On the mechanism of solid-state phase transitions in molecular crystals - the role of cooperative motion in (quasi)racemic linear amino acids.

During single-crystal-to-single-crystal (SCSC) phase transitions, a polymorph of a compound can transform to a more stable form while remaining in the solid state. By understanding the mechanism of these transitions, strategies can be developed to control this phenomenon. This is particularly important in the pharmaceutical industry, but also relevant for other industries such as the food and agrochemical industries. Although extensive literature exists on SCSC phase transitions in inorganic crystals, it is unclear whether their classications and mechanisms translate to molecular crystals, with weaker interactions and more steric hindrance. A comparitive study of SCSC phase transitions in aliphatic linear-chain amino acid crystals, both racemates and quasi-racemates, is presented. A total of 34 transitions are considered and most are classified according to their structural change during the transition. Transitions without torsional changes show very different characteristics, such as transition temperature, enthalpy and free energy, compared with transitions that involve torsional changes. These differences can be rationalized using classical nucleation theory and in terms of a difference in mechanism; torsional changes occur in a molecule-by-molecule fashion, whereas transitions without torsional changes involve cooperative motion with multiple molecules at the same time.

Complex Geometric Structure of a Simple Solid-Liquid Interface: GaN(0001)-Ga.

The equilibrium atomic interface structure between Ga and GaN(0001) is shown to contain substrate surface vacancies followed by substrate-induced layering and preferential lateral ordering in the liquid. The uncovered presence of point defects, in the form of vacancies at both sides of the solid-liquid interface, is an important structural feature which governs the local physical properties. Our x-ray diffraction study reveals that the layering is very stable and persists up to a temperature of 1123 K and a nitrogen pressure of 32 bar. The Ga layer spacing agrees remarkably well with the Friedel oscillation period for this system.

Metal diffusion barriers for GaAs solar cells.

In this study accelerated ageing testing (AAT), J-V characterization and TEM imaging in combination with phase diagram data from literature are used to assess the potential of Ti, Ni, Pd and Pt as diffusion barriers for Au/Cu-based metallization of III-V solar cells. Ni barriers show the largest potential as at an AAT temperature of 250 °C both cells with 10 and 100 nm thick Ni barriers show significantly better performance compared to Au/Cu cells, with the cells with 10 nm Ni barriers even showing virtually no degradation after 7.5 days at 250 °C (equivalent to 10 years at 100 °C at an Ea of 0.70 eV). Detailed investigation shows that Ni does not act as a barrier in the classical sense, i.e. preventing diffusion of Cu and Au across the barrier. Instead Ni modifies or slows down the interactions taking place during device degradation and thus effectively acts as an 'interaction' barrier. Different interactions occur at temperatures below and above 250 °C and for thin (10 nm) and thick (100 nm) barriers. The results of this study indicate that 10-100 nm thick Ni intermediate layers in the Cu/Au based metallization of III-V solar cells may be beneficial to improve the device stability upon exposure to elevated temperatures.

Degradation mechanism(s) of GaAs solar cells with Cu contacts.

Substrate-based GaAs solar cells having a dense Au/Cu front contact grid with 45% surface coverage were exposed to accelerated life testing at temperatures between 200 and 300 °C. TEM analysis of the front contacts was used to gain a better understanding of the degradation process. During accelerated life testing at 200 °C only intermixing of the Au and Cu in the front contact occurs, without any significant influence on the J-V curve of the cells, even after 1320 h (55 days) of accelerated life testing. At temperatures ≥250 °C a recrystallization process occurs in which the metals of the contact and the GaAs front contact layer interact. Once the grainy recrystallized layer starts to approach the window, diffusion via grain boundaries to the window and into the active region of the solar cells occurs, causing a decrease in Voc due to enhanced non-radiative recombination via Cu trap levels introduced in the active region of the solar cell. To be a valid simulation of space conditions the accelerated life testing temperature should be <250 °C in future experiments, in order to avoid recrystallization of the metals with the GaAs contact layer.

