Johannes Will

Nanoscale Structure of Si/SiO2/Organics Interfaces

X-ray reflectivity measurements of increasingly more complex interfaces involving silicon (001) substrates reveal the existence of a thin low-density layer intruding between the single-crystalline silicon and the amorphous native SiO2 terminating it. The importance of accounting for this layer in modeling silicon/liquid interfaces and silicon-supported monolayers is demonstrated by comparing fits of the measured reflectivity curves by models including and excluding this layer. The inclusion of this layer, with 6-8 missing electrons per silicon unit cell area, consistent with one missing oxygen atom whose bonds remain hydrogen passivated, is found to be particularly important for an accurate and high-resolution determination of the surface normal density profile from reflectivities spanning extended momentum transfer ranges, now measurable at modern third-generation synchrotron sources.

Diffusion-driven precipitate growth and ripening of oxygen precipitates in boron doped silicon by dynamical x-ray diffraction

X-ray Pendellosung fringes from three silicon single crystals measured at 900 °C are analyzed with respect to density and size of oxygen precipitates within a diffusion-driven growth model and compared with TEM investigations. It appears that boron doped (p+) material shows a higher precipitate density and a higher strain than moderately (p-) boron crystals. In-situ diffraction reveals a diffusion-driven precipitate growth followed by a second growth regime in both materials. An interpretation of the second growth regime in terms of Ostwald ripening yields surface energy values (around 70 erg/cm2) similar to published data. Further, an increased nucleation rate by a factor of ∼13 is found in the p+ sample as compared to a p- sample at a nucleation temperature of 450 °C.

Oxygen diffusivity in silicon derived from dynamical X-ray diffraction

Thickness dependent Pendellosung oscillations are highly sensitive to strain fields from defects in a host crystal. Based on this, we present a novel technique to measure the precipitation kinetics of oxygen in silicon already at its early stage of clustering at high temperatures. At 900 °C, precipitates with a radius smaller than 4 nm and with a density of 1 ± 0.5 × 1013 1/cm3 were observed. The technique was calibrated by complementary scanning transmission electron microscope and energy dispersive X-ray measurements in the range of normal diffusivity yielding a diffusion constant of 1.7 ± 0.1×10−12cm2/s, which is close to the literature value of 2.074×10−12cm2/s. The measurements have been made with the characteristic Kα1-line of a high voltage tungsten X-ray tube at 59.31 keV, which provides the opportunity to illuminate through complex sample environments like high temperature scattering furnaces.

Thickness dependence of the integrated Bragg intensity for statistically disturbed silicon crystals

The thickness dependence of the integrated Bragg intensities for Czochralski-grown silicon was measured with the characteristic tungsten Kα1-line at 59.3 keV. In contrast to previous experiments the sample is wedge shaped, which allows to take data over a wide range of Pendellosung fringes in one exposure only and without any mechanical movement of the sample. The period length, the oscillation amplitude, and the mean value of the Bragg intensity can be explored to identify the presence of point defects, and the temperature dependence of the period length allows to quantify the thermal Debye-coefficient with high precision.

Evidence of Tailoring the Interfacial Chemical Composition in Normal Structure Hybrid Organohalide Perovskites by a Self-Assembled Monolayer

Current-voltage hysteresis is a major issue for normal architecture organo-halide perovskite solar cells. In this manuscript we reveal a several-angstrom thick methylammonium iodide-rich interface between the perovskite and the metal oxide. Surface functionalization via self-assembled monolayers allowed us to control the composition of the interface monolayer from Pb poor to Pb rich, which, in parallel, suppresses hysteresis in perovskite solar cells. The bulk of the perovskite films is not affected by the interface engineering and remains highly crystalline in the surface-normal direction over the whole film thickness. The subnanometer structural modifications of the buried interface were revealed by X-ray reflectivity, which is most sensitive to monitor changes in the mass density of only several-angstrom thin interfacial layers as a function of substrate functionalization. From Kelvin probe force microscopy study on a solar cell cross section, we further demonstrate local variations of the potential on different electron-transporting layers within a solar cell. On the basis of these findings, we present a unifying model explaining hysteresis in perovskite solar cells, giving an insight into one crucial aspect of hysteresis for the first time and paving way for new strategies in the field of perovskite-based opto-electronic devices.

