Jakoah Brgoch

An Efficient, Thermally Stable Cerium-Based Silicate Phosphor for Solid State White Lighting

A novel cerium-substituted, barium yttrium silicate has been identified as an efficient blue-green phosphor for application in solid state lighting. Ba9Y2Si6O24:Ce(3+) was prepared and structurally characterized using synchrotron X-ray powder diffraction. The photoluminescent characterization identified a major peak at 394 nm in the excitation spectrum, making this material viable for near-UV LED excitation. An efficient emission, with a quantum yield of ≈60%, covers a broad portion (430-675 nm) of the visible spectrum, leading to the blue-green color. Concentration quenching occurs when the Ce(3+) content exceeds ≈3 mol %, whereas high temperature photoluminescent measurements show a 25% drop from the room temperature efficiency at 500 K. The emission of this compound can be red-shifted via the solid solution Ba9(Y(1-y)Sc(y))(1.94)Ce(0.06)Si6O24 (y = 0.1, 0.2), allowing for tunable color properties when device integration is considered.

Average and Local Structural Origins of the Optical Properties of the Nitride Phosphor La3–xCexSi6N11 (0 < x ≤ 3)

Structural intricacies of the orange-red nitride phosphor system La(3-x)Ce(x)Si6N11 (0 < x ≤ 3) have been elucidated using a combination of state-of-the art tools, in order to understand the origins of the exceptional optical properties of this important solid-state lighting material. In addition, the optical properties of the end-member (x = 3) compound, Ce3Si6N11, are described for the first time. A combination of synchrotron powder X-ray diffraction and neutron scattering is employed to establish site preferences and the rigid nature of the structure, which is characterized by a high Debye temperature. The high Debye temperature is also corroborated from ab initio electronic structure calculations. Solid-state (29)Si nuclear magnetic resonance, including paramagnetic shifts of (29)Si spectra, are employed in conjunction with low-temperature electron spin resonance studies to probes of the local environments of Ce ions. Detailed wavelength-, time-, and temperature-dependent luminescence properties of the solid solution are presented. Temperature-dependent quantum yield measurements demonstrate the remarkable thermal robustness of luminescence of La2.82Ce0.18Si6N11, which shows little sign of thermal quenching, even at temperatures as high as 500 K. This robustness is attributed to the highly rigid lattice. Luminescence decay measurements indicate very short decay times (close to 40 ns). The fast decay is suggested to prevent strong self-quenching of luminescence, allowing even the end-member compound Ce3Si6N11 to display bright luminescence.

Average and Local Structure, Debye Temperature, and Structural Rigidity in Some Oxide Compounds Related to Phosphor Hosts

The average and local structure of the oxides Ba2SiO4, BaAl2O4, SrAl2O4, and Y2SiO5 are examined to evaluate crystal rigidity in light of recent studies suggesting that highly connected and rigid structures yield the best phosphor hosts. Simultaneous momentum-space refinements of synchrotron X-ray and neutron scattering yield accurate average crystal structures, with reliable atomic displacement parameters. The Debye temperature ΘD, which has proven to be a useful proxy for structural rigidity, is extracted from the experimental atomic displacement parameters and compared with predictions from density functional theory calculations and experimental low-temperature heat capacity measurements. The role of static disorder on the measured displacement parameters, and the resulting Debye temperatures, are also analyzed using pair distribution function of total neutron scattering, as refined over varying distance ranges of the pair distribution function. The interplay between optimal bonding in the structure, structural rigidity, and correlated motion in these structures is examined, and the different contributions are delineated.

