Subsequent Annealing Research Articles

Effect of Annealing Temperature on Microstructure and Properties of Solid Solution Extruded Mg–2.0Zn–1.0Y–0.5Zr Alloys

In this investigation, the effects of different annealing temperatures (180, 200, 220, 240, 260, and 280 °C) on the microstructure evolution and properties of an extruded Mg–2.0Zn–1.0Y–0.5Zr (wt%) magnesium alloys were determined. Optical microscopy (OM), scanning electron microscopy (SEM), immersion corrosion, electrochemical corrosion experiments, and tensile testing were performed. Research has found that combining hot extrusion with subsequent low-temperature annealing significantly improves the strength, plasticity, and corrosion resistance of alloys due to grain refinement and a reduced dislocation density. The alloy was completely recrystallized at an annealing temperature of 240 °C for 4 h after solid solution extrusion, and the grains were fine and uniform, demonstrating the best comprehensive properties. Its corrosion rate, ultimate tensile strength, yield strength, and elongation were 0.454 ± 0.023 mm/y, 346.7 ± 8.9 MPa, 292.4 ± 6.9 MPa, and 19.0 ± 0.4%, respectively. The corrosion mechanism of the specimens under extruded and annealed conditions was analyzed. After annealing at 240 °C for 4 h, the dislocation and bimodal grain structure of the samples were almost eliminated, resulting in uniform and fine grains, which were conducive to the formation of a more uniform and denser oxide film, thus improving the corrosion resistance of the alloy.

P-type Gallium nitride creation through O+ implantation

P-type GaN was successfully achieved by vertically implanting positive monovalent cations of oxygen (O[Formula: see text]) into undoped (native n-type with an electron concentration of [Formula: see text][Formula: see text]cm[Formula: see text]) (0001) monocrystalline GaN. This implantation was carried out with an energy of 200[Formula: see text]keV and a dose of [Formula: see text] ions/cm2. In the absence of subsequent rapid thermal annealing (RTA) or when exposed to RTA at 950°C for 10[Formula: see text]s in a nitrogen ambient environment, temperature-dependent Hall measurements in a vacuum consistently indicated stable p-type conductivity. For the sample that underwent subsequent RTA, the room-temperature Hall hole concentration measured [Formula: see text][Formula: see text]cm[Formula: see text], the Hall resistivity was 0.44[Formula: see text][Formula: see text][Formula: see text]⋅[Formula: see text]cm, the Hall hole mobility reached 17.81[Formula: see text]cm2[Formula: see text]⋅[Formula: see text]V[Formula: see text][Formula: see text]⋅[Formula: see text]s[Formula: see text], and the acceptor ionization energy was determined to be 0.08[Formula: see text]eV. The doping efficiency was calculated at 5.5%. O[Formula: see text] ions effectively serve as acceptors, whether annealed or not. The p-type conductivity induced by O[Formula: see text] implantation in GaN is notably advantageous and holds practical significance for the ongoing development of future device technology.

Tellurization of Pd(111) revisited: Formation of a TePd[formula omitted] surface alloy but no PdTe[formula omitted] monolayer

In a recent publication [2D Materials, 8, 045033 (2021)], it was reported that the growth of a monolayer PdTe2 in ultra-high vacuum could be achieved by deposition of tellurium on a palladium (111) crystal surface and subsequent thermal annealing. By means of low-energy electron diffraction intensity (LEED-IV) structural analysis, we show that the obtained 3×3R30° superstructure is in fact a TePd2 surface alloy. Attempts to produce a PdTe2 layer in ultra-high vacuum by increasing the Te content on the surface were not successful.

Photoluminescence studies of the charge states of nitrogen vacancy centers in diamond after arsenic ion implantation and subsequent annealing

In this work, nitrogen vacancy (NV) centers of high nitrogen diamond implanted with arsenic ions were investigated by photoluminescence spectroscopy. The transition of the NV center charge state was discussed by the regularly changing laser excitation power and measurement temperature following high-temperature annealing. After high-temperature annealing, the amorphous layer generated by arsenic ion implantation is transformed into a graphitization layer, resulting in a decrease in the NV yield. The electric neutral NV (NV0) center and negatively charged NV (NV−) center are affected by both radiation recombination and Auger recombination with increasing laser power. Accompanied by the increasing measurement temperature, the intensities of NV centers gradually decreased and eventually quenched. In addition, the charge states of NV− and NV0 centers were undergoing a transition. The zero phonon line positions of NV centers were also red shift, it was attributed to the dominant role of electron–phonon interaction in the temperature-dependent displacement of diamond energy gaps. The full width at half maxima of NV center were broadened significantly at higher temperatures.

