable level of thermal stress in the crystal is easily reached due to the inhomogeneous expansion as the crystal cools down. Shapes of the phase boundaries, temperature field and elastic material properties determine the thermal stress distribution in the solid mono crystalline silicon during cylindrical growth. Excessive stress can lead to fracture, generation of dislocations and altered distribution of intrinsic point defects. Although appearance of ridges on the crystal surface is the decisive factor of a dislocation-free growth, the influence of these ridges on the stress field is not completely clear. Here we present the results of thermal stress analysis for 4” and 5” diameter crystals using a quasi-stationary three dimensional mathematical model including the material anisotropy and the presence of experimentally observed ridges which cannot be addressed with axis-symmetric models. The ridge has a local but relatively strong influence on thermal stress therefore its relation to the origin of fracture is hypothesized. In addition, thermal stresses at the crystal rim are found to increase for a particular position of the crystal radiation reflector.

Production and annealing of the paramagnetic defects in as-grown and oxygen doped floating zone silicon irradiated with high fluence 3.5 MeV and 27 MeV electrons

The production and thermal stability of the irradiation paramagnetic point defects (IPPDs) in the as-grown, standard float-zone silicon (STFZ) and oxygen doped float-zone silicon (DOFZ) irradiated at room temperature with high fluence 3.5 MeV (1 × 1017 cm−2) low energy and 27 MeV (2 × 1016 cm−2) high energy electrons were investigated by Electron Spin Resonance (ESR). The nature and concentration of the IPPDs identified in the as-irradiated and isochronally annealed up to 300 °C samples by ESR measurements under intense above the gap 1.06 µm in-situ laser illumination, were found to depend on oxygen concentration and electrons energy. While irradiation of STFZ with electrons produced as main IPPDs, besides divacancies, larger tetravacancy and pentavacancy cluster defects, irradiation of DOFZ resulted mainly in divacancies, vacancy-oxygen and interstitial oxygen-carbon impurity pairs. The observed variation in the nature of the main resulting IPPDs with the concentration of incorporated oxygen is explained by differences in the dominant defects production mechanisms. Thus in STFZ with lower oxygen concentration (1 × 1016 cm−3) the dominant production mechanisms are the direct defects formation from a chain of neighboring vacancies by a cascade of secondary recoils across the path of the high energy irradiating particle and the divacancies diffusion and trapping/aggregation. Meanwhile, in DOFZ with larger oxygen content (1.2 × 1017 cm−3) the primary vacancy and interstitial trapping by the oxygen and carbon impurities is the dominant defect production mechanism. Variations in the concentration and nature of the IPPDs observed during isochronal annealing are discussed in terms of defects thermal activated diffusion and recombination processes.

Ultra-high Q terahertz whispering-gallery modes in a silicon resonator

We report on the first experimental demonstration of terahertz (THz) whispering-gallery modes (WGMs) with an ultra-high quality factor of 1.5 × 104 at 0.62 THz. The WGMs are observed in a high resistivity float zone silicon spherical resonator coupled to a sub-wavelength silica waveguide. A detailed analysis of the coherent continuous wave THz spectroscopy measurements combined with a numerical model based on Mie-Debye-Aden-Kerker theory allows us to unambiguously identify the observed higher order radial THz WGMs.

2D tomographic terahertz imaging using a single pixel detector.

A 2D tomographic terahertz imaging set-up using a single pixel imaging approach is realized, where a liquid helium cooled bolometer is utilized as a bucket detector and a mercury-arc lamp serves as a broadband terahertz source. The different patterns of the terahertz radiation, which are necessary for the single pixel imaging approach, are realized by spatially addressed photodoping of a high resistivity float zone silicon window, employing a near-infrared laser diode, which is spatially modulated by a digital micromirror device. The two investigated sample objects have cylindrical and cuboid shapes and consist of polypropylene. Both sample shapes cause strong influences of refraction, reflection and diffraction, which distort the measured projections and thus have to be considered in the tomographic reconstruction. In order to consider these effects, a model is developed which combines refraction and diffraction effects by a hybrid approach using ray tracing and scalar diffraction theory yielding finally projections of the sample objects. These simulated projections are compared to the measured projections and show a good agreement between the experimental results and the developed model. In accordance with this result, an optimization problem is formulated, which offers an approach for tomographic reconstruction using the developed model.

3D numerical simulation of free surface shape during the crystal growth of floating zone (FZ) silicon

In FZ growth processes, the stability of the free surface is important in the production of single crystal silicon with high quality. To investigate the shape of the free surface in the FZ silicon crystal growth, a 3D numerical model that included gas and liquid phases was developed. In this present study, 3D Young-Laplacian equations have been solved using the Volume of Fluid (VOF) Model. Using this new model, we predicted the 3D shape of the free surface in FZ silicon crystal growth. The effect of magnetic pressure on shape of free surface has been considered. In particular, the free surface of the eccentric growth model, which could not be previously solved using the 2D Young-Laplacian equations, was solved using the VOF model. The calculation results are validated by the experimental results.