Misfit strain of oxygen precipitates in Czochralski silicon studied with energy-dispersive X-ray diffraction

Annealed Czochralski Silicon wafers containing SiOx precipitates have been studied by high energy X-ray diffraction in a defocused Laue setup using a laboratory tungsten tube. The energy dispersive evaluation of the diffracted Bragg intensity of the 220 reflection within the framework of the statistical dynamical theory yields the static Debye-Waller factor E of the crystal, which gives access to the strain induced by the SiOx precipitates. The results are correlated with precipitate densities and sizes determined from transmission electron microscopy measurements of equivalent wafers. This allows for the determination of the constrained linear misfit e between precipitate and crystal lattice. For samples with octahedral precipitates the values ranging from e = 0.39 (+0.28/−0.12) to e = 0.48 (+0.34/−0.16) indicate that self-interstitials emitted into the matrix during precipitate growth contribute to the lattice strain. In this case, the expected value calculated from literature values is e = 0.26 ± 0.05....

Growth and nucleation regimes in boron doped silicon by dynamical x-ray diffraction

The oxygen precipitation of highly (17.5 mΩ cm) and moderately (4.5 Ω cm) boron (B) doped silicon (Si) crystals at 780 °C is investigated by following in-situ the evolution of diffraction Pendellosung oscillations. All samples show an initial diffusion-driven growth process which may change over into Ostwald ripening. For the highly doped sample and involving a nucleation step at 450 °C for 30 h, the precipitate density ρ is enhanced by a factor of 8 as compared to the moderately doped sample. The influence of a high B concentration on ρ is dramatically higher for the samples directly heated to 780 °C, where an enhancement factor of 80 is found. Considering Ostwald ripening as a second growth regime reveals consistent ripening rates and surface energies σ with those found at 900 °C in a previous publication.

In Situ Observation of the Oxygen Nucleation in Silicon with X-Ray Single Crystal Diffraction

The measurement of Pendellösungs oscillations was used to observe the time dependent nucleation of oxygen in a Czochralski grown single crystal at 750°C. It is shown, that the theoretical approach of the statistical dynamical theory describes the data well. Within the framework of this theory it is possible to determine the static Debye-Waller-factor as a function of the annealing time by evaluating the mean value of the Bragg intensity and the period length. The temperature influence on the Pendellösungs distance was corrected for by measurement of a Float-zone sample at the same temperature.

Structural Defect Studies of Semiconductor Crystals with Laue Topography

A defocused Laue diffractometer setup operating with the white beam of a high energy X-ray tube has been used for a topographic visualization of structural defects in semiconductor wafers. The laboratory white beam X-ray topograph of a Czochralski Si wafer with oxygen precipitates grown in an annealing process is compared to a μPCD image. Further, the dislocation network in a VGF GaAs wafer is studied under thermal annealing up to 1140°C and the in-situ capability of the setup is demonstrated.

Sample thickness effect of thermal vibration correction within X-ray dynamical theory for germanium-doped silicon

As of today, highly germanium doped Czochralski silicon crystals are used in applications. However, it is not clear how a germanium content in the range of 1018 atoms/cm3 influences the oxygen precipitation behavior, which is highly relevant for the gettering potential of the wafer. In this context, high energy X-ray diffraction is a promising tool to monitor real-time the strain introduced by the oxygen agglomeration and growth. Nevertheless, in particular, in the dynamical limit of X-ray diffraction and at elevated temperatures, the strain originating from the precipitation process has to be clearly distinguished from the intensity contribution of thermal vibrations. In Laue geometry, dynamical effects can even lead to an increment of the integrated intensity with temperature completely unexpected in the kinematical limit, where temperature is tackled solely by a Debye-Waller factor. In the following, an approach is presented allowing us to completely correct the influence of thermal vibrations in the d...