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Tetrahedron‐based nitrides offer a wide range of properties and applications. Highly condensed nitridophosphates are examples of nitrides that exhibit fascinating luminescence properties when doped with Eu2+, making them appealing for industrial applications. Here, we present the first nitridomagnesophosphate solid solution series Ba3−xSrx[Mg2P10N20] : Eu2+ (x=0–3), synthesized by a high‐pressure high‐temperature approach using the multianvil technique (3 GPa, 1400 °C). Starting from the binary nitrides P3N5 and Mg3N2 and the respective alkaline earth azides, we incorporate Mg into the P/N framework to increase the degree of condensation κ to 0.6, the highest observed value for alkaline earth nitridophosphates. The crystal structure was elucidated by single‐crystal X‐ray diffraction, powder X‐ray diffraction, energy‐dispersive X‐ray spectroscopy (EDX), and solid‐state NMR. DFT calculations were performed on the title compounds and other related highly condensed nitridophosphates to investigate the influence of Mg in the P/N network. Eu2+‐doped samples of the solid solution series show a tunable narrow‐band emission from cyan to green (492–515 nm), which is attributed to the preferred doping of a single crystallographic site. Experimental confirmation of this assumption was provided by overdoping experiments and STEM‐HAADF studies on the series as well on the stoichiometric compound Ba2Eu[Mg2P10N20] with additional atomic resolution energy‐dispersive X‐ray spectroscopy (EDX) mapping. [ABSTRACT FROM AUTHOR]

In the field of nitride phosphors, which are crucial for phosphor‐converted light‐emitting diodes, mixed tetrahedral networks hold a significant position. With respect to the wide range of compositions, the largely unexplored (Si, P)–N networks are investigated as potential host structures. In this work, two highly condensed structures, namely Sr2SiP2N6 and Sr5Si2P6N16 are reported to address the challenges that arise from the similarities of the network‐forming cations Si4+ and P5+ in terms of charge, ionic radius, and atomic scattering factor, a multistep workflow is employed to elucidate their structure. Using single‐crystal X‐ray diffraction, energy‐dispersive X‐ray spectroscopy (EDX), atomic‐resolution scanning transmission electron microscopy (STEM)‐EDX maps, and straightforward crystallographic calculations, it is found that Sr2SiP2N6 is the first ordered, and Sr5Si2P6N16 the first disordered, anionic tetrahedral (Si, P)–N network. After doping with Eu2+, Sr2SiP2N6:Eu2+ shows narrow cyan emission (λmax = 506 nm, fwhm = 60 nm/2311 cm−1), while for Sr5Si2P6N16:Eu2+ a broad emission with three maxima at 534, 662, and 745 nm upon irradiation with ultraviolet light is observed. An assignment of Sr sites as probable positions for Eu2+ and their relation to the emission bands of Sr5Si2P6N16:Eu2+ is discussed. [ABSTRACT FROM AUTHOR]

Light‐emitting diodes (LEDs) producing pure, highly saturated colors are the industry standard for efficient backlighting of high‐color gamut displays. Vivid color reproduction, matching the eye's perception of nature, is the central paradigm in the design of narrow‐band emitting phosphors. To cover a wide range of naturally occurring color tones, expansion of the color gamut in the green spectral region, and therefore an advanced applicable green phosphor, is highly desired. Herein, the oxonitridoberyllosilicate Ba[BeSiON2]:Eu2+ showing outstanding narrow‐band green emission (λmax ≈526 nm with FWHM ≈1600 cm−1 (≈45 nm), x = 0.212, y = 0.715) when excited with InGaN‐based blue LEDs is presented. High quantum efficiency and low thermal quenching (>90% rel. quantum efficiency at 100 °C) as well as excellent scalability make the material suitable for industrial application in high color‐gamut LED displays. A prototype phosphor‐converted‐LED (pc‐LED), with green‐emitting Ba[BeSiON2]:Eu2+ and K2SiF6:Mn4+ as red phosphor shows an extraordinary coverage in the CIE 1931 color space of 109% compared to the DCI‐P3 standard, topping the widely applied β‐SiAlON:Eu2+ phosphor (104%), making it suitable for use in phone displays, monitors, and television screens. [ABSTRACT FROM AUTHOR]

