Microelectronics Reliability Research Articles

Dependence of the Multi-Component Nature of Bias Temperature Instability in MOSFETs on Oxide and Device Type

Advanced metal-oxide-semiconductor field effect transistors, MOSFETs, have shown increasing sensitivity to microelectronic reliability based degradation phenomena and in particular, to negative bias temperature instability, NBTI. Previously [1] we have reported on a methodology to extract three distinct components of NBTI; recoverable charge, RC (oxide traps which discharge once the gate bias is zero), field recoverable charge, FRC (switching traps which seemingly discharged under positive gate bias), and interface state charge, IS (associated with the breaking of silicon-hydrogen bonds at the interface and do not discharge in an experimental time frame for temperatures below 180° C). Here we will report new results for NBTI for different oxide types and thicknesses and we will expand the methodology to include positive bias temperature instability, PBTI, oxide charging caused by the application of large positive biases. Both NBTI and PBTI will be examined for both p-channel and n-channel MOSFETS for each oxide type and thickness, which requires the measurement to be made in both accumulation and inversion modes.NBTI “Pseudo DC” measurements using the methodology discussed previously [1] have been made at 120° C on p-channel and n-channel MOSFETs to extract the three components of BTI after 1500 s of stress. The stressing bias was chosen so that |Vgs,stress|/tox = 3.25 V/3.4nm in order to keep the approximately the same fields. Measurements of the source – drain current, Ids, were made in the linear regime and the measured Ids variations with stress were converted into threshold voltage shifts, DVth [1]. Measurements were performed on devices fabricated using an IBM proprietary process with gate widths of 5 mm and gate length/oxide thicknesses of 130 nm/3.4nm, 240 nm/6.2 nm, 90 nm/2.4 nm, and 240 nm/6.2 nm (processed with 90 nm technology) with a oxynitride gate. Measurements were also performed on HP devices with gate widths of 10 mm, gate lengths ranging from 350-500 nm and a Si02 oxide thickness of 7 nm.It is worth noting that the sign of the trapped charges of each type depends upon the component being measured. In the case of IS, the sign of the charge can be inferred from the mechanism since dangling bonds are amphoteric. They will take on a charge based on the measurement Vgs, and thus for PMOS devices, the IS have positive trapped charge (negative voltage shift) whilst for NMOS the IS are negatively charged (positive voltage shift). The FRC charge component is always charged by holes and the RC charge is positive (negative voltage shift) except for PBTI in an NMOS. A sample table for the 130nm/3.4nm oxynitrided gate is shown below.The existence of positive charge injection, for a PMOS under PBTI can be explained by realizing that PMOS devices usually have a p-type polysilicon gate electrode. When a positive gate bias is applied, electrons will be drawn to the interface between the gate oxide and the substrate; thus there are no holes present to tunnel into the oxide; however, the same field will drive holes from the poly silicon/oxide interface and this is where the positive charge is coming from under these circumstances.A more puzzling result is that an NMOS under PBTI shows IS creation. Standard models of IS creation involve positive charge which either directly or through a complex process breaks the Si-H bond. These holes can come from the substrate for NBTI, or the polysilicon gate for a PMOS in accumulation, but the mechanism of hole injection for an NMOS undergoing PBTI is unclear.[1] C. Mayberry, D. D. Nguyen, C. Kouhestani, K. E. Kambour, H. P. Hjalmarson and R. A. B. Devine, “Measurement and Identification of Three Contributing Charge Terms in Negative Bias Temperature Instability,” ECS Trans., 50 (4), 223-232 (2012). Acknowledgements D. D. Nguyen and C. Kouhestani are with COSMIAC Kirtland, AFB, New Mexico USA 87117. This material is based on research sponsored by Air Force Research Laboratory (AFRL) under agreement number FA9453-08-2-0259. The U.S. Government is authorized to reproduce and distribute reprints for Governmental purposes notwithstanding any copyright notation thereon. The work performed by K. E. K. was supported by the US Air Force under contract FA9453-08-C-0245 sponsored, monitored, and managed by: United States Air Force Air Force Material Command, Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, NM 87117-5776. Table 1 A matrix showing the threshold voltage shift for the various BTI components and type of charge trapped by each component.