Phase transition driven discontinuity in thermodynamic size selection.

We show how an order-disorder phase transition in a two-dimensional system can discontinuously alter the shape and size of stress-stabilized self-assembled nanostructures. Low energy electron microscopy was used to study the dealloying of the Cu(111)-sqrt[3]×sqrt[3]-R30°-Bi surface alloy. The gradual expulsion of embedded bismuth from the alloy with increasing temperature induces a hard-hexagon-type order-disorder transition in the surface alloy. Our low energy electron microscopy results demonstrate how the loss of long-range order induces enormous changes in the domain patterns that the alloy forms with a Bi overlayer phase. We propose that the occurrence of phase transitions in one of the two surface phases that constitute a self-assembled domain pattern, provides a general, largely unexplored, mechanism that can be used to influence the morphological details of two-dimensional nanostructures.

Generic nano-imprint process for fabrication of nanowire arrays.

A generic process has been developed to grow nearly defect-free arrays of (heterostructured) InP and GaP nanowires. Soft nano-imprint lithography has been used to pattern gold particle arrays on full 2 inch substrates. After lift-off organic residues remain on the surface, which induce the growth of additional undesired nanowires. We show that cleaning of the samples before growth with piranha solution in combination with a thermal anneal at 550 degrees C for InP and 700 degrees C for GaP results in uniform nanowire arrays with 1% variation in nanowire length, and without undesired extra nanowires. Our chemical cleaning procedure is applicable to other lithographic techniques such as e-beam lithography, and therefore represents a generic process.

The solubility behaviour and thermodynamic relations of the three forms of Venlafaxine free base.

The polymorphic and solubility behaviour of the active pharmaceutical ingredient Venlafaxine free base, which is used as an antidepressant, is studied. Using differential scanning calorimetry and slurry experiments, an enantiotropic relation between the three forms was found. Transition temperatures were determined using solubility data and compared with calculated transition temperatures based on the melting enthalpies and temperatures of the different forms. The solubility of Venlafaxine in heptane, toluene and methanol shows a large deviation from ideal behaviour. The deviations are to a large extent determined by the temperature dependence of the difference in fusion enthalpy of the undercooled melt and the solid.

Experimental and computational morphology of three polymorphs of the free base of Venlafaxine: a comparison of morphology prediction methods.

In this paper the experimental and the computational studies of the morphology of three polymorphs of the free base of Venlafaxine ((N,N-dimethyl)-2-(1-hydroxy cyclohex-1-yl)-2-(4-methoxyphenyl) ethylamine) are reported. The morphology of all polymorphs has been predicted using the Bravais-Friedel-Donnay-Harker method, the attachment energy method and kinetic Monte Carlo growth simulations and these predictions have been compared with experimental observations. The Monte Carlo simulations allow for a detailed simulation of the growth process, including driving force and growth mechanism, which leads to a semi-quantitative prediction of the growth morphologies of all three phases. For phase I two distinct growth habits are found experimentally under the same conditions. This is explained by the occurrence of a spiral growth mechanism in one of the two, which was observed using AFM and which is also supported by the Monte Carlo simulations. The habit of phase II could only be explained from simulations when a spiral growth mechanism is assumed; the shape of phase III could not be modeled accurately from the Monte Carlo simulations. Although the shape of the crystal is reproduced accurately, some of the indices of the faces predicted are not in agreement with the indices measured. The deviations are interpreted to be due to the presence of domains in the crystals as a result of the layered structure.

Crystal growth in a three-phase system: diffusion and liquid-liquid phase separation in lysozyme crystal growth.