We have previously presented a computational protocol that is based on an embedded cluster model and operates in the framework of TD-DFT in conjunction with the excited state dynamics (ESD) approach. The protocol is able to predict the experimental absorption and emission spectral shapes of Eu2+-doped phosphors. In this work, the applicability domain of the above protocol is expanded to Eu2+-doped phosphors bearing multiple candidate Eu doping centers. It will be demonstrated that this protocol provides full control of the parameter space that describes the emission process. The stability of Eu doping at various centers is explored through local energy decomposition (LED) analysis of DLPNO-CCSD(T) energies. This enables further development of the understanding of the electronic structure of the targeted phosphors, the diverse interactions between Eu and the local environment, and their impact on Eu doping probability, and control of the emission properties. Hence, it can be employed to systematically improve deficiencies of existing phosphor materials, defined by the presence of various intensity emission bands at undesired frequencies, towards classes of candidate Eu2+-doped phosphors with desired narrow band red emission. For this purpose, the chosen study set consists of three UCr4C4-based narrow-band phosphors, namely the known alkali lithosilicates RbNa[Li3SiO4]2:Eu2+ (RNLSO2), RbNa3[Li3SiO4]4:Eu2+ (RNLSO) and their isotypic nitridolithoaluminate phosphors consisting of CaBa[LiAl3N4]2:Eu2+ (CBLA2) and the proposed Ca3Ba[LiAl3N4]4:Eu2+ (CBLA), respectively. The theoretical analysis presented in this work led us to propose a modification of the CBLA2 phosphor that should have improved and unprecedented narrow band red emission properties. Finally, we believe that the analysis presented here is important for the future rational design of novel Eu2+-doped phosphor materials, with a wide range of applications in science and technology. [ABSTRACT FROM AUTHOR]

Oxonitridophosphates exhibit the potential for broad structural diversity, making them promising host‐compounds in phosphor‐converted light‐emitting diode applications. The novel monophyllo‐oxonitridophosphate β‐MgSrP3N5O2 was obtained by using the high‐pressure multianvil technique. The crystal structure was solved and refined based on single‐crystal X‐ray diffraction data and confirmed by powder X‐ray diffraction. β‐MgSrP3N5O2 crystallizes in the orthorhombic space group Cmme (no. 67, a=8.8109(6), b=12.8096(6), c=4.9065(3) Å, Z=4) and has a structure related to that of Ba2CuSi2O7. DFT calculations were performed to investigate the phase transition from α‐ to β‐MgSrP3N5O2 and to confirm the latter as the corresponding high‐pressure polymorph. Furthermore, the luminescence properties of Eu2+ doped samples of both polymorphs were investigated and discussed, showing blue and cyan emission, respectively (α‐MgSrP3N5O2; λmax=438 nm, fwhm=46 nm/2396 cm−1; β‐MgSrP3N5O2; λmax=502 nm, fwhm=42 nm/1670 cm−1). [ABSTRACT FROM AUTHOR]