Low temperature crystallization of atomic-layer-deposited SrTiO3 films with an extremely low equivalent oxide thickness of sub-0.4 nm

Despite SrTiO3(STO) possessing a high dielectric constant, its application as a capacitor dielectric in dynamic random-access memory(DRAM) capacitors faces challenges due to the high-temperature annealing for crystallization, its compositional inhomogeneity, and the high leakage currents of STO films. To address these issues, we employ atomic layer deposition(ALD) of STO films onto Pt substrates at elevated temperatures(340–380 °C). The use of low-reactivity Pt electrodes effectively mitigates the initial growth of excess Sr, ensuring enhanced compositional uniformity along the film growth direction. Coupled with ALD at high temperatures, this approach facilitates the crystallization of STO films in the as-grown state, further enhancing the crystallinity with increasing film thickness. Subsequent low-temperature post-deposition annealing (PDA) at 400 and 500 °C achieves full crystallization. This process results in a remarkable increase in the dielectric constant, reaching approximately 150. Furthermore, the absence of microcracks after PDA, attributed to the formation of adequately dense films, contributes to substantially improved dielectric properties. Consequently, these STO films exhibit an exceptionally low equivalent oxide thickness of 0.34 nm coupled with an ultralow leakage current of 3.7 × 10−8 A/cm2 at an operation voltage of 0.8 V, promising for advancing DRAM capacitors. This study presents a pathway for the sustainable scaling of DRAMs, addressing challenges in ALD-grown STO films.

Reversible wettability of thermally treated Hanji decorated with supersonically sprayed ZnO nanoparticles

In this study, we aimed at transforming naturally superhydrophilic Hanji, a traditional Korean Han paper into its superhydrophobic version. This change is crucial for applications requiring water damage resistance, such as mold growth, abrasion, and degradation. The resulting superhydrophobic Hanji shows potential for diverse applications, including fabricating wallpaper, traditional window covers, and high-end wrapping paper. To achieve this, ZnO nanoparticles (NPs) were deposited on the surface of Hanji via supersonic spraying, resulting in morphological curvatures capable of accommodating nanoscale air pockets. Additionally, supersonic spraying facilitated the robust adhesion of ZnO NPs to the Hanji cellulose fibers. Notably, the hydroxyl groups from both ZnO and Hanji were removed through subsequent annealing, resulting in superhydrophobic ZnO-Hanji. The annealing-induced shrinkage and densification of Hanji enhanced its superhydrophobicity, a property not achieved using regular A4 paper. This substantiated the unique benefits of using Hanji to realize superhydrophobicity. The superhydrophobicity reverted to superhydrophilicity upon exposure to ultra-violet irradiation, initiating reactions of the –OH group from atmospheric moisture with electron–hole pairs on the ZnO surfaces. Consequently, tunable/reversible wettability of ZnO-decorated Hanji was achieved via simple supersonic spraying and annealing, without any chemical modifications.

In-situ welding and thermal activation enabled robust nanofibers based triboelectric nanogenerator for sustainable energy harvesting

Nanofiber-based triboelectric nanogenerators (TENGs) show great promise in energy harvesting and sensing applications. However, the poor strength and the instability of the nanofiber structures lead to the constraints on the durability and the lack of stability in the output performance. In this study, BaTiO3@PVDF-HFP nanofibers were prepared by electrospinning, in which BaTiO3 nanoparticles enhanced the charge trapping ability of the nanofibers and provided nucleation sites for β-phase growth. Subsequent solvent and annealing treatment in-situ welded the nanofibers, which greatly improved the mechanical strength and stability of the nanofiber membranes. The annealing process further thermally activated the electroactive β-phase in the PVDF-HFP, which increased the surface charge density of the nanofibers. A flexible TENG based on BaTiO3@PVDF-HFP-p nanofiber was prepared to harvest mechanical energy, which could achieve a maximum output of 482.5 V and 1.9 W m−2, the voltage is more than 1.2–1.5 times higher compared to uncrosslinked nanofibers. The BaTiO3@PVDF-HFP-p-based TENG maintains ultra-stable Voc generation over 7000 cycles compared to the nanofibers without solvent and annealing treated. Finally, its practical application in harvesting ambient mechanical energy was demonstrated, which can harvest wind energy to power LEDs and small electronic devices such as temperature and humidity sensors.