In the phase diagram of the protein hen egg-white lysozyme, a region is present in which the lysozyme solution demixes and forms two liquid phases. In situ observations by optical microscopy show that the dense liquid droplets dissolve when crystals grow in this system. During this process the demixed liquid region retracts from the crystal surface. The spatial distribution of the dense phase droplets present special boundary conditions for Fick's second law for diffusion. In combination with the cylindrical symmetry provided by the kinetically roughened crystals, this system allows for a full numerical analysis. Using experimental data for setting the boundary conditions, a quasi-steady-state solution for the time-dependent concentration profile was shown to be valid. Comparison of kinetically rough growth in a phase separated system and in a nonseparated system shows that the growth kinetics for a three-phase system differs from a two-phase system, in that crystals grow more slowly but the duration of growth is prolonged.

On the definition of a Monte Carlo model for binary crystal growth.

We show that consistency of the transition probabilities in a lattice Monte Carlo (MC) model for binary crystal growth with the thermodynamic properties of a system does not guarantee the MC simulations near equilibrium to be in agreement with the thermodynamic equilibrium phase diagram for that system. The deviations remain small for systems with small bond energies, but they can increase significantly for systems with large melting entropy, typical for molecular systems. These deviations are attributed to the surface kinetics, which is responsible for a metastable zone below the liquidus line where no growth occurs, even in the absence of a 2D nucleation barrier. Here we propose an extension of the MC model that introduces a freedom of choice in the transition probabilities while staying within the thermodynamic constraints. This freedom can be used to eliminate the discrepancy between the MC simulations and the thermodynamic equilibrium phase diagram. Agreement is achieved for that choice of the transition probabilities yielding the fastest decrease of the free energy (i.e., largest growth rate) of the system at a temperature slightly below the equilibrium temperature. An analytical model is developed, which reproduces quite well the MC results, enabling a straightforward determination of the optimal set of transition probabilities. Application of both the MC and analytical model to conditions well away from equilibrium, giving rise to kinetic phase diagrams, shows that the effect of kinetics on segregation is even stronger than that predicted by previous models.

Crystal structure prediction of organic pigments: quinacridone as an example.

The structures of the alpha, beta and gamma polymorphs of quinacridone (Pigment Violet 19) were predicted using Polymorph Predictor software in combination with X-ray powder diffraction patterns of limited quality. After generation and energy minimization of the possible structures, their powder patterns were compared with the experimental ones. On this basis, candidate structures for the polymorphs were chosen from the list of all structures. Rietveld refinement was used to validate the choice of structures. The predicted structure of the gamma polymorph is in accordance with the experimental structure published previously. Three possible structures for the beta polymorph are proposed on the basis of X-ray powder patterns comparison. It is shown that the alpha structure in the Cambridge Structural Database is likely to be in error, and a new alpha structure is proposed. The present work demonstrates a method to obtain crystal structures of industrially important pigments when only a low-quality X-ray powder diffraction pattern is available.

Observation of a liquid phase with an orthorhombic orientational order.

Using surface x-ray diffraction, we have determined the structure of liquid Bi monolayers on Cu(111) for a range of coverages. By combining diffuse scattering data from the liquid with information from the substrate scattering, the ordering properties of Bi have been fully determined. Even though the substrate is hexagonal, we find that the liquid does not show hexatic order but has an orthorhombic orientational order that occurs in three domains. Simultaneously, Bi has partial solidlike properties, even well above its melting point.

Epitaxial 2D nucleation of the stable polymorphic form of the steroid 7alphaMNa on the metastable form: implications for Ostwald's rule of stages.

This paper presents in situ observations of the epitaxial nucleation and growth of the stable polymorph of a steroid, 7alphaMna, on a specific face of the metastable form at low supersaturation, using optical microscopy and in situ Raman spectroscopy. The presence of the metastable polymorph is essential for the nucleation and growth of the stable one. The order of the metastable zones of the stable and metastable polymorphs is reversed for the epitaxial growth process as compared to the case of 3D nucleation. The rate of transformation of the metastable polymorph to the stable one can be controlled by the supersaturation.

Experimental and computational growth morphology of two polymorphs of a yellow isoxazolone dye.