Charge Trapping Characterization of LaLuO3/p-Si Interfaces at Cryogenic Temperatures

Ternary rare-earth oxide LaLuO3 shows clear experimental evidence of being one of the most perspective gate dielectrics for application in upcoming MOSFET technology [1]. On the one hand, these oxides are thermally stable in the amorphous phase and possess high permittivity, and, on the other hand, complex composition of the oxide leads to more heterogeneity and defectiveness of the dielectric – semiconductor transition layer (TL). Therefore the study of electronic processes in the transition layers LaLuO3/Si is one of the major challenges associated with further implementation of the LaLuO3in CMOS technology. In this article we present an experimental investigation of charge trapping and emission from shallow traps in the TL of the LaLuO3 /p-Si structures in the temperature range 6– 40 K, which allows us to estimate quality of the gate dielectric TL. The experimental approach adopted in this work is based on the techniques of thermally stimulated charge release (TSCR), isothermal transient emission currents (ITC), dynamic I(V) characteristics and extends on our previous reports of applying the technique to study charge trapping in TL of LaSiOx /Si, GdSiOx /Si [2], HfO2/Si [3] and SiO2/Si structures [4]. The dielectric layers in the Pt/LaLuO3/p-Si(100) MOS structures were deposited by molecular beam deposition. Evaporation of La and Lu in O2 was performed at a substrate temperature of 450°C. Nominal physical thicknesses of LaLuO3 were 6.5 nm and 20 nm. The Pt gates (area - 1×10-4 cm2 ) were prepared by e-gun evaporation through a shadow mask. The MOS stacks were annealed in forming gas at 400°C for 10 minutes (10% H2). The TSCR spectra for the Pt/LaLuO3 /p-Si structure for different charging temperatures are presented in Fig. 1. Regimes of trap’s charging are depicted on the field of Fig.1. Some peculiarities of thermally stimulated currents need to be point out. At first, the TSC peak shifts towards lower temperatures, when charging temperature decreases. At second, amplitude of the TSC peak grows steadily when accumulation charging voltage (Vch) increases (not shown here). The activation energy of the TSC process was found using the initial rise method. Activation energies for hole traps have been as much as 24.3–27.9 meV, 30.3–30.6 meV and 36–39 meV (LaLuO3 thickness - 6.5nm) and 12.3-12.4 meV, 21.1-22meV, 23.4-24.4 meV (LaLuO3 thickness - 20nm). The total concentration of hole shallow traps is as large as 6.2×1010cm-2 for LaLuO3 thickness 6.5nm and 4.1×1010cm-2 for thickness 20nm. The strong current relaxation has been found to occur after Vthswitching-off (see Fig.2). Approximating relaxation time by exponential decay function from 1/τ~ f(1/kT) dependence activation energy of relaxation processes (8.8 meV) have been determined. Formation of TSCR spectra in the LaLuO3/p-Si structures is supposed to result from the recharging of traps, localized in the transition layer. The process of recharging of the traps may be due to the tunnel – activation mechanism assisted by phonons localized on the defects in transition layer. This work was partially supported by NAS of Ukraine (the project No. 53-32-10). The authors from Tyndall National Institute acknowledge the financial support of Science Foundation Ireland through the project 09/IN.1/I2633.1. E. Durğun Őzben, J.M.J. Lopes, A. Nichau, M. Schnee, S. Lenk, A. Besmehn, K.K. Bourdelle, Q.T. Zhao, J. Schubert and S. Mantl, IEEE Electron. Dev. Lett., 32 15 (2011).2 I.P. Tyagulskii, S.I. Tyagulskii, A.N. Nazarov, V.S. Lysenko, K. Cherkaoui, P.K. Hurley, Microelectronic Engineering, 109 31 (2013).3. I.P. Tyagulskyy, I.N. Osiyuk, V.S. Lysenko, A.N. Nazarov, S. Halb, O. Buiu, Y. Lu, R. Potter, P. Chalker Microelectronics Reliability, 47 726 (2007).4. V.S. Lysenko, T.N. Sytenko, V.I. Zimenko, I.P. Tyagulskyy, O.V. Snitko, I.N. Osiyuk, A.N. Nazarov, T.E. Rudenko, Solid State Commun., 57 171 (1986).