Understanding electronic structure properties of narrow-band emitting phosphor materials is important for finding and tailoring novel materials for fabrication of phosphor converted (pc)-LEDs. Thereby, illumination quality can be improved while further reduction in worldwide energy consumption is achieved. In pc-LEDs, the energetic position of the Eu2+ 5d1 states with respect to conduction band and valence band of the host lattice determines the electronic structure and the optical properties, such as thermal quenching and quantum efficiency under application conditions. Here, we experimentally determine the energetic position of the Eu2+ 5d1 state for the narrow-band red-emitting phosphor SrLi2Al2O2N2:Eu2+ (SALON) employing resonant inelastic X-ray scattering (RIXS) measurements. The position of the 5d1 energy level of the dopant Eu2+ is determined directly from RIXS measurements at the N K- and O K-edges and is found to be 0.53 ± 0.04 eV (N K-edge) and 0.48 ± 0.10 eV (O K-edge) below the conduction band. We further use X-ray excited optical luminescence measurements to provide a deeper understanding of the energy levels and radiative processes involved in SALON, as the method allows determination of the 4f7 energy levels thus confirming the narrow-band luminescence in the red spectral region at 610 nm due to the 4f65d1 → 4f7 transition. [ABSTRACT FROM AUTHOR]

The oxonitridosilicate La7Sr[Si10N19O3] : Eu2+ and its substitutional variants RE8‐xAEx[Si10N20‐xO2+x] : Eu2+ with RE=La, Ce; AE=Ca, Sr, Ba and 0≤x≤2 were synthesized starting from REN, SrN/Ca3N2/Ba2N, SiO2, amorphous Si3N4 and Eu2O3 as doping agent at 1600 °C in a radiofrequency furnace. The crystal structure of La7Sr[Si10N19O3] was solved and refined based on single‐crystal X‐ray diffraction data. La7Sr[Si10N19O3] crystallizes in the orthorhombic space group Pmn21 (no. 31). The crystal structures of the isotypic compounds RE8‐xAEx[Si10N20‐xO2+x] were confirmed by Rietveld refinements based on powder X‐ray diffraction data using the single‐crystal data of La7Sr[Si10N19O3] as starting point. Crystal structure elucidation reveals a 3D network of vertex sharing SiN4 and SiN2(N1/2‐x/4O1/2+x/4)2 (0≤x≤2) tetrahedra. When excited with UV to blue light, La7Sr[Si10N19O3] : Eu2+ shows amber luminescence with λem=612 nm and fwhm=84 nm/2194 cm−1, which makes it interesting for application in amber phosphor‐converted light emitting diodes. [ABSTRACT FROM AUTHOR]

The nitridoberylloaluminate Ba2[BeAl3N5]:Eu2+ and solid solutions Sr2−xBax[BeAl3N5]:Eu2+ (x=0.5, 1.0, 1.5) were synthesized in a hot isostatic press (HIP) under 50 MPa N2 atmosphere at 1200 °C. Ba2[BeAl3N5]:Eu2+ crystallizes in triclinic space group P1‾ (no. 2) (Z=2, a=6.1869(10), b=7.1736(13), c=8.0391(14) Å, α=102.754(8), β=112.032(6), γ=104.765(7)°), which was determined from single‐crystal X‐ray diffraction data. The lattice parameters of the solid solution series have been obtained from Rietveld refinements and show a nearly linear dependence on the atomic ratio Sr : Ba. The electronic properties and the band gaps of M2[BeAl3N5] (M=Sr, Ba) have been investigated by a combination of soft X‐ray spectroscopy and density functional theory (DFT) calculations. Upon irradiation with blue light (440–450 nm), the nitridoberylloaluminates exhibit intense orange to red luminescence, which can be tuned between 610 and 656 nm (fwhm=1922–2025 cm−1 (72–87 nm)). In contrast to the usual trend, the substitution of the smaller Sr2+ by larger Ba2+ leads to an inverse‐tunable luminescence to higher wavelengths. Low‐temperature luminescence measurements have been performed to exclude anomalous emission. [ABSTRACT FROM AUTHOR]