Bulk lifetime characterization of corona charged silicon wafers with high resistivity by means of microwave detected photoconductivity

Minority carrier lifetime (lifetime) measurements are performed on corona-charged silicon wafers by means of Microwave Detected Photoconductivity (MDP). The corona charge is deposited on the front and back sides of oxidized wafers in order to adjust accumulation conditions. Once accumulation is established, interface recombination is suppressed and bulk lifetimes are obtained. Neither contacts nor non-CMOS compatible preparation techniques are required in order to achieve accumulation conditions, which makes the method ideally suited for inline characterization. The novel approach, termed ChargedMDP (CMDP), is used to investigate neutron transmutation doped (NTD) float zone silicon with resistivities ranging from 6.0 to 8.2 kΩ cm. The bulk properties of 150 mm NTD wafers are analyzed in detail by performing measurements of the carrier lifetime and the steady-state photoconductivity at various injection levels. The results are compared with MDP measurements of uncharged wafers as well as to the established charged microwave detected Photoconductance Decay (charge-PCD) method. Besides analyzing whole wafers, CMDP measurements are performed on oxide test-structures on a patterned wafer. Finally, the oxide properties are characterized by means of charge-PCD as well as capacitance-voltage measurements. With CMDP, average bulk lifetimes up to 33.1 ms are measured, whereby significant variations are observed among wafers, which are produced out of the same ingot but oxidized in different furnaces. The observed lifetime variations are assumed to be caused by contaminations, which are introduced during the oxidation process. The results obtained by CMDP were neither accessible by means of conventional MDP measurements of uncharged wafers nor with the established charge-PCD method.

Understanding the light‐induced degradation at elevated temperatures: Similarities between multicrystalline and floatzone p‐type silicon

AbstractThis paper discusses degradation phenomena in crystalline silicon. We present new investigations of the light‐ and elevated temperature‐induced degradation of multicrystalline silicon. The investigations provide insights into the defect parameters as well as the diffusivity and solubility of impurity species contributing to the defect. We discuss possible defect precursor species and can rule out several metallic impurities. We find that an involvement of hydrogen in the defect could explain the characteristic observations for light‐ and elevated temperature‐induced degradation. Furthermore, we demonstrate analogies to the light‐induced degradation mechanisms at elevated temperatures observed in floatzone silicon, where several experimental results also indicate an involvement of hydrogen in the defect. Based on the similarities between multicrystalline and floatzone silicon, we suggest that both degradation phenomena might be caused by the same or similar defects. As we do not expect large concentrations of metals in floatzone silicon, we suggest that complexes of hydrogen and a species introduced during crystal growth might cause both degradation phenomena.

Production and aging of paramagnetic point defects in P-doped floating zone silicon irradiated with high fluence 27 MeV electrons

Enhancing the long term stable performance of silicon detectors used for monitoring the position and flux of the particle beams in high energy physics experiments requires a better knowledge of the nature, stability, and transformation properties of the radiation defects created over the operation time. We report the results of an electron spin resonance investigation in the nature, transformation, and long term stability of the irradiation paramagnetic point defects (IPPDs) produced by high fluence (2 × 1016 cm−2), high energy (27 MeV) electrons in n-type, P-doped standard floating zone silicon. We found out that both freshly irradiated and aged (i.e., stored after irradiation for 3.5 years at 250 K) samples mainly contain negatively charged tetravacancy and pentavacancy defects in the first case and tetravacancy defects in the second one. The fact that such small cluster vacancy defects have not been observed by irradiation with low energy (below 5 MeV) electrons, but were abundantly produced by irradiation with neutrons, strongly suggests the presence of the same mechanism of direct formation of small vacancy clusters by irradiation with neutrons and high energy, high fluence electrons, in agreement with theoretical predictions. Differences in the nature and annealing properties of the IPPDs observed between the 27 MeV electrons freshly irradiated, and irradiated and aged samples were attributed to the presence of a high concentration of divacancies in the freshly irradiated samples, defects which transform during storage at 250 K through diffusion and recombination processes.