We report on the crystal structures and the experimentally found and the computationally predicted growth morphologies of two polymorphs of a yellow isoxazolone dye. The stable polymorph I has a blocklike habit, and the metastable polymorph II grows as fine needles, nucleating only by heterogeneous or contact nucleation. The habits of both polymorphs depend on the supersaturation during growth. The experimental observations are compared with predictions of the attachment energy model and kinetic Monte Carlo lattice simulations in which the growth is modeled as an "atomistic process", governed by surface energetics. These Monte Carlo simulations correctly predict the shape and the dependence on supersaturation of the crystal morphology for both polymorphs: for polymorph I, a strong dependence on supersaturation is found from the simulations. For polymorph II, the order of morphological importance is reproduced correctly, as well as the needlelike morphology.

Thickness-dependent ordering of water layers at the NaCl(100) surface.

We have determined the ordering properties of water adsorbed at room temperature on the rock salt (100) surface under four different conditions: ultrahigh vacuum, dry nitrogen atmosphere, 45% and 75% relative humidity. Details of the atomic structure are determined for both sides of the solid-liquid interface. The top most layer of NaCl shows a small relaxation that changes from an expansion to a contraction with increasing humidity. Under all measured conditions water monolayers with different ordering properties are present at the interface. Surprisingly, we find that the amount of ordering in the first layer is increasing with increasing thickness of the water film. At a solid-liquid interface, the ordering appears to be correlated with the solubility.

Liquid order at the interface of KDP crystals with water: evidence for icelike layers.

We present a surface x-ray diffraction study on the KDP-water interface in which the structure of both the crystalline and liquid part of the interface has been measured. We have been able to determine the ordering components in the liquid in both the perpendicular and parallel directions. We find interface-induced ordering in the first four layers of water molecules. The first two layers behave icelike and are strongly bound to the surface. The next two layers are more diffuse and show only minor lateral and perpendicular ordering. Subsequent layers are found to behave similar to a bulk liquid.

New (sqrt3 xsqrt 3)R30 degrees phase of Pb on Ge(111) and its consequence for the melting transition.

Depending on the preparation method, we find two different structures of the Pb/Ge(111) system at a nominal coverage of 4 / 3 monolayer that exhibit different melting points. One is the well studied beta phase that melts at 270 degrees C, but the other is a new and metastable phase that melts at 330 degrees C. Using surface x-ray diffraction the atomic structure of both phases is found to be surprisingly similar. The difference in melting points can be explained by the distribution of the excess Pb present on the surface, which has a direct effect on the vacancy density. We propose a modified phase diagram, in which the melting temperature of the beta phase depends strongly on coverage.

Controlling crystal surface termination by cleavage direction.

We have investigated the cleaving behavior of potassium bichromate (K(2)Cr(2)O(7)) crystals using atomic force microscopy. This crystal has a double layered AB structure along [001]. We find that, upon cleavage along the [001] plane in the <100> directions, one side is completely A terminated, while the other is B terminated. Moreover, the cleavage plane (between an A and a B layer, or between B and A) depends on the imposed direction of cleavage, i.e., [100] or [*100]. This means that the molecular layer that terminates the crystal surface can be controlled by choosing the macroscopic direction of the cleavage force. One of the two terminations is metastable and partly reconstructs to the stable termination.

The Dutch-Belgian beamline at the ESRF.

A brief description is given of the design principles and layout of the Dutch-Belgian beamline at the ESRF. This beamline optimizes the use of the available bending-magnet radiation fan by splitting the beam into two branches, each accommodating two experimental techniques.

Slits as adjustable pinholes for coherent X-ray scattering experiments.

The combination of accurate translation stages with carefully polished slit blades leads to slits that have many advantages as pinholes for coherent X-ray scattering experiments. The size is adjustable and can be made as small as 0.5 mum. Setting up is easy, while the blade thickness (1 mm tungsten) also makes the slits useful for hard X-rays. A relation between the slit-sample distance and the minimum beam size, together with the corresponding slit size, is derived. This shows that a micrometer-sized beam can be achieved with this type of slits.