We present the first nitridic analogs of micas, namely AESi3P4N10(NH)2 (AE=Mg, Mg0.94Ca0.06, Ca, Sr), which were synthesized under high‐pressure high‐temperature conditions at 1400 °C and 8 GPa from the refractory nitrides P3N5 and Si3N4, the respective alkaline earth amides, implementing NH4F as a mineralizer. The crystal structure was elucidated by single‐crystal diffraction with microfocused synchrotron radiation, energy‐dispersive X‐ray spectroscopic (EDX) mapping with atomic resolution, powder X‐ray diffraction, and solid‐state NMR. The structures consist of typical tetrahedra–octahedra–tetrahedra (T‐O‐T) layers with P occupying T and Si occupying O layers, realizing the rare motif of sixfold coordinated silicon atoms in nitrides. The presence of H, as an imide group forming the SiN4(NH)2 octahedra, is confirmed by SCXRD, MAS‐NMR, and IR spectroscopy. Eu2+‐doped samples show tunable narrow‐band emission from deep blue to cyan (451–492 nm). [ABSTRACT FROM AUTHOR]

The nitridosilicate CaLu[Si4N7–2xCxOx] (x≈0.3) was synthesized by carbothermal reduction and nitridation starting from CaH2, Lu2O3, graphite and amorphous Si3N4 at 1550 °C in a radiofrequency furnace. CaLu[Si4N7–2xCxOx] (x≈0.3) crystallizes isotypically to many previously known MIIMIIISi4N7 compounds in the space group P63mc, as was confirmed by Rietveld refinement based on powder X‐ray diffraction data. Incorporation of carbon into the crystal structure as a result of the carbothermal synthesis route was confirmed by 13C and 29Si MAS NMR spectroscopy. For the first time in the MIIMIIISi4N7 compound class, complementary EDX measurements suggest that simultaneous incorporation of oxygen compensates for the negative charge excess induced by carbon, resulting in an adjusted sum formula, CaLu[Si4N7–2xCxOx] (x≈0.3). When excited with UV‐to‐blue light, CaLu[Si4N7–2xCxOx] (x≈0.3) shows an emission maximum in the blue spectral region (λem=484 nm; fwhm=4531 cm−1) upon doping with Ce3+, whereas Eu2+‐doped CaLu[Si4N7–2xCxOx] (x≈0.3) exhibits a yellow‐green emission (λem=546 nm; fwhm=3999 cm−1). [ABSTRACT FROM AUTHOR]

The recently introduced nitridophosphate synthesis in a hot isostatic press (HIP) enabled simple access to large‐scale product quantities starting from exclusively commercially available starting materials. Herein, we show that this method is suitable for the synthesis of highly condensed functional nitridophosphates, as well. Hence, the syntheses of the nitridophosphate zeolites Ba3P5N10X (X=Cl, Br) are presented as proof of concept for this innovative access. Furthermore, samples of unprecedented Sr3P5N10X (X=Cl, Br) were prepared and characterized to demonstrate the advantages of this synthetic approach over commonly used methods. Luminescence investigations on Eu2+‐doped samples of AE3P5N10X (AE=Sr, Ba; X=Cl, Br) were carried out and characteristics of observed emission bands are discussed. [ABSTRACT FROM AUTHOR]

Recent developments in solid‐state lighting lead to a demand for new phosphors with excellent thermal stability, exhibiting large bandgaps for highly efficient emission. A detailed characterization of the luminescent material AELi2Be4O6:Eu2+ (AE = Ba, Sr) is presented using soft X‐ray absorption spectroscopy, X‐ray emission spectroscopy, X‐ray excited optical luminescence (XEOL) spectroscopy, and density functional theory (DFT) calculations. The experimental indirect bandgap for both BaLi2Be4O6:Eu2+ (BLBO:Eu) and SrLi2Be4O6:Eu2+ (SLBO:Eu) is found to be 6.5 ± 0.3 eV, which agrees well with the DFT calculations (6.8 eV for BLBO:Eu and 7.4 eV for SLBO:Eu). The crucial Eu2+ 5d to conduction band energy separation is determined to be 0.21 ± 0.10 and 0.25 ± 0.10 eV for BLBO:Eu and SLBO:Eu, respectively, using resonant inelastic X‐ray scattering. These measured values are in good agreement with the thermal quenching measurements (0.20 ± 0.03 eV for BLBO:Eu and 0.26 ± 0.03 eV for SLBO:Eu). Finally, the XEOL measurement confirms the Eu2+ 5d14f6 → 4f7 transition, which is responsible for the ultranarrow band (full width at half‐maximum: 25 nm) blue optical luminescence at 455–457 nm for both compounds. With these measurements and calculations, deep insights are gained into the key properties of those two phosphors. [ABSTRACT FROM AUTHOR]

