Synthesis of Hexagonal Yb3+,Er3+‐Doped NaYF4 Nanocrystals at Low Temperature

Nanocrystals of NaYF₄ doped with Yb³⁺ and Er³⁺ are synthesized in oleylamine using Y₂(CO₃)₃, Yb₂(CO₃)₃, Er₂(CO₃)₃, Na₂CO₃, and NH₄F as precursors. In contrast to other starting materials normally used for such syntheses, these precursors react even at room temperature to form hexagonal‐phase (β‐phase) NaYF₄:Er,Yb nanoparticles. Cubic‐phase (α‐phase) NaYF₄:Yb,Er particles are formed only at elevated temperatures (>250 °C). The formation of the cubic phase at high temperatures can be suppressed by replacing pure oleylamine with oleic acid/oleylamine mixtures. Under optimized reaction conditions, particles with an average particle size of about 7 nm are generated in 84% yield. Heat treatment (30 min, 280 °C) of the particles significantly increases the luminescence efficiency. A transparent solution of the heat‐treated, nanometer‐sized phosphor in toluene shows intense visible light emission upon excitation in the near infrared.     

Dual Phase‐Controlled Synthesis of Uniform Lanthanide‐Doped NaGdF4 Upconversion Nanocrystals Via an OA/Ionic Liquid Two‐Phase System for In Vivo Dual‐Modality Imaging

A novel OA/ionic liquid two‐phase system combining the merits of thermal decomposition method, the IL‐based strategy, and the two‐phase approach is introduced to synthesize high‐quality lanthanide‐doped NaGdF₄ upconversion nanocrystals with different crystal‐phases in OA‐phase and IL‐phase through a one‐step controllable reaction. Oil‐dispersible cubic‐phase NaGdF₄:Yb, Er (Ho, Tm) nanocrystals with ultra‐small size (～5 nm) and monodispersity are obtained in the OA phase of the two‐phase system via an IL‐based reaction. More importantly, water‐soluble hexagonal‐phase NaGdF₄:Yb, Er nanocrystals are obtained in the same system simply by adopting an extremely facile method to complete the dual phase‐transition (crystal‐phase transition and OA‐phase to IL‐phase transition) simultaneously. The synthesized lanthanide‐doped NaGdF₄ upconversion nanocrystals are effective for dual‐mode UCL imaging and CT imaging in vivo.     

Synthesis of NaYF4 Nanocrystals with Predictable Phase and Shape

In this Full Paper, a water/alcohol/oleic acid system was developed to prepare NaYF₄ nanocrystals with predictable size, shape and phase. The structural and kinetic factors that govern the phase and shape evolution of NaYF₄ nanocrystals have been carefully studied, and the influence of NaF to Y³⁺ ratio, reaction time and temperature on the phase and shape evolution of the as‐prepared NaYF₄ samples was systematically investigated and discussed. It was found that the NaF to Y³⁺ ratio was responsible for the shape evolution while temperature and reaction time was the key for the phase control of the NaYF₄ nanocrystals. This study would be suggestive for the precisely controlled growth of inorganic nanocrystals, especially for those usually crystallizing in diverse crystal structures.     

Electrospinning Preparation and Drug‐Delivery Properties of an Up‐conversion Luminescent Porous NaYF4:Yb3+, Er3+@Silica Fiber Nanocomposite

Up‐conversion (UC) luminescent porous silica fibers decorated with NaYF₄:Yb³⁺, Er³⁺ nanocrystals (NCs) (denoted as NaYF₄:Yb³⁺, Er³⁺@silica fiber) are prepared by the electrospinning process using cationic surfactant P123 as a template. Monodisperse and hydrophobic oleic acid capped β‐NaYF₄: Yb³⁺, Er³⁺ NCs are prepared by thermal decomposition methodology. Then, these NCs are transferred into aqueous solution by employing cetyltrimethylammonium bromide (CTAB) as secondary surfactant. The water‐dispersible β‐NaYF₄:Yb³⁺, Er³⁺ NCs are dispersed into precursor electrospinning solution containing P123 and tetraethyl orthosilicate (TEOS), followed by preparation of precursor fibers via electrospinning. Finally, porous α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber nanocomposites are obtained after annealing the precursor fibers containing β‐NaYF₄:Yb³⁺, Er³⁺ at 550 °C. The as‐prepared α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber possesses porous structure and UC luminescence properties simultaneously. Furthermore, the obtained nanocomposites can be used as a drug delivery host carrier and drug storage/release properties are investigated, using ibuprofen (IBU) as a model drug. The results indicate that the IBU–loaded α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber nanocomposites show UC emission of Er³⁺ under 980 nm NIR laser excitation and a controlled release property for IBU. Meanwhile, the UC emission intensity of IBU–α‐NaYF₄:Yb³⁺, Er³⁺@silica fiber system varies with the released amount of IBU.     