Anionic Chemistry of Noble Gases: Formation of Mg–NG (NG = Xe, Kr, Ar) Compounds under Pressure

While often considered to be chemically inert, the reactivity of noble gas elements at elevated pressures is an important aspect of fundamental chemistry. The discovery of Xe oxidation transformed the doctrinal boundary of chemistry by showing that a complete electron shell is not inert to reaction. However, the reductive propensity, i.e., gaining electrons and forming anions, has not been proposed or examined for noble gas elements. In this work, we demonstrate, using first-principles electronic structure calculations coupled to an efficient structure prediction method, that Xe, Kr, and Ar can form thermodynamically stable compounds with Mg at high pressure (≥125, ≥250, and ≥250 GPa, respectively). The resulting compounds are metallic and the noble gas atoms are negatively charged, suggesting that chemical species with a completely filled shell can gain electrons, filling their outermost shell(s). Moreover, this work indicates that Mg2NG (NG = Xe, Kr, Ar) are high-pressure electrides with some of the electrons localized at interstitial sites enclosed by the surrounding atoms. Previous predictions showed that such electrides only form in Mg and its compounds at very high pressures (>500 GPa). These calculations also demonstrate strong chemical interactions between the Xe 5d orbitals and the quantized interstitial quasiatom (ISQ) orbitals, including the strong chemical bonding and electron transfer, revealing the chemical nature of the ISQ.

Local structure and structural rigidity of the green phosphor β-SiAlON:Eu2+

Eu2+ inserted in β-Si3−xAlxOxN4−x is a material that shows exceptional promise as a green-emitting phosphor. Synchrotron X-ray and neutron scattering, in conjunction with first-principles calculations and Eu L3 X-ray absorption measurements, yield a consistent picture of the composition, and the favorable position for Eu2+ substitution in the crystal structure. The Debye temperature ΘD, which is a proxy for structural rigidity relating to effectiveness as a phosphor, is very high for the starting β-Si3N4 framework and is determined to decrease only slightly for the small amounts of Al3+ and O2− co-substitution that are required for charge balance associated with Eu2+ insertion.

Structure–composition relationships and optical properties in cerium-substituted (Sr,Ba)3(Y,La)(BO3)3 borate phosphors

Relationships between the structure and composition, and their influence on the optical properties, of a family of cerium-substituted borate compounds with formula A3RE(BO3)3 (A = Ba, Sr; RE = Y, La) are studied using a combination of high resolution synchrotron X-ray powder diffraction and photoluminescence. Examination of the coordination environment of the Ce3+ active site polyhedra coupled with photoluminescence at 77 K reveal three distinct excitation bands corresponding to Ce3+ located on three distinct crystallographic sites. Comparing the position of these excitation bands with crystal field splitting effects due to changes in polyhedral volumes and distortions suggest an assignment of the three excitation bands. These compounds are efficiently excited by UV light (≈340 nm) with blue emission at a maximum wavelength of 413 nm for Ba3Y(BO3)3:Ce3+,Na+, 422 nm for Sr3Y(BO3)3:Ce3+,Na+, and 440 nm for Sr3La(BO3)3:Ce3+,Na+. The most efficient compound was determined to be Sr3La(BO3)3:Ce3+,Na+ with a quantum yield of 50%.

Scaffolding, ladders, chains, and rare ferrimagnetism in intermetallic borides: synthesis, crystal chemistry and magnetism.

Single-phase polycrystalline samples and single crystals of the complex boride phases Ti(8)Fe(3)Ru(18)B(8) and Ti(7)Fe(4)Ru(18)B(8) have been synthesized by arc melting the elements. The phases were characterized by powder and single-crystal X-ray diffraction as well as energy-dispersive X-ray analysis. They are new substitutional variants of the Zn(11)Rh(18)B(8) structure type, space group P4/mbm (no. 127). The particularity of their crystal structure lies in the simultaneous presence of dumbbells which form ladders of magnetically active iron atoms along the [001] direction and two additional mixed iron/titanium chains occupying Wyckoff sites 4h and 2b. The ladder substructure is ca. 3.0 Å from the two chains at the 4h, which creates the sequence chain-ladder-chain, establishing a new structural and magnetic motif, the scaffold. The other chain (at 2b) is separated by at least 6.5 Å from this scaffold. According to magnetization measurements, Ti(8)Fe(3)Ru(18)B(8) and Ti(7)Fe(4)Ru(18)B(8) order ferrimagnetically below 210 and 220 K, respectively, with the latter having much higher magnetic moments than the former. However, the magnetic moment observed for Ti(8)Fe(3)Ru(18)B(8) is unexpectedly smaller than the recently reported Ti(9)Fe(2)Ru(18)B(8) ferromagnet. The variation of the magnetic moments observed in these new phases can be adequately understood by assuming a ferrimagnetic ordering involving the three different iron sites. Furthermore, the recorded hysteresis loops indicate a semihard magnetic behavior for the two phases. The highest H(c) value (28.6 kA/m), measured for Ti(7)Fe(4)Ru(18)B(8), lies just at the border of those of hard magnetic materials.