The nitridophosphates AEP8N14 (AE=Ca, Sr, Ba) were synthesized at 4–5 GPa and 1050–1150 °C applying a 1000 t press with multianvil apparatus, following the azide route. The crystal structures of CaP8N14 and SrP8N14 are isotypic. The space group Cmcm was confirmed by powder X‐ray diffraction. The structure of BaP8N14 (space group Amm2) was elucidated by a combination of transmission electron microscopy and diffraction of microfocused synchrotron radiation. Phase purity was confirmed by Rietveld refinement. IR spectra are consistent with the structure models and the chemical compositions were confirmed by X‐ray spectroscopy. Luminescence properties of Eu2+‐doped samples were investigated upon excitation with UV to blue light. CaP8N14 (λem=470 nm; fwhm=1380 cm−1) and SrP8N14 (λem=440 nm; fwhm=1350 cm−1) can be classified as the first ultra‐narrow‐band blue‐emitting Eu2+‐doped nitridophosphates. BaP8N14 shows a notably broader blue emission (λem=417/457 nm; fwhm=2075/3550 cm−1). [ABSTRACT FROM AUTHOR]

Nitridophosphates exhibit an intriguing structural diversity with different structural motifs, for example, chains, layers or frameworks. In this contribution the novel nitridophosphate Sr3P3N7 with unprecedented dreier double chains is presented. Crystalline powders were synthesized using the ammonothermal method, while single crystals were obtained by a high‐pressure multianvil technique. The crystal structure of Sr3P3N7 was solved and refined from single‐crystal X‐ray diffraction and confirmed by powder X‐ray methods. Sr3P3N7 crystallizes in monoclinic space group P2/c. Energy‐dispersive X‐ray and Fourier‐transformed infrared spectroscopy were conducted to confirm the chemical composition, as well as the absence of NHx functionality. The optical band gap was estimated to be 4.4 eV using diffuse reflectance UV/Vis spectroscopy. Upon doping with Eu2+, Sr3P3N7 shows a broad deep‐red to infrared emission (λem=681 nm, fwhm≈3402 cm−1) with an internal quantum efficiency of 42 %. [ABSTRACT FROM AUTHOR]

The ortho‐oxonitridophosphate Ba2PO3N was synthesized under ammonobasic conditions (T = 1070 K, p = 120 MPa) in custom‐built high‐temperature autoclaves, starting from red phosphorus, BaO, NaN3 and KOH. Thus, single crystals of up to several hundred µm were obtained, which were used for single‐crystal X‐ray diffraction. Ba2PO3N [Pnma (no. 62), a = 7.596(2), b = 5.796(1), c = 10.212(3) Å, Z = 4] crystallizes in the β‐K2SO4 structure type with non‐condensed [PO3N]4– ions and is isotypic to its lighter homologues EA2PO3N (EA = Ca, Sr). Powder X‐ray diffraction, energy dispersive X‐ray and Fourier Transformed Infrared spectroscopy corroborate the crystal structure. The optical band gap was determined by means of diffuse reflectance UV/Vis spectroscopy to be 4.3 eV. Eu2+ doped samples show green luminescence (λem = 534 nm, fwhm = 85 nm/2961 cm–1) when irradiated with UV light (λexc = 420 nm). However, Ba2PO3N:Eu2+ shows strong thermal quenching, even at room temperature. [ABSTRACT FROM AUTHOR]