Synthesis and Optical Properties of KYF4/Yb,Er Nanocrystals,and their Surface Modification with Undoped KYF4

KYF₄/Yb³⁺, Er³⁺ nanocrystals with a mean diameter of approximately 13 nm were synthesized at 200 °C in the high boiling organic solvent N‐(2‐hydroxyethyl)ethylenediamine (HEEDA). The particles crystallize in the cubic phase known from α‐NaYF₄ and form transparent colloidal solutions in tetraethylene glycol (TEG) or propanol. Solutions containing 1 wt % of the nanocrystals in TEG display visible upconversion emission upon continuous wave (CW) excitation at 978 nm. Growing undoped KYF₄ on the surface of the KYF₄/Yb³⁺, Er³⁺ nanocrystals increases the upconversion efficiency by more than a factor of 20. The XRD data of these particles, display a slight increase in the mean particle size from 13 to 15.5 nm, indicating that only a part of the subsequently added KYF₄ shell material is deposited onto the particle surface. Nevertheless the performed surface modification obviously leads to core/shell structured particles.     

Up‐Conversion Luminescent and Porous NaYF4:Yb3+, Er3+@SiO2 Nanocomposite Fibers for Anti‐Cancer Drug Delivery and Cell Imaging

Up‐conversion (UC) luminescent and porous NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanocomposite fibers are prepared by electrospinning process. The biocompatibility test on L929 fibrolast cells reveals low cytotoxicity of the fibers. The obtained fibers can be used as anti‐cancer drug delivery host carriers for investigation of the drug storage/release properties. Doxorubicin hydrochloride (DOX), a typical anticancer drug, is introduced into NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanocomposite fibers (denoted as DOX‐NaYF₄:Yb³⁺, Er³⁺@SiO₂). The release properties of the drug carrier system are examined and the in vitro cytotoxicity and cell uptake behavior of these NaYF₄:Yb³⁺, Er³⁺@SiO₂ for HeLa cells are evaluated. The release of DOX from NaYF₄:Yb³⁺, Er³⁺@SiO₂ exhibits sustained, pH‐sensitive release patterns and the DOX‐NaYF₄:Yb³⁺, Er³⁺@SiO₂ show similar cytotoxicity as the free DOX on HeLa cells. Confocal microscopy observations show that the composites can be effectively taken up by HeLa cells. Furthermore, the fibers show near‐infrared UC luminescence and are successfully applied in bioimaging of HeLa cells. The results indicate the promise of using NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanocomposite fibers as multi‐functional drug carriers for drug delivery and cell imaging.     

Accurate Control of Core–Shell Upconversion Nanoparticles through Anisotropic Strain Engineering

The effect of anisotropic interfacial strain on epitaxial growth and optical emission of sodium rare‐earth fluoride core–shell nanoparticles is investigated. A variety of sodium rare‐earth fluoride shells are grown on hexagonal‐phase NaYF₄:Yb/Er core for providing anisotropic tuning of interfacial strains. Using high‐resolution transmission electron microscopy and X‐ray diffraction characterizations, the correlations between the epitaxial habits and the interfacial strains are quantitatively addressed. Furthermore, the growth affinity is tuned by controlling precursor concentration in conjunction with Ca²⁺ doping, which results in accurate regulation of the anisotropic growth. The lattice strain resulting from mismatched epitaxy is found to enhance luminescence response of the nanoparticles to temperature change.     