Using Statistics of Extremes for Electromigration and Time-Dependent Dielectric Breakdown

This paper deals with the extreme values statistics use for metal interconnect and dielectric reliability in microelectronics. For electromigration reliability on Cu lines, experimental failure times are obtained by using an especially designed test structure (multilink) allowing determination of successive lower failure times on a large set of samples. It is shown that the experimental statistical distributions of minima failure times using our multilink structures are deductible from the usual single Cu lines lognormal distribution with the help of extreme values and order statistics. The analytical transformations from single interconnect lognormal distribution to the successive first, second, and third minima failure time distributions are derived with the help of scaling parameters. In particular, the first failure time's distribution is a Weibull distribution whose parameters are a simple expression of the total number of links and the parent lognormal distribution parameters. Since time-dependent dielectric breakdown follows also Weibull statistics, the origin of parent distribution and its analytical possible form are similarly discussed in the framework of extreme values statistics. The statistics of successive breakdown are also derived from order statistics.

Thermo-Mechanical Reliability Evaluation of PLCC Packaging

Thermo-mechanical failure is the main factor to impact the microelectronic packaging reliability. Under thermal loads, the microelectronic packaging is easy to produce cracks, delamination, voids, and other defects, which can emerge and grow under thermo-mechanical stresse caused by the different coefficients of thermal expansion (CTE). Firstly, a geometric model of Plastic Leaded Chip Carrier (PLCC) packaging was established and the thermo-mechanical property of PLCC packaging was analyzed using finite element analysis (FEA) software ANSYS. Then, the thermal cycling test on a set of PLCC packaging was conducted according to the MIL-STD-883H Microcircuits Test Method Standard with temperature range from-65°C to 150°C, and the crack growth rate of PLCC packaging was studied experimentally using Scanning Acoustic Microscopy (SAM). Finally, the Anand model was adopted to predict thermal fatigue life, which was consistent with the experimental results. With these researches, the thermo-mechanical reliability evaluation of the PLCC packaging was investigated using finite element analysis (FEA) combined with analytical methods.

Introduction to the Special Issue on the 50th International Reliability Physics Symposium

On April 15-19, 2012, the 50th Annual IEEE International Reliability Physics Symposium was held in Garden Grove, CA, USA, commemorating a significant milestone for IRPS as the preeminent conference in the area of microelectronics reliability. The technical program included 29 invited talks, in addition to 75 contributed talks and 70 posters, and was witnessed by 408 attendees. Unique to this conference, all prior 49 years of symposium materials were shared with the attendees in a newly digitized format. The papers at The Symposium showcased a range topics, covering fundamental reliability of transistors, interconnects, back-end dielectrics, and packaging. State-of-the-art developments in reliability of memory devices, circuits (including but not limited to BTI, ESD, and latchup and soft errors), product qualification, failure analysis, process and integration impact on reliability, compound semiconductors, high voltage, and thin-film devices used in commercial, industrial, and harsh or unusual environmental conditions were shown. Applications of reliability assessment pertinent to those found in space, automobiles, renewable energy sources, and medical applications were also highlighted. While it is difficult to properly sample such a wide variety of technical contents, this Special Issue features four extended papers based on the original Symposium submission. In each case, the impact of intrinsic reliability failure mechanism(s) on device or circuit reliability is described, topics that should be of ongoing and lasting interest to the reliability community. An overview of the technical articles is given.

Dependence of the hardness of AlxGa1−xAs on composition and effect of oxidation

The mechanical properties of semiconductor materials determine the reliability of microelectronics. The hardness of Al1−xGaxAs is investigated together with oxidation and its effect on this parameter. A structure consisting of three AlxGa1−xAs layers of different composition separated by In0.01Ga0.99As etch stops was deposited via metal-organic vapor phase epitaxy. High resolution x-ray diffraction determined the composition of the baseline layers to be Al0.9Ga0.1As, Al0.8Ga0.2As and Al0.7Ga0.3As. Nanoindentation measurements demonstrated that hardness decreases with aluminum content following a linear correlation. To study the effect of oxidation on hardness, two samples of Al0.8Ga0.2As were oxidized in air at 475°C for 2 and 4h. The surface morphology of the oxide imaged using atomic force microscopy was granular. X-ray diffraction simulated curves estimated the Al0.8Ga0.2As thickness decrease due to oxidation. The growth of the oxide layer was linear with time indicating that the process is reaction-rate limited and the layer is porous. The hardness of the (Al0.8Ga0.2)2O3 oxide was extrapolated to be more than twice the value of the baseline sample.