Molecular dynamics simulation study of nitrogen vacancy color centers prepared by carbon ion implantation into diamond

Nitrogen vacancy (NV) color centers in diamond have useful applications in quantum sensing and fluorescent marking. They can be generated experimentally by ion implantation, femtosecond lasers, and chemical vapor deposition. However, there is a lack of studies of the yield of NV color centers at the atomic scale. In the molecular dynamics simulations described in this paper, NV color centers are prepared by ion implantation in diamond with pre-doped nitrogen and subsequent annealing. The differences between the yields of NV color centers produced by implantation of carbon (C) and nitrogen (N) ions, respectively, are investigated. It is found that C-ion implantation gives a greater yield of NV color centers and superior location accuracy. The effects of different pre-doping concentrations (400–1500 ppm) and implantation energies (1.0–3.0 keV) on the NV color center yield are analyzed, and it is shown that a pre-doping concentration of 1000 ppm with 2 keV C-ion implantation can produce a 13% yield of NV color centers after 1600 K annealing for 7.4 ns. Finally, a brief comparison of the NV color center identification methods is presented, and it is found that the error rate of an analysis utilizing the identify diamond structure + coordination analysis method is reduced by about 7% compared with conventional identification methods.

Achieving Excellent Strength–Ductility Synergy by Tailoring the Grain Size Distribution in a Metastable Austenitic Stainless Steel

Ultrafine/fine‐grained austenitic stainless steel (ASS) is prepared through severe cold rolling (CR) and subsequent annealing. The microstructure evolution and tensile deformation behavior is investigated, focusing on the influence of grain size distribution on the mechanical properties and strain‐hardening behavior of the ASS. In the results, it is revealed that obvious ultrafine/fine‐grained hierarchical microstructure forms after annealing at 650 °C for 80 and 110 min, respectively. And, the CR‐80 sample with more ultrafine grains (UFGs) (86%) exhibits good combination of strength and ductility. The yield strength (YS), ultimate tensile strength, and total elongation are 954 MPa, 1030 MPa, and 43.4%, respectively. The high YS mainly originates from the retained martensite and grain refinement strengthening, while the ductility enhancement can be attributed to the postponed transformation‐induced plasticity (TRIP) effect, which is a consequence of the significant number fraction of UFGs in the hierarchical microstructure. In this study, a new strategy is provided to solve the strength–ductility tradeoff in TRIP‐assisted metallic materials by tailoring the grain size distribution.

Design strategy to simultaneously enhance electrical conductivity and strength: Cold-drawn copper-based composite wire with in-situ graphene

We proposed a unique wire-production process by rolling up and drawing chemical vapor deposition copper/graphene (Cu/Gr) foils, and a good strength-conductivity trade-off was achieved originating from the dispersed Gr in Cu matrix and the high-quality heterointerfaces. The 1.14 mm cold-drawn composite wire exhibited a tensile strength of 455 ± 5 MPa and a conductivity of 98.18 ± 0.16 % of the International Annealed Copper Standard (IACS), and the tensile strength was 250 ± 2 MPa with a satisfied electrical conductivity of 101.68 ± 0.52 % IACS upon annealing. The microstructure involution during the preparing process was revealed, and the reinforcement mechanisms in the yield strength and conductivity due to the introduced Gr were clarified. The results indicated that the Gr plays a role in pinning dislocations and preventing grain boundary movement during deformation and the subsequent annealing, thereby enhancing the strength of the Cu matrix. Meanwhile, the Cu-Gr coupling interfaces exhibited an electronic doping effect, enhancing the conductive properties. Our work presented a feasible method for preparing Cu/Gr composite wire with comprehensive electrical conductivity and strength optimization.

Microstructure evolution and twinning behavior of AZ31 magnesium alloy sheets with bimodal texture during cold deep-drawing deformation

Cold deep drawing experiments were conducted on AZ31 magnesium (Mg) alloy sheets with bimodal texture, which were prepared by the newly developed equal channel angular rolling and continuous bending and subsequent annealing (ECAR-CB-A) process. The results showed that the sheet could be successfully deep-drawn at a limiting drawing ratio (LDR) of 1.6, and the forming performance was better than that of the as-rolled base-texture sheet at room temperature. The microstructure after deep-drawing deformation was investigated by X-ray diffraction (XRD), optical microstructure (OM), and electron backscatter diffraction (EBSD). A large number of {10−12} extension twins (ETs) are observed in the outer shoulder region. Due to the bimodal texture, the activated {10−12} ET variants and the basal slip within the matrix have a higher Schmid Factor (SF) value when the outer shoulder region is under radial tensile stress, this enables the shoulder of the drawn cup to maintain good deformability. In addition, some {10−11} contraction twins (CTs) and {10−11}-{10−12} double twins (DTs) can be observed in this region, which is activated by the local strain accommodation between the twins and the slip systems, and the multiaxial stress. Due to different stress conditions, the volume fractions of {10−12} ETs in the inner shoulder region are less than that in the outer region. The stress concentration caused by {10−11}-{10−12} DTs that occurred in the edge region is the reason for the fracture of the drawn cups at a drawing ratio(DR) of 1.7.

