arXiv subjects

Detlef Klimm

Publications and source records attributed to Detlef Klimm.

At least 19 recordsLinked to original sources

arXiv2025

Floating zone growth of high-purity MgO substrate single crystals

MgO single crystals with diameters between 3.5 and 5 mm and lengths up to 40 mm were grown by the optical floating zone technique (OFZ). Despite challenging material properties such as the high melting point of 2825 {\deg}C, very high evaporation rate and perfect {100} cleaving characteristics, crack-free crystals were grown at high growth rates exceeding 40 mm/h and at high thermal gradients. Chemical investigations revealed that the OFZ technique is suitable for the preparation of substrate crystals with a purity of 5N to facilitate the development of novel demonstrator devices based on epitaxially grown thin films. The achieved purity level is improved by more than one order of magnitude if compared to commercial MgO substrate single crystals graded as high purity.

cond-mat.mtrl-sci↗

arXiv2024

Ferroelectric to paraelectric structural transition in LiTaO$_3$ and LiNbO$_3$

The ferroelectric to paraelectric phase transition in LiTaO$_3$ and in pure as well as Mg doped LiNbO$_3$ is investigated theoretically by atomistic calculations in the framework of the density functional theory, as well as experimentally by calorimetry and electrical conductivity measurements. First principles models within the stochastic self-consistent harmonic approximation (SSCHA) allow to consider anharmonic effects and thus to obtain a realistic estimate of the Curie temperature $T_C$ of both ferroelectrics. \textit{Ab initio} molecular dynamics (AIMD) calculations performed on large supercells confirm the Curie temperatures estimated with the SSCHA approach. Moreover, they also suggest that the structural phase transition is a continuous process beginning at temperatures well below $T_C$. According to AIMD, significant ionic displacements occurr already at temperatures of about 100\,K and 300\,K below $T_C$ in LiTaO$_3$ and LiNbO$_3$, respectively. To asses whether and how far the ionic displacements affect the materials properties, the AIMD results are compared with measurements of the electrical conductivity and of the heat capacity across the phase transition. Our first principles calculations moreover show that Mg ions, a frequently employed dopant, raise the Curie temperature in LiNbO$_3$.

cond-mat.mtrl-sci↗

arXiv2024

Phase Transformation in Lithium Niobate-Lithium Tantalate Solid Solutions (LiNb$_{1-x}$Ta$_x$O$_3$)

The investigation of the structural phase transition in the vicinity of the Curie temperature $T_c$ of LiNb$_{1-x}$Ta$_x$O$_3$ crystals is motivated by the expected combination of advantageous high-temperature properties of LiNbO$_3$ and LiTaO$_3$, including high piezoelectric modules and remarkable high-temperature stability, respectively. $T_c$ marks the ultimate limit for exploiting the piezoelectric properties, however transition related structural modifications might impact this and other properties even below $T_c$. Remarkably, the phase transition from the ferroelectric to the paraelectric phase, whose temperature strongly depends on the composition $x$, shows a significant drop in the activation energy of the electrical conductivity. The magnitude, temperature dependence and underlying mechanisms of this drop are discussed from a microscopic perspective. Molecular dynamics calculations in the framework of the density functional theory show that substantial displacements of the cations occur below $T_c$ for both the end compounds LiNbO$_3$ and LiTaO$_3$, and might thus affect the electrical conductivity. Above $T_c$, the migration of lithium ions is presumably facilitated by a shortened diffusion path for the most favorable jump of the lithium ions. Electronic contributions to the conductivity, which become important above 900 K, are explained within the polaronic picture by the formation and migration of free small polarons.

cond-mat.mtrl-sci↗

arXiv2024

Evaluation and thermodynamic optimization of phase diagram of lithium niobate tantalate solid solutions

The phase diagram of the lithium niobate and lithium tantalate solid solutions was investigated using experimental data from differential thermal analysis (DTA) and crystal growth. We used XRF analysis to determine the elemental composition of crystals. Based on the Neumann-Kopp rule, essential data of end members lithium niobate (LN) and lithium tantalate (LT) was created. The heats of fusion of end members given by DTA measurements of LN (103 kJ/mol at 1531 K) and LT (289 kJ/mol at 1913 K) were given as input parameters to generate the data. This data served as the basis for calculating a phase diagram for LN and LT solid solutions. Finally, based on the experimental data and thermodynamic solution model, the phase diagram was optimized in the Calphad Factsage module. We also generated thermodynamic parameters for Gibb's excess energy of the solid solution. A plot of segregation coefficient as a function of Ta concentration was derived from the phase diagram.