Large Upconversion Enhancement in the “Islands” Au–Ag Alloy/NaYF4: Yb3+, Tm3+/Er3+ Composite Films,and Fingerprint Identification

The surface plasmon (SP) modulation is a promised way to highly improve the strength of upconversion luminescence (UCL) and expand its applications. In this work, the “islands” Au–Ag alloy film is prepared by an organic removal template method and explored to improve the UCL of NaYF₄: Yb3+, Tm³⁺/Er³⁺. After the optimization of Au–Ag molar ratio (Au_1.25–Ag_0.625) and the size of NaYF₄ nanoparticles (NPs, ≈7 nm), an optimum enhancement as high as 180 folds is obtained (by reflection measurement) for the overall UCL intensity of Tm³⁺. Systematic studies indicate that the UCL enhancement factor (EF) increases with the increased size of metal NPs and the increase of diffuse reflection, with the decreased size of NaYF₄ NPs, with the decreased power density of excitation light and with improving order of multiphoton populating. The total decay rate varies only ranging of about 20% while EF changes significantly. All the facts above indicate that the UCL enhancement mainly originates from coupling of SP with the excitation electromagnetic field. Furthermore, the fingerprint identification based on SP‐enhanced UCL is realized in the metal/UC system, which provides a novel insight for the application of the metal/UC device.     

Electrochromic Switch Devices Mixing Small‐ and Large‐Sized Upconverting Nanocrystals

The hasty progress in smart, portable, flexible, and transparent integrated electronics and optoelectronics is currently one of the driving forces in nanoscience and nanotechnology. A promising approach is the combination of transparent conducting electrode materials (e.g., silver nanowires, AgNWs) and upconverting nanoparticles (UCNPs). Here, electrochromic devices based on transparent nanocomposite films of poly(methyl methacrylate) and AgNWs covered by UCNPs of different sizes and compositions are developed. By combining the electrical control of the heat dissipation in AgNW networks with size‐dependent thermal properties of UCNPs, tunable electrochromic transparent devices covering a broad range of the chromatic diagrams are fabricated. As illustrative examples, devices mixing large‐sized (>70 nm) β‐NaYF₄:Yb,Ln and small‐sized (<15 nm) NaGdF₄:Yb,Ln@NaYF₄ core@shell UCNPs (Ln = Tm, Er, Ce/Ho) are presented, permitting to monitor the temperature‐dependent emission of the particles by the intensity ratio of the Er^{3+ 2}H_11/2 and ⁴S_3/2 → ⁴I_15/2 emission lines, while externally controlling the current flow in the AgNW network. Moreover, by defining a new thermometric parameter involving the intensity ratio of transitions of large‐ and small‐sized UCNPs, a relative thermal sensitivity of 5.88% K^?1 (at 339 K) is obtained, a sixfold improvement over the values reported so far.     

Anomalous Raman Scattering of Colloidal Yb3+,Er3+ Codoped NaYF4 Nanophosphors and Dynamic Probing of the Upconversion Luminescence

Size‐dependent Raman spectra of the hexagonal (β)‐phase Yb³⁺,Er³⁺ codoped NaYF₄ nanophosphors and dynamic probing of the upconversion luminescence (UCL) are reported. Raman scattering results show the normal red shifts of Raman peaks but anomalous line narrowing with decreasing the particle sizes. The phonon confinement effects are believed to be dominated by the surface vibrational energies in affecting UCL. Dynamic decay data are then applied to quantitatively verify the surface effects and size‐dependent UCL. Dynamic probing is shown to be an efficient tool to both qualitatively and quantitatively characterize the upconversion nanophorphors (UCNPs) that have no “quantum efficiency.” The findings are relevant to the engineering of the nanostructures of the UCNPs for the applications of the bioimaging and photodynamic therapy.     