Processing of high-strength thermal-resistant Al-2.2% cerium-1.3% lanthanum alloy rods with high electric conductivity by High Pressure Torsion Extrusion

A novel severe plastic deformation (SPD) process of High Pressure Torsion Extrusion (HPTE) was applied to the rods of the Al-2.2 wt.% Ce-1.3 wt.% La (Al–3.5RE) alloy. The microstructure, microhardness, the mechanical strength, thermal stability, and electrical conductivity of the alloy after HPTE and subsequent annealing have been investigated. It was demonstrated that HPTE processing can simultaneously increase yield strength from 127 to 225 MPa and electrical conductivity from 54.7% IACS to 55.7% IACS in this alloy. Such a remarkable combination of properties was achieved thanks to significant refinement of microstructure constituents: grain size of Al matrix was reduced down to 0.9 µm and initially continuous network of Al11RE3 phase was broken to micrometer- and nanometer-sized particles. Furthermore, the yield strength of the HPTE-processed Al–3.5 RE alloy remains stable at 230 °C for 1 h due to micrometer- and nanometer-sized particles that pin the grain boundaries. Therefore, HPTE processing of Al–RE alloys has a high application potential in the electric power industry.Graphical abstract

Developing a novel Mg[sbnd]2Zn[sbnd]3Li[sbnd]1Gd alloy sheet with high room-temperature formability by introducing an elliptical texture distribution

In recent years, modification of texture distribution has been considered a valid approach to improve the room-temperature (RT) formability of magnesium (Mg) alloys. In this study, a novel Mg2Zn3Li1Gd alloy sheet with weak elliptical-texture was fabricated by cold rolling and subsequent annealing, and it showed an excellent Erichsen (IE) value near 7.1 mm. Both quasi-in-situ electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM) analysis indicate that considerable basal and pyramidal dislocations can be activated in the cold rolling process. During annealing, these dislocations can induce nucleation and then cause preferential misorientation relationships around 〈uvt0〉 concerning the nuclei and parent grains, which can facilitate the formation of elliptical texture. Furthermore, the particle-stimulated nucleation (PSN) mechanism and the co-segregation of Zn and Gd at grain boundaries (GB) further weak texture intensity. Finally, the mechanical properties of the Mg2Zn3Li1Gd alloy sheet are significantly improved.

Stabilizing metastable ferroelectric tungsten trioxide phase at room temperature via solvothermal synthesis and millisecond pulsed laser irradiation

Epsilon tungsten trioxide (ε-WO3) has drawn much attention for its unique gas sensing and ferroelectric properties. However, the strong metastability of ε-phase makes it extremely difficult to stabilize the phase at room temperature. For a long time, it was believed that the ε-phase can only be stabilized by rapid solidification processing. In this study, ε-WO3 was stabilized by employing solvothermal synthesis and subsequent annealing, with the help of Cr- and Ti-dopants. Structural characterization using XRD, Raman and TEM analysis revealed that the as-annealed powders are a mixture of ε-WO3 and γ-WO3 and the fraction of ε-WO3 is directly correlated with the Cr- and Ti-doping levels. Rietveld refinement suggests that the maximum obtainable fractions of ε-phase in as-annealed WO3 are ∼68 % for Cr-doping and ∼87 % for Ti-doping. The growth mechanism is that solvothermal synthesis produced Cr- and Ti-doped W18O49 and subsequent annealing resulted in phase transition from W18O49 to ε-WO3. The XPS analysis reveals the phase stabilization mechanism to involve the interstitial sites of WO3 being occupied by Cr3+ and Ti4+ dopants, resulting in structure distortions. The fraction of ε-WO3 can be further improved to almost 100 % by introducing kinetic constraints using pulsed laser irradiation to rapidly melt and solidify the WO3 (in several milliseconds). A viable solvothermal synthesis route for ε-WO3 and the feasibility to produce ε-phase via additive manufacturing are illustrated in this work.