First results on DEPFET Active Pixel Sensors fabricated in a CMOS foundry—a promising approach for new detector development and scientific instrumentation

DEPFET Active Pixel Sensors (APS) have been introduced as focal plane detectors for X-ray astronomy already in 1996. Fabricated on high resistivity, fully depleted silicon and back-illuminated they can provide high quantum efficiency and low noise operation even at very high read rates. In 2009 a new type of DEPFET APS, the DSSC (DEPFET Sensor with Signal Compression) was developed, which is dedicated to high-speed X-ray imaging at the European X-ray free electron laser facility (EuXFEL) in Hamburg. In order to resolve the enormous contrasts occurring in Free Electron Laser (FEL) experiments, this new DSSC-DEPFET sensor has the capability of nonlinear amplification, that is, high gain for low intensities in order to obtain single-photon detection capability, and reduced gain for high intensities to achieve high dynamic range for several thousand photons per pixel and frame. We call this property “signal compression”.Starting in 2015, we have been fabricating DEPFET sensors in an industrial scale CMOS foundry maintaining the outstanding proven DEPFET properties and adding new capabilities due to the industrial-scale CMOS process. We will highlight these additional features and describe the progress achieved so far. In a first attempt on double-sided polished 725 μm thick 200 mm high resistivity float zone silicon wafers all relevant device related properties have been measured, such as leakage current, depletion voltage, transistor characteristics, noise and energy resolution for X-rays and the nonlinear response. The smaller feature size provided by the new technology allows for an advanced design and significant improvements in device performance. A brief summary of the present status will be given as well as an outlook on next steps and future perspectives.

Superacid-Treated Silicon Surfaces: Extending the Limit of Carrier Lifetime for Photovoltaic Applications

Minimizing carrier recombination at interfaces is of extreme importance in the development of high-efficiency photovoltaic devices and for bulk material characterization. Here, we investigate a temporary room temperature superacid-based passivation scheme, which provides surface recombination velocities below 1 cm/s, thus placing our passivation scheme amongst state-of-the-art dielectric films. Application of the technique to high-quality float-zone silicon allows the currently accepted intrinsic carrier lifetime limit to be reached and calls its current parameterization into doubt for 1 Ω·cm n-type wafers. The passivation also enables lifetimes up to 65 ms to be measured in high-resistivity Czochralski silicon, which, to our knowledge, is the highest ever measured in Czochralski-grown material. The passivation strategies developed in this work will help diagnose bulk lifetime degradation under solar cell processing conditions and also help quantify the electronic quality of new passivation schemes.

Minimising bulk lifetime degradation during the processing of interdigitated back contact silicon solar cells

AbstractIn this work, we develop a fabrication process for an interdigitated back contact solar cell using BBr3 diffusion to form the p+ region and POCl3 diffusion to form the n+ regions. We use the industry standard technology computer‐aided design modelling package, Synopsys Sentaurus, to optimize the geometry of the device using doping profiles derived from electrochemical capacitance voltage measurements. Cells are fabricated using n‐type float‐zone silicon substrates with an emitter fraction of 60%, with localized back surface field and contact holes. Key factors affecting cell performance are identified including the impact of e‐beam evaporation, dry etch damage, and bulk defects in the float zone silicon substrate. It is shown that a preoxidation treatment of the wafer can lead to a 2 ms improvement in bulk minority carrier lifetime at the cell level, resulting in a 4% absolute efficiency boost.

Bulk and surface instabilities in boron doped float-zone samples during light induced degradation treatments

Float-zone silicon is often used as a supposedly stable high lifetime reference material. Here it is shown, however, that boron doped float-zone samples that underwent a fast firing step may suffer from a severe degradation in bulk lifetime during illumination at elevated temperatures. Furthermore, it is observed that silicon nitride related passivation may be affected by a long-term decrease in chemical passivation quality. A time and injection resolved visualization is introduced to quickly distinguish between these degradation features. Both bulk lifetime and chemical passivation quality are shown to recover at the same treatment conditions after longer treatment times.

Stability of effective lifetime of float-zone silicon wafers with AlOx surface passivation schemes under illumination at elevated temperature

For solar cell application, the stability of interface passivation quality to in-field conditions is crucial. We have performed an experiment to test the resilience of different aluminium oxide based passivation schemes to illumination at 75 °C. Different thermal treatments to activate the passivation and/or simulate contact firing were performed before light soaking. The experiment was performed on 1 Ωcm float-zone silicon of both p- and n-type doping. The study demonstrates that good passivation quality can be achieved both by atomic layer deposition and by PECVD and that addition of silicon nitride capping layers greatly enhances thermal stability. On p-type wafers a severe but temporary degradation of the electrical quality of the wafer bulk was observed during the first hours upon application of such capping layers. Besides this effect, reasonable temporal stability of the effective lifetime was observed for p-type samples while n-type samples featured excellent long-term stability.