NaYF_4:Er/Yb上转换材料的优化制备及其特性研究

针对第3代太阳电池用上转换材料,采用改良的水热技术优化制备了掺杂稀土离子的纳米氟化钇钠(NaYF4)上转换荧光材料。主要关注了有机溶剂和螯合剂对制备上转换材料性能的影响。测试结果表明:有机溶剂乙醇可以有效地抑制YF3等杂峰;螯和剂乙二胺四乙酸二钠(EDTA)可以分散颗粒达到增大颗粒表面积的作用;制备获得了具有六角晶向结构的Yb3+/Er3+共掺上转换材料,其上转换发射出能够被太阳电池有效吸收利用的红光(653 nm)和绿光(5205、40 nm)。     

Room‐Temperature Partial Conversion of α‐FAPbI3 Perovskite Phase via PbI2 Solvation Enables High‐Performance Solar Cells

The two‐step conversion process consisting of metal halide deposition followed by conversion to hybrid perovskite has been successfully applied toward producing high‐quality solar cells of the archetypal MAPbI₃ hybrid perovskite, but the conversion of other halide perovskites, such as the lower bandgap FAPbI₃, is more challenging and tends to be hampered by the formation of hexagonal nonperovskite polymorph of FAPbI₃, requiring Cs addition and/or extensive thermal annealing. Here, an efficient room‐temperature conversion route of PbI₂ into the α‐FAPbI₃ perovskite phase without the use of cesium is demonstrated. Using in situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) and quartz crystal microbalance with dissipation (QCM‐D), the conversion behaviors of the PbI₂ precursor from its different states are compared. α‐FAPbI₃ forms spontaneously and efficiently at room temperature from P₂ (ordered solvated polymorphs with DMF) without hexagonal phase formation and leads to complete conversion after thermal annealing. The average power conversion efficiency (PCE) of the fabricated solar cells is greatly improved from 16.0(±0.32)% (conversion from annealed PbI₂) to 17.23(±0.28)% (from solvated PbI₂) with a champion device PCE > 18% due to reduction of carrier recombination rate. This work provides new design rules toward the room‐temperature phase transformation and processing of hybrid perovskite films based on FA⁺ cation without the need for Cs⁺ or mixed halide formulation.     

Crystal Phase Control of Luminescing α‐NaGdF4:Eu3+and β‐NaGdF4:Eu3+ Nanocrystals

NaGdF₄:Eu³⁺, NaEuF₄, and NaGdF₄ nanocrystals were synthesized in the high‐boiling coordinating solvent N‐(2‐hydroxyethyl)‐ethylenediamine (HEEDA). Phase pure nanomaterials, crystallizing either in the cubic α‐phase or the hexagonal β‐phase, were obtained by adjusting one reaction parameter only, i.e., the molar ratio between metal and fluoride ions in the synthesis. The hexagonal β‐phase is formed, if this molar ratio is close to stoichiometric, whereas the cubic α‐phase is obtained in the presence of excess metal ions. The optical properties of the Eu³⁺ doped samples are different for the two crystal phases. The results indicate an increased number of oxygen impurities close to Eu³⁺ ions, if excess metal ions are used in the synthesis.     

Phase relations in Cu- RO1.5- O (R < Ho,Er, Yb) and gibbs energy of formation of Cu2R2O5 (R < Ho,Er, Yb) between 1000 and 1325K