Unexpected texture transition induced by grain growth during static annealing of a dilute Mg-1Al alloy

Conventional rolled Mg-Al alloy sheets typically exhibit strong basal textures that remain and may even strengthen after recrystallization annealing due to the preferential growth of basal-oriented grains, resulting in poor formability at room temperature. Therefore, the knowledge of recrystallization and grain growth is critical for modifying textures of Mg-Al alloy sheets. The static recrystallization and texture evolution in a cold-rolled dilute Mg-1Al (wt.%) alloy during various annealed temperatures ranging from 300 °C to 450 °C, have been investigated using the quasi in-situ electron backscatter diffraction (EBSD) method. The as-rolled Mg-1Al alloy shows a dominant basal texture, which weakens and broadens in the rolling direction (RD) during the subsequent annealing, accompanied by the formation of 〈101¯0〉 texture component. Particularly, the 〈101¯0〉 texture component is more pronounced after annealing at high temperatures. The quasi in-situ EBSD results show that recrystallized grains are mainly induced by shear bands, which exhibit a wide spectrum of orientations with c-axis tilt angles ranging 20°-45° from the normal direction (ND). Orientations of shear band-induced recrystallized grains are retained during the entire recrystallization process, resulting in a reduction in the texture intensity. Moreover, recrystallized grains belonging to the 〈101¯0〉 texture component grow preferentially compared to those with other orientations, which is attributed to low energy grain boundaries, especially grain boundaries with ∼30° misorientation angles. Furthermore, the high temperature annealing facilitates the rapid growth of grain boundaries having a 30° misorientation angle, leading to the occurrence of distinct 〈101¯0〉 texture after annealing at 450 °C for 1 h. The results provide insights for texture modification of rare earth-free low-alloyed Mg alloys by controlling annealing parameters.

Structure-led manifestation of photocatalytic activity in magnetically recoverable spinel CuFe2O4 nanoparticles and its application in degradation of industrial effluent dyes under solar light

An efficient removal of the photocatalysts used in the decontamination of water is crucial after its application beside its expected visible light sensitive activities. This study presents the synthesis of magnetically separable CuFe2O4 nanoparticles (CFNPs) with enhanced photoactivity under AM 1.5 G sunlight. A simple two-step process involving co-precipitation and hydrothermal treatment is employed, with subsequent annealing at temperatures from 200 °C to 1000 °C to synthesize the CFNPs. The characteristic features of the highest photoactive tetragonal phase of CFNP are confirmed by powder XRD studies with Rietveld refinement. This scheme strategically controls the growth of a highly photoactive tetragonal phase with predominant (224) facets over other less active facets in cubic CuFe2O4. Mott–Schottky analysis confirms the p-type semiconducting nature of CFNPs. A favourable direct optical band gap of 1.73 eV, as well as photoluminescence emission quenching for visible photons, show that the (224) oriented CFNPs are good photocatalysts in the visible spectrum with demonstrated organic dye degradations, including methylene blue and others. A density functional theory-based approach validates that the adsorption of such dye is thermodynamically more favourable on (224) facets of CuFe2O4 to facilitate the redox action by the excitons.

Thermal annealing gradient tailoring on ammonium nitrate-capped CdS nanospheres synthesized via green precipitation

This study explores the impact of thermal annealing gradients on the physical properties and structural evolution of cadmium sulphide (CdS) nanospheres capped with ammonium nitrate as a modifier, which were fabricated through precipitation and subsequent annealing within 160–480 °C temperature range. The properties were characterized using X-ray diffraction (XRD), ultraviolet–visible (UV–Vis), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques The XRD results show that the present CdS exhibits superior crystallinity compared to pure CdS without capping, transitions from a cubic to a hexagonal phase structure, and increases in crystallite size and crystallinity with increasing temperature. The FTIR spectra postulate that a vibrational band presence evidences ammonium nitrate capping on CdS, with another distinct band that represents CdS in the lower wavenumber region, both intensifying at elevated temperatures. The UV–Vis analysis reveals that CdS exhibits strong ultraviolet (UV) absorption suitable for effective photoreaction under UV light and has a broader band gap compared to bulk CdS. SEM images show an extensive distribution of homogeneous nanospheres over the surface, with increased growth in size when capped with ammonium nitrate and at higher temperatures. As validated by TGA and DSC results, CdS with a smaller crystallite size improves thermal stability and energy transfer, as evidenced by reduced weight loss and a lower endothermic temperature, respectively. Varying the annealing temperature with ammonium nitrate capping can improve the structural and physical properties of CdS, which are beneficial for varied applications such as optoelectronics, energy storage, and photocatalysts.