Fabrication and Modeling of High-Efficiency Front Junction N-Type Silicon Solar Cells With Tunnel Oxide Passivating Back Contact

This paper reports on in-depth understanding, modeling, and fabrication of 23.8% efficient 4 cm2 n-type Float Zone (FZ) silicon cells with a selective boron emitter and photolithography contact on front and tunnel oxide passivating contact on the back. Tunnel oxide passivating contact composed of a very thin chemically grown silicon oxide (∼15 A) capped with plasma-enhanced chemical vapor deposition (PECVD) grown 20 nm n+ poly Si gave excellent surface passivation and carrier selectivity with very low saturation current density (∼5 fA/cm2). A high-quality boron selective emitter was formed using ion implantation and solid source diffusion to minimize metal recombination and emitter saturation current density. Process optimization resulted in a cell $V_{{\rm{oc}}}$ of 712 mV, $J_{{\rm{sc}}}$ of 41.2 mA/cm2, and FF of 0.811. A simple methodology is used to model these cells which replaces tunnel oxide passivating contact region by electron and hole recombination velocities extracted from measured saturation current density of tunnel oxide passivating contact region and analysis. Using this approach and two-dimensional device modeling gave an excellent match between the measured and simulated cell parameters and efficiency, supporting excellent passivation and carrier selectivity of these contacts. Extended simulations showed that 26% cell efficiency can be achieved with this cell structure by further optimization of wafer quality, emitter profile, and contact design.

Temporal stability of a-Si:H and a-SiNx:H on crystalline silicon wafers

The temporal stability of single layer thin films of hydrogenated amorphous silicon (a-Si:H) and silicon nitride (a-SiNx:H) passivated crystalline silicon wafers have been investigated over 18 months. The thin films were deposited at low temperature with plasma-enhanced chemical vapor deposition (PECVD) onto different substrates, including float zone (FZ) p-type and Czochralski (CZ) n-type silicon. For a-SiNx:H, we investigate the temporal stability dependence on the flow rate of silane (SiH4) used during deposition. This was varied from 13 sccm to 50 sccm. The thickness of the a-Si:H and a-SiNx:H thin films was characterized by spectroscopic ellipsometry (SE), whereas the minority carrier effective lifetime (τeff) and the uniformity of the wafer were measured through carrier density imaging (CDI). We found that for both p-type FZ and n-type CZ silicon substrates, the a-Si:H passivation performance degrades after 150 h and reached a minimum value around 350 h, whereafter the lifetime recovered to a level of 1.1 ms (-16% compare to the initial state) and 1.6 ms (-4%), respectively. Similar trends were also seen on a-SiNx:H passivated samples, but the lowest value was reached after around 550 h. For both p- and n-type substrates passivated by a-SiNx:H passivation, as the flow rate of SiH4 increased, the temporal stability of passivated samples enhanced.

Long-Term Stability of Aluminum Oxide Based Surface Passivation Schemes Under Illumination at Elevated Temperatures

The stability of passivation layers under the conditions of field application of solar modules is a crucial parameter. We have performed an experiment to test the stability of aluminum oxide based passivation schemes under halogen lamp illumination of 1 sun equivalent intensity at 75 °C. We compare aluminum oxide layers with atomic layer deposition and plasma-enhanced chemical vapor deposition with and without an amorphous silicon nitride capping layer. Different thermal treatments are performed to activate the passivation or simulate solar cell contact firing. All passivation schemes are tested on full four inch 1 Ω·cm p- and n-type float-zone silicon wafers. The quality and stability of the surface passivation are tested by means of repeated charge carrier lifetime measurements. No significant surface passivation degradation due to light-soaking is evident on capped samples for several hundred hours. N-type samples are demonstrated to maintain excellent passivation quality for at least 3700 h and only slight degradation of p-type samples is found.

Effective passivation of crystalline silicon surfaces by ultrathin atomic-layer-deposited TiOx layers

We characterize the surface passivation properties of ultrathin titanium oxide (TiOx) films deposited by atomic layer deposition (ALD) on crystalline silicon by means of carrier lifetime measurements. We compare different silicon surface treatments prior to TiOx deposition, such as native silicon oxide (SiOy), chemically grown SiOy and thermally grown SiOy. The best passivation quality is achieved with a native SiOy grown over 4 months and a TiOx layer thickness of 5 nm, resulting in an effective lifetime of 1.2 ms on 1.3 Ωcm p-type float-zone silicon. The measured maximum lifetime corresponds to an implied open-circuit voltage (iVoc) of 710 mV. For thinner TiOx layers the passivation quality is reduced, however, samples passivated with only 2 nm of TiOx still show a lifetime of 612 μs and an iVoc of 694 mV. The contact resistivity of the TiOx including the SiOy interlayer between the silicon wafer and the TiOx is below 0.8 Ωcm2. The combination of excellent surface passivation and low contact resistivity has the potential for silicon solar cells with efficiencies exceeding 26%.