cond-mat.mtrl-sci↗

arXiv2022

Adsorption-controlled plasma-assisted molecular beam epitaxy of LaInO3 on DyScO3(110): Growth window, strain relaxation, and domain pattern

We report the growth of epitaxial LaInO3 on DyScO3(110) substrates by adsorption-controlled plasma-assisted molecular beam epitaxy (PA-MBE). The adsorption-controlled growth was monitored using line-of-sight quadrupole mass spectrometry. In a thermodynamics of MBE (TOMBE) diagram, the experimental growth window was found to be significantly narrower than the predicted one. We found the critical thickness for strain relaxation of the LaInO3 layer (lattice mismatch $\approx$ -4$\%$) to be of 1 nm using in-situ RHEED analysis. Substrate and film possess an orthorhombic crystal structure which can be approximated by a pseudo-cubic lattice. X-ray-diffraction (XRD) analysis revealed the pseudo-cube-on-pseudo-cube epitaxial relationship ofthe LaInO3 films to the DyScO3 substrates. This relation was confirmed by transmission electron microscopy (TEM), which further resolved the presence of rotational orthorhombic domains - the majority of which have coinciding c-axis with that of the substrate. Raman spectroscopy further confirmed the presence of a LaInO3 layer. Our findings open up the possibility for 2-dimensional electron gases at the MBE-grown heterointerface with BaSnO3.

cond-mat.mtrl-sci↗

arXiv2020

Phase diagram studies for the growth of (Mg,Zr):SrGa$_{12}$O$_{19}$ crystals

By differential thermal analysis a concentration field suitable for the growth of Zr, Mg codoped strontium hexagallate crystals was observed that corresponds well with experimental results from Mateika and Laurien, J. Crystal Growth 52 (1981) 566-572. It was shown that the melting point of doped crystal is ca. 60 K higher than that of undoped crystals. This higher melting points indicates hexagallate phase stabilization by Zr, Mg codoping, and increases the growth window, compared to undoped SrO-Ga$_2$O$_3$ melts.

cond-mat.mtrl-sci↗

arXiv2019

Growth of CuFeO$_2$ Single Crystals by the Optical Floating-Zone Technique

CuFeO$_2$ single crystals up to 50 mm in length and up to 10 mm in diameter were grown by the optical floating-zone method. Stoichiometric polycrystalline rods with a diameter of 6-12 mm were used as feed materials to produce crystals of sufficient size to be used as substrates for the growth of thin films of delafossites. For stable growth along the $c$-axis, low growth rates of 0.4 mm/h are necessary. Due to the incongruent melting behavior of CuFeO$_2$, a stable melt zone requires adjustment of the lamp power during growth. The melting of CuFeO$_2$ is not simply incongruent because the thermodynamic equilibrium includes more than two solid phases and the melt; the gas phase is also involved. The crystals were characterized by X-ray diffraction and X-ray fluorescence measurements.

cond-mat.mtrl-sci↗

arXiv2018

Thermal analysis and crystal growth of doped Nb$_2$O$_5$

The systems Nb$_2$O$_5$-Ta$_2$O$_5$ and Nb$_2$O$_5$-V$_2$O$_5$ were investigated using thermal analysis, X-ray powder diffraction and thermodynamic simulations. Solid solution formation is possible for both systems; furthermore, both contain one intermediate compound, VNb$_9$O$_{25}$ or Ta$_2$Nb$_4$O$_{15}$, respectively. Phase relationships for pure niobium(V)-oxide and tantalum(V)-oxide were studied under ambient pressure. It was found that both compounds can occur in two stable solid modifications. For niobium(V)-oxide this are the monoclinic high-temperature modification (H-Nb$_2$O$_5$) and an orthorhombic low-temperature modification (T-Nb$_2$O$_5$) and for tantalum(V)-oxide a tetragonal high-temperature form ($α$-Ta$_2$O$_5$) and an orthorhombic low-temperature form ($β$-Ta$_2$O$_5$). Based on these results, crystal growth experiments with various compositions from both systems were carried out using the optical floating zone (OFZ) technique.

cond-mat.mtrl-sci↗

arXiv2018

Investigation of the Nd$_2$O$_3$--Lu$_2$O$_3$--Sc$_2$O$_3$ phase diagram for the preparation of perovskite-type mixed crystals NdLu$_{1-x}$Sc$_x$O$_3$