Introducing a scale structure to correlate quality and reliability

The most important reliability in microelectronics is the reliability that the end customer experiences. In order to improve or build-in reliability, measurements are needed as early in semiconductor processing as possible. Often, quality and capability of a semiconductor wafer are the earliest available measurements. This work describes a test structure that converts physical attributes into parametric variables. This double conversion can further be correlated from quality to reliability by conventional or wafer level aging. The result is an early and efficient method of assessing reliability.

Material property effects on solder failure analyses

The effects of material properties modeling on the solder failure analyses by numerical simulations are studied. The packaging structure of plastic ball grid array on printed circuit board was modeled. Two different types of molding compounds and two different types of substrates were employed and combined for the plastic ball grid array package modeling. The material properties were assumed as temperature dependent elastic and viscoelastic, and finite element method was used to calculate and analyze the strain energy densities of the solder balls. The chip warpage was also studied, and related with the solder ball reliability analyses by discussing the viscoelastic characteristics of the materials and their influences on the deformations. The results showed that the warpage developments of the packaging structure showed very different behaviors, and the mechanism of the strain energy density accumulations in the solder balls were also different depending on the material properties modeling and their combinations. This study demonstrates that appropriate modeling of the material properties is critical for the interpretation and understanding the microelectronics reliability mechanisms.

Performance, reliability, radiation effects, and aging issues in microelectronics – From atomic-scale physics to engineering-level modeling

The development of engineering-level models requires adoption of physical mechanisms that underlie observed phenomena. This paper reviews several cases where parameter-free, atomic-scale, quantum mechanical calculations led to the identification of specific physical mechanisms for phenomena relating to performance, reliability, radiation effects, and aging issues in microelectronics. More specifically, we review recent calculations of electron mobilities that are based on atomic-scale models of the Si–SiO 2 interface and elucidate the origin of strain-induced mobility enhancement. We then review extensive work that highlights the role of hydrogen as the primary agent of reliability phenomena such as negative bias temperature instability (NBTI) and radiation effects, such as enhanced low-dose radiation sensitivity (ELDRS) and dopant deactivation. Finally, we review atomic-scale simulations of recoils induced by energetic ions in Si and SiO 2. The latter provide a natural explanation for single-event gate rupture (SEGR) in terms of defects with energy levels in the SiO 2 band gap.

Microelectronic packaging reliability using the RSM technique

Purpose The purpose of this paper is to identify the critical parameters that influence ball grid array and chip size package fatigue life in a random vibration environment by using a design of experimental (DOE) approach using simulation results. Design/methodology/approach The use of DOE and analysis of variation to identify the critical parameters and a response surface to generate a functional form for global modeling would be determined. Once the global modeling’s functional form was known, it can be used as boundary condition, which would be input to a local model. Knowing the critical stress, one would estimate the fatigue life from a damage model. It is the curvature of the printed wiring board in the region of the component of interest that is driving the component’s solder joint damage. The approach in this present work involves global-local modeling approaches. In the global model approach, the vibration response of the printed circuit board (PCB) will be determined. Findings This global model will give the response of the PCB at specific component locations of interest. This response is then fed into a local stress analysis for accurate assessment of the critical stresses in the solder joints of interest. The stresses are then fed into a fatigue damage model to predict the life. Originality/value The analysis proposed in this paper uses a failure type approach to damage analysis and involves global and local model approaches.

Microstructure evolution of Al-1% Si bonding wire for microelectronic reliability

In order to determine the reliability of Al-1% Si bonding wires, the microstructure of an annealed wire, including grain morphology and secondary phases, was investigated by conventional transmission electron microscopy (TEM) and high-resolution electron microscopy (HREM). The grains are extremely long and thin parallel to the drawn direction, and the average grain size is about 600 nm to 700 nm. Nano-sized thin plate-like Si crystals of about 10 nm length and a few monolayers thickness were observed, and their crystallography and morphology are discussed in this paper.