Peierls‐Distorted Monoclinic MnB4 with a MnMn Bond

Tetraborides of chromium and manganese exhibit an unusual boron-atom framework that resembles the hypothetical tetragonal diamond. They are believed to be very hard. Single crystals of MnB4 have now been grown. The compound crystallizes in the monoclinic crystal system (space group P21 /c) with a structure that has four crystallographically independent boron-atom positions, as confirmed by (11) B MAS-NMR spectroscopy. An unexpected short distance between the Mn atoms suggests a double Mn-Mn bond and is caused by Peierls distortion. The structure was solved using group-subgroup-relationships. DFT calculations indicate Mn(I) centers and paramagnetism, as confirmed by magnetic measurements. The density of states shows a pseudo-band gap at the Fermi energy and semiconducting behavior was observed for MnB4 .

Identifying a Structural Preference in Reduced Rare-Earth Metal Halides by Combining Experimental and Computational Techniques

The structures of two new cubic {TnLa(3)}Br(3) (Tn = Ru, Ir; I4(1)32, Z = 8; Tn = Ru: a = 12.1247(16) Å, V = 1782.4(4) Å(3); Tn = Ir: a = 12.1738(19) Å, V = 1804.2(5) Å(3)) compounds belonging to a family of reduced rare-earth metal halides were determined by single-crystal X-ray diffraction. Interestingly, the isoelectronic compound {RuLa(3)}I(3) crystallizes in the monoclinic modification of the {TnR(3)}X(3) family, while {IrLa(3)}I(3) was found to be isomorphous with cubic {PtPr(3)}I(3). Using electronic structure calculations, a pseudogap was identified at the Fermi level of {IrLa(3)}Br(3) in the new cubic structure. Additionally, the structure attempts to optimize (chemical) bonding as determined through the crystal orbital Hamilton populations (COHP) curves. The Fermi level of the isostructural {RuLa(3)}Br(3) falls below the pseudogap, yet the cubic structure is still formed. In this context, a close inspection of the distinct bond frequencies reveals the subtleness of the structure determining factors.

Manganese Tetraboride, MnB4: High‐Temperature Crystal Structure, p–n Transition, 55Mn NMR Spectroscopy, Solid Solutions, and Mechanical Properties

The structural and electronic properties of MnB4 were studied by high-temperature powder X-ray diffraction and measurements of the conductivity and Seebeck coefficient on spark-plasma-sintered samples. A transition from the room-temperature monoclinic structure (space group P2(1)/c) to a high-temperature orthorhombic structure (space group Pnnm) was observed at about 650 K. The material remained semiconducting after the transition, but its behavior changed from p-type to n-type. (55)Mn NMR measurements revealed an isotropic chemical shift of -1315 ppm, confirming an oxidation state of Mn close to I. Solid solutions of Cr(1-x)Mn(x)B4 (two phases in space groups Pnnm and P2(1)/c) were synthesized for the first time. In addition, nanoindentation studies yielded values of (496±26) and (25.3±1.7) GPa for the Youngs modulus and hardness, respectively, compared to values of 530 and 37 GPa obtained by DFT calculations.