Based on differential thermal analysis (DTA) and X-ray powder diffraction (XRD), a description of the system Nd$_2$O$_3$--Lu$_2$O$_3$--Sc$_2$O$_3$ was obtained by thermodynamic assessment. Four fields of primary crystallization could be identified; from melt compositions close to the Lu$_2$O$_3$--Sc$_2$O$_3$ edge the rare-earth oxide C-phase crystallizes first, which is stable down to room temperature. From Nd$_2$O$_3$ rich melts the X-phase forms, which is stable only at high temperatures. An additional field, where the alternative high-temperature phase H solidifies as primary product touches the Nd$_2$O$_3$--Lu$_2$O$_3$ edge of the concentration triangle. From melts close to the composition NdScO$_3$, the P-phase (perovskite) can be crystallized and mixed crystals with second end member NdLuO$_3$ have been grown from the melt. Crystals of this mixed perovskite were grown by the micro-pulling-down and Czochralski methods.

cond-mat.mtrl-sci↗

arXiv2018

On melt solutions for the growth of CaTiO$_3$ crystals

When calcium titanate crystals are grown from stoichiometric melts, they crystallize in the cubic perovskite structure. Upon cooling to room temperature they undergo subsequent phase transitions to tetragonal and orthorhombic modifications. These phase transitions are disruptive and result in severely damaged crystals. This paper presents differential thermal analysis data for several prospective solvents, with the aim to identify a system offering the possibility to perform crystal growth of undistorted CaTiO$_3$ crystals by crystallizing them significantly below the melting point directly in the low temperature modification. From mixtures CaF$_2$:TiO$_2$:CaTiO$_3$ = 3:1:1 (molar ratio) the growth of undistorted, at least millimeter-sized CaTiO$_3$ crystals is possible.

cond-mat.mtrl-sci↗

arXiv2017

Thermal conductivity of rare-earth scandates in comparison to other oxidic substrate crystals

High-temperature thermal properties of three neighboring rare-earth scandates DyScO$_3$, TbScO$_3$ and GdScO$_3$ were compared to La$_{0.29}$Sr$_{0.71}$Al$_{0.65}$Ta$_{0.35}$O$_3$ (LSAT) and sapphire. To calculate thermal conductivity, heat capacity and thermal diffusivity were measured by differential scanning calorimetry and laser flash technique, respectively. DyScO$_3$ and TbScO$_3$ showed an untypical rise in the thermal conductivity above 900\,K, while for GdScO$_3$, LSAT and sapphire the expected decrease at elevated temperatures could be observed. These results lead to the proposal of a new type of heat transport by migrating ions.

cond-mat.mtrl-sci↗

arXiv2017

Thermodynamic investigations on the growth of CuAlO$_2$ delafossite crystals

Simultaneous differential thermal analysis (DTA) and thermogravimetric (TG) measurements with copper oxide/aluminum oxide mixtures were performed in atmospheres with varying oxygen partial pressures and with crucibles made of different materials. Only sapphire and platinum crucibles proved to be stable under conditions that are useful for the growth of CuAlO$_2$ delafossite single crystals. Then the ternary phase diagram Al$_2$O$_3$-CuO-Cu and its isopleth section Cu$_2$O-Al$_2$O$_3$ were redetermined. Millimeter sized crystals could be obtained from copper oxide melts with 1-2 mol % addition of aluminum oxide that are stable in platinum crucibles held in oxidizing atmosphere containing 15-21 % oxygen.

cond-mat.mtrl-sci↗

arXiv2015

On the influence of inversion on thermal properties of magnesium gallium spinel

Measurements of thermal diffusivity \k{appa} (using laser flash analysis) for temperatures from 100 °C to 1200 °C and of the inversion parameter x (using X-ray analysis) for the single crystal spinel MgGa2O4 have been performed. X-ray analysis showed a small change in x for samples annealed at 800 °C (x = 0.838) and 1200 °C (x = 0.834). Thermal diffusivity revealed a significant rise of \k{appa} for temperatures higher than 950 °C, deviating from the typical 1/T drop of \k{appa}. An additional systematic rise of \k{appa} with time is observed for temperatures between 950 °C and 1100 °C. A connection between cation disordering processes typical for spinels at elevated temperatures and the observed deviation of \k{appa} is proposed: Data indicate that cations changing their occupancy site at equilibration processes contribute significantly to \k{appa} and therefore represent a new type of heat transport.