Performance, Reliability, Radiation Effects, and Aging Issues in Microelectronics - From Atomic-Scale Physics to Engineering-Level Modeling

The development of engineering-level models requires adoption of physical mechanisms that underlie observed phenomena. This paper reviews several cases where parameter-free, atomic-scale, quantum mechanical calculations led to the identification of specific physical mechanisms for phenomena relating to performance, reliability, radiation effects, and aging issues in microelectronics. More specifically, we review recent calculations of electron mobilities that are based on atomic-scale models of the Si-SiO2 interface and elucidate the origin of strain-induced mobility enhancement. We then review extensive work that highlights the role of hydrogen as the primary agent of reliability phenomena such as Negative Bias Temperature Instability (NBTI) and radiation effects, such as Enhanced Low Dose Radiation Sensitivity (ELDRS) and dopant deactivation. Finally, we review atomic-scale simulations of recoils induced by energetic ions in Si and SiO2. The latter provide a natural explanation for single-event gate rupture (SEGR) in terms of defects with energy levels in the SiO2 band gap.

Performance, Reliability, Radiation Effects, and Aging Issues in Microelectronics - From Atomic-scale Physics to Engineering-level Modeling

not Available.

Correlating Drop Impact Simulations With Drop Impact Testing Using High-Speed Camera Measurements

The increased use of mobile appliances such as mobile phones and navigation systems in today’s society has resulted in an increase in reliability issues related to drop performance. Mobile appliances are dropped several times during their lifespan and the product is required to survive common drop accidents. A widely accepted method to assess the drop reliability of microelectronics on board-level is the drop impact test. This test has been standardized by international councils such as Joint Electron Device Engineering Council and is widely adopted throughout the industry. In this research the solder loading is investigated by combining high-speed camera measurements of several drop impact tests with verified finite element models. These simulation models are developed in order to gain an insight on the loading pattern of solder joints based on interconnect layout, drop conditions, and product specifications prior to physical prototyping. Deflections and frequencies during drop testing are measured using a high-speed camera setup. The high-speed camera experiments are performed on two levels: machine level (rebounds with and without a catcher) and product level (with different levels of energy and different pulse times). Parametric (dynamic and quasistatic) 3D models are developed to predict the drop impact performance. The experimental results are used to verify and enhance the simulation models, e.g., by tuning the damping parameters. As a result, the verified models can be used to determine the location of the critical solder joint and to obtain estimates of the solder lifetime performance.

Investigating direction characteristics of the heat transfer coefficient in forced convection reflow oven

In this paper, we investigate the heating capability of forced convection reflow ovens and the effect of the ovens’ construction on it. This parameter depends on the heat transfer coefficient ( α) which is mainly determined by the gas flow parameters. First of all we studied the gas flow circumstances in the reflow oven using a stationary and isothermal gas flow model. The conclusions of the model are then proved by experimental results as well. Our experiments were based on measuring the temperature changes on different points which are located around the centre of the ovens’ processing area. From these data, direction characteristics of α were calculated using the heat equation of the investigated reflow oven. Our results are important for effective thermal modelling of the reflow soldering process [B. Illés, G. Harsányi, 3D thermal model to investigate component displacement phenomenon during reflow soldering, Microelectronics Reliability 48 (2008) 1062–1068] and are useful to calibrate reflow ovens. In this project we examined the latest reflow ovens constructed with nozzle-matrix blower system.

The Effects of Hardness Variation on a CMP Model of Copper thin Films

AbstractWith the rapid change of materials systems and decreased feature size, thin film microstructure and mechanical properties have become critical parameters for microelectronics reliability. An example of a major driver of this new technology is the data storage community who is pushing for 1 Terabit/square inch on its magnetic disk hard drives. This requires inherent knowledge of the mechanical properties of materials and in depth understanding of the tribological phenomena involved in the manufacturing process. Chemical mechanical polishing (CMP) is a semi-conductor manufacturing process used to remove or planarize ultra-thin metallic, dielectric, or barrier films (copper) on silicon wafers. The material removal rate (MRR), which ultimately effects the surface topography, corresponding to CMP is given by the standard Preston Equation, which contains the load applied, the velocity of the pad, the Preston coefficient which includes chemical dependencies, and the hardness of the material. Typically the hardness, a bulk material constant, is taken as a constant throughout the wafer and thereby included in the Preston coefficient. Through metallurgy studies, on the micro and nano scale, it has been proven that the hardness is dependent upon grain size and orientation. This research served to first relate the crystallographic orientation to a specific hardness value and secondly use the hardness variation in the previously developed particle augmented mixed-lubrication (PAML) model to simulate the surface topography and MRR during CMP. Recent test and results show that currently there is no empirical formula to relate the crystallographic orientation and thereby a critically resolved shear stress (CRSS) to a specific hardness value. The second part of this investigation utilized the variation in hardness values from the initial study and incorporated these results into the PAML numerical model that incorporates all the physics of chemical mechanical polishing (CMP). Incorporation of the variation of hardness resulted in a surface topography with a difference in roughness (Ra) from the bulk constant hardness value of 60 nm. The material removal rate (MRR) of the process differs by 2.17 μm3/s.