Synthesis of graphene mesosponge using CaO nanoparticles formed from CaCO3

While graphene mesosponge (GMS) is a new type of mesoporous material with the potential for a variety of applications, its synthesis process requires costly templates such as Al2O3 and MgO nanoparticles. In this study, we present a new synthesis method for GMS, which achieves a high specific surface area of 1720 m2 g1 by employing calcium oxide (CaO) nanoparticles as templates. The CaO nanoparticles with an approximate diameter of 86 nm are formed through the thermal decomposition of calcium carbonate nanoparticles. However, the calcium carbonate nanoparticles contain a small amount of Mg (2 wt %), and the thermal decomposition process also yields impurities, including Mg. When the CaO nanoparticles, including the Mg-based impurities, are subjected to chemical vapor deposition, the CaO surface can be coated with a thin carbon layer, primarily consisting of single-layer graphene through the specific catalysis of the CaO surface in facilitating the CH4-to-C conversion reactions. However, at the same time, the presence of Mg-based impurities leads to the formation of low-crystalline carbons, which have a detrimental effect on the subsequent high-temperature annealing at 1800 °C, following the template removal process, resulting in an excessive number of edge sits in the GMS. We have found that the harmful low-crystalline carbons can be eliminated through heat treatment in air at 350 °C. By adopting such a removal process, high-quality GMS with a minimal number of edge sites can be produced.

Evolution of Structure and Texture Formation in Thermomechanically Treated Ti-Zr-Nb Shape Memory Alloys

Biomedical Ti-22Nb-6Zr, Ti-18Zr-15Nb, and Ti-41Zr-12Nb (at.%) shape memory alloys were subjected to cold rolling (CR) and subsequent post-deformation annealing (PDA). The evolutions of phase and structure states, crystallographic texture, and crystallographic limit of recovery strain were studied using EBSD, TEM, and XRD analyses. The study found that CR (e = 1.5) and PDA at 800 °C for 30 min results in fine- and coarse-grained structures. Severe CR (e = 3.0) and PDA at 550 °C for 5 min results in a recrystallized, equiaxed, predominantly ultrafine-grained structure of the β-phase with a small amount of low-angle boundaries. Increasing the degree of CR from moderate (e = 0.3) to severe (e = 3.0) results in a favorable strong {111}β<110>β recrystallization texture. Alloys with low Zr content are more susceptible to this type of crystallographic texture formation during TMT, primarily due to a higher Nb content. The Ti-41Zr-12Nb alloy shows the highest crystallographic limit of recovery strain (εrmax ≈ 6%). The limit decreases to ≈5% (for Ti-18Zr-15Nb) and ≈3% (for Ti-22Nb-6Zr) when transitioning from high- to low-Zr alloys. The transition of Ti-Zr-Nb alloys from coarse-grained to ultrafine-grained structures of the β-phase and a decrease in grain size do not affect the crystallographic limit of recovery strain in the studied grain size ranges.

Na3Ge2P3: A Zintl Phase Featuring [P3Ge-GeP3] Dimers as Building Blocks.

Recently, ternary lithium phosphidotetrelates have attracted interest particularly due to their high ionic conductivities, while corresponding sodium and heavier alkali metal compounds have been less investigated. Hence, we report the synthesis and characterization of the novel ternary sodium phosphidogermanate Na3Ge2P3, which is readily accessible via ball milling of the elements and subsequent annealing. According to single crystal X-ray structure determination, Na3Ge2P3 crystallizes in the monoclinic space group P21/c (no. 14.) with unit cell parameters of a = 7.2894(6) Å, b = 14.7725(8) Å, c = 7.0528(6) Å, β = 106.331(6)° and forms an unprecedented two-dimensional polyanionic network in the b/c plane of interconnected [P3Ge-GeP3] building units. The system can also be interpreted as differently sized ring structures that interconnect and form a two-dimensional network. A comparison with related ternary compounds from the corresponding phase system as well as with the binary compound GeP shows that the polyanionic network of Na3Ge2P3 resembles an intermediate step between highly condensed cages and discrete polyanions, which highlights the structural variety of phosphidogermanates. The structure is confirmed by 23Na- and 31P-MAS NMR measurements and Raman spectroscopy. Computational investigation of the electronic structure reveals that Na3Ge2P3 is an indirect band gap semiconductor with a band gap of 2.9 eV.