cond-mat.mtrl-sci↗

arXiv2014

Ce3+:CaSc2O4 Crystal Fibers for Green Light Emission: Growth Issues and Characterization

Ce3+ is known to show broad optical emission peaking in the green spectral range. For the stabilization of 3-valent cerium in ceramic phosphors such as calcium scandate CaSc2O4, often co-doping with sodium for charge compensation is performed (Na+, Ce3+ = 2 Ca2+). At the melting point of CaSc2O4 (ca. 2110 deg C), however, alkaline oxides evaporate completely and co-doping is thus no option for crystal growth from the melt. It is shown that even without co-doping Ce3+:CaSc2O4 crystal fibers can be grown from the melt by laser-heated pedestal growth (LHPG) in a suitable reactive atmosphere. Reactive means here that the oxygen partial pressure is a function of temperature and pO2(T) rises for this atmosphere in such a way that Ce3+ is kept stable for all T. Crystal fibers with ca. 1 mm diameter and up to 50 mm length were grown and characterized. Differential thermal analysis (DTA) was performed in the pseudo-binary system CaO-Sc2O3, and the specific heat capacity cp(T) of CaSc2O4 was measured up to 1240 K by differential scanning calorimetry (DSC). Near and beyond the melting point of calcium scandate significant evaporation of calcium tends to shift the melt composition towards the Sc2O3 side. Measurements and thermodynamic calculations reveal quantitative data on the fugacities of evaporating species.

cond-mat.mtrl-sci↗

arXiv2014

Single crystal fiber growth of cerium doped strontium yttrate, SrY2O4:Ce3+

First single crystal fibers of cerium doped strontium yttrate are fabricated using the laser-heated pedestal growth technique. Through thermodynamic equilibrium calculations and by high-temperature mass spectrometry suitable growth conditions can be determined. The atmosphere plays an important role during crystallization. It affects the composition shift, on the one hand, and the valence state of cerium, on the other hand. These properties can be explained by combining X-ray diffraction, elemental analysis, and optical spectroscopy. Crystallization in slightly reducing nitrogen atmosphere proves to be a reasonable choice, because evaporation is suppressed and trivalent cerium is stabilized. Strong green emission that depends on the oxygen fugacity during crystallization can be excited using UV light. Optical transmission of SrY2O4:Ce3+ is measured for the first time.

cond-mat.mtrl-sci↗

arXiv2013

Top-seeded solution growth of SrTiO3 crystals and phase diagram studies in the SrO-TiO2 system

The TiO2 rich part of the (1-x) SrO + x TiO2 phase diagram 0.5 <= x <= 1.0 was redetermined and the eutectic point between SrTiO3 and TiO2 was found at x_eut=0.7700+/-0.0001; T_eut=(1449+/-3) deg C. From TiO2 rich melt solutions, x=0.75 centimeter-sized single crystals could be grown. The best crystals with etch pit density <2 x 10^4/cm^2 were obtained for growth directions <110> and <100>. AFM investigation of the interface reveals layer-by-layer growth.

cond-mat.mtrl-sci↗

arXiv2013

Growth of Self Organized Eutectic Fibers from LiF-Rare Earth Fluoride Systems

Eutectic fibers consisting of an ordered arrangement of LiF fibrils inside a LiREF4 matrix (RE = Y, Gd) can be grown with the micro-pulling-down method at sufficiently large pulling rate exceeding 120 mm/h. The distance between individual fibrils could be scaled down to 1 micrometer at 300 mm/h pulling. LiF-LiYF4 has stronger tendency to form facetted eutectic colonies than LiF-LiGdF4, explained by the larger entropy of melting of the former.

cond-mat.mtrl-sci↗

arXiv2012

On the effect of oxygen partial pressure on the chromium distribution coefficient in melt-grown ruby crystals

Small ruby crystals were grown by the Czochralski technique in different atmospheres and their actual chromium content was analysed by a wet chemical method. The chromium distribution coefficient k was found to be strongly dependent on oxygen partial pressure p(O2). It ranges from k=0.3 in a reducing atmosphere to k=1.2 in a slightly oxidizing atmosphere and to a good approximation k depends linearly on log(p(O2)). The experimental data are discussed on the basis of thermodynamic equilibrium calculations.

cond-mat.mtrl-sci↗