Constraining Effects of Lead-Free Solder Joints During Stress Relaxation

Reliability and quality control of microelectronics depend on a detailed understanding of the complex thermomechanical properties of miniaturized lead-free solder joints. With the continuous reduction in size of modern electronic devices, including also the size of the solder joints themselves, mechanical constraint effects may become of importance for the reliability of the joints. In the present study stress relaxation tests in tensile mode were performed on model solder joints consisting of eutectic Sn-3.5Ag solder between Cu substrates. The gap size of the joints was varied between 750 μm and 150 μm in order to investigate the variation of the mechanical properties as a function of the gap size. As it turned out, stress relaxation was dramatically reduced when the solder gaps became smaller due to constraint effects already well known from earlier measurements of the tensile strength. By employing a traditional creep model, the stress exponents and the activation energies were derived and compared with available data in the literature. The consequences of these constraint effects for the case of thermomechanical fatigue are discussed.

Heating characteristics of convection reflow ovens

The inhomogeneous temperature distribution in the reflow oven can cause soldering failures. In this project, we investigate how the construction of a convection reflow oven has an affect on its heating characteristics. In the convection reflow oven itself, the heating capability is mainly dependent on the heat transfer coefficient, which in turn is mostly determined by the gas flow parameters. Therefore, we study how the construction of the reflow oven affects the flow of gas in the oven. Our conclusions are then verified with experimental results. During our experiments, temperature changes were measured at different points located around the centre of the processing area in the oven. From this data, the 3D directional characteristics of the heat transfer coefficient was calculated using the heat equation of the investigated reflow oven. We consider that our results are important for the effective thermal modelling of the reflow soldering process [B. Illés, G. Harsányi, 3D Thermal model to investigate component displacement phenomenon during reflow soldering, Microelectronics Reliability 48 (2008) 1062–1068] and are also useful when calibrating and designing reflow ovens. During our work, we examine the latest reflow ovens constructed with the nozzle-matrix blower system.

Low-K Dielectric Compatible Wafer-Level Compliant Chip-to-Substrate Interconnects

Performance, power, size, and cost requirements in the microelectronics industry are pushing for smaller feature size, innovative on-chip dielectric materials, higher number of interconnects at a reduced pitch, etc., without compromising the microelectronics reliability. Compliant off-chip interconnects show great potential to address these needs. G-Helix is a lithography-based electroplated compliant interconnect that can be fabricated at the wafer level. G-Helix interconnects exhibit excellent compliance in all three orthogonal directions, and can accommodate the coefficient of thermal expansion (CTE) mismatch between the silicon die and the organic substrate without requiring an underfill material. These compliant interconnects are beneficial for integrated circuits (ICs) with low-K dielectric material. They are also potentially cost effective as they can be fabricated using conventional wafer fabrication infrastructure. In this paper we discuss the assembly and experimental reliability assessment, through thermal cycling, of G-Helix interconnects assembled on an organic substrate. Results from mechanical characterization experiments are also presented. It is shown that the proposed interconnects are not likely to delaminate or crack the low-K dielectric material. Also, a unique integrative approach is discussed, with interconnects having varying compliance for optimum electrical and mechanical performance.

On the effect of Kirkendall voids on solder joint reliability

AbstractA model for the theoretical description of Kirkendall voiding is presented based on vacancy diffusion and plastic deformation of spherical voids. We start with a phenomenological explanation of the Kirkendall phenomenon and discuss its consequences on microelectronic reliability. After that a constitutive model for void growth is introduced, which, for instances, can be used in order to predict the temporal development of a certain void distribution. We end this paper with exemplary numerical studies. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)