Phase relations in Cu-RO_1.5-O(R < Ho,Er,Yb) ternary systems at 1273K have been established by isothermal equilibration of samples containing different ratios of Cu:R(R < Ho,Er,Yb) in flowing air or high purity argon atmosphere for four days. The samples were then rapidly cooled to ambient temperature and the coexisting phases were identified by powder x-ray diffraction analysis. Only one ternary oxide, Cu₂R₂O₅(R < Ho,Er,Yb) was found to be stable. The chemical potential of oxygen for the coexistence of the three phase assemblage, Cu₂O + R₂O₃ + Cu₂R₂O₅(R < Ho,Er,Yb) has been measured by employing the solid-state galvanic cells,< (−) Pt, Cu₂O + Ho₂O₃+ Cu₂Ho₂O₅//CSZ//Air (Po₂< 2.12 × 10⁴ Pa), Pt (+) (−) Pt, Cu₂O + Er₂O₃+ Cu₂Er₂O//CSZ//Air (Po₂< 2.12 × 10⁴ Pa), Pt (+) (−) Pt, Cu₂O + Yb₂O₃ + Cu₂Yb₂O₅//CSZ//Air (Po₂ < 2.12 × 10⁴ Pa), Pt (+) in the temperature range of 1000 to 1325K. Combining the measured emf of the above cells with the chemical potential of oxygen at the reference electrode, using the Nernst relationship, gives for the reactions, 2Cu₂O(s) + 2Ho₂O₃(s) + O₂(g) → 2Cu₂Ho₂O₅(s) (1) 2Cu₂O(s) + 2Er₂O₃(s) + O₂(g) → 2Cu₂Er₂O₅(s) (2) and 2Cu₂O(s) + 2Yb₂O₃(s) + O₂(g) → 2Cu₂Yb₂O₅(s) (3) δΜo₂ = −219,741.3 + 145.671 T (±100) Jmol⁻¹ (4) δΜo₂ = −222,959.8 + 147.98 T(±100) Jmol⁻¹ (5) and δΜo₂ = −231,225.2 + 151.847 T(±100) Jmol⁻¹ (6) respectively. Combining the chemical potential of oxygen for the coexistence of Cu₂O + R₂O₃ + Cu₂R₂O₅(R− Ho,Er,Yb) obtained in this study with the oxygen potential for Cu₂O + CuO equilibrium gives for the reactions, 2 CuO(s) + Ho₂O₃(s) → Cu₂Ho₂O₅(s) (7) 2 CuO(s) + Er₂O₃(s) → Cu₂Er₂O₅(s) (8) and 2 CuO(s) + Yb₂O₃(s) → Cu₂Yb₂O₅(s) (9) δG‡ < 22,870.3 − 23.160 T (±100) Jmol⁻¹ (10) δG‡ < 21,261.1 − 22.002 T (±100) Jmol⁻¹ (11) and δG‡ < 17,128.4 - 20.072 T (±100) Jmol^-1 (12) It can be clearly seen that the formation of Cu₂R₂O₅R < Ho,Er,Yb) from the component oxides is endothermic. Further, Cu₂R₂O₅(R < Ho,Er,Yb) are an entropy stabilized phases. Based on the results obtained in this study, the oxygen potential diagram for Cu-R-O(R < Ho,Er,Yb) ternary system at 1273K has been composed.     

One‐Pot Synthesis of Au25(SG)18 2‐ and 4‐nm Gold Nanoparticles and Comparison of Their Size‐Dependent Properties

A one‐pot synthesis of glutathione (denoted as ‐SG) capped gold nanoparticles, including Au₂₅(SG)₁₈ (ca. 1 nm in diameter) 2‐ and 4‐nm particles is reported. These nanoparticles are isolated by methanol‐induced precipitation with a controlled amount of added methanol. Except for their particle size, these nanoparticles have an identical chemical composition (i.e., gold and ‐SG content), synthetic history, and surface conditions, which allows for precise comparison of their size‐dependent properties, in particular the magnetic property as this could be attributed to contamination by trace iron impurities. Specifically, the structure, optical, and magnetic properties of these gold nanoparticles are compared. A trend from non‐fcc (fcc = face centered cubic) Au₂₅(SG)₁₈ nanoclusters (ca. 1 nm) to 2‐ and 4‐nm fcc‐crystalline Au nanocrystals is revealed. The Au₂₅(SG)₁₈ nanoparticles resemble molecules and exhibit multiple optical absorption peaks ascribed to one‐electron transitions, whereas the 4‐nm nanoparticles exhibit surface plasmon resonance at around 520 nm related to the collective excitation of conduction electrons upon optical excitation. The transition from the non‐fcc cluster state to the fcc crystalline state occurs at around 2 nm. Interestingly, both 2‐ and 4‐nm particles exhibit paramagnetism, whereas the Au₂₅(SG)₁₈ (anionic) clusters are diamagnetic. The information attained on the evolution of the properties of nanoparticles from nanoclusters to fcc‐structured nanocrystals is of major importance and provides insight into structure—property relationships.     

Near‐Infrared Light‐Emitting Diodes (LEDs) Based on Poly(phenylene)/Yb‐tris(β‐Diketonate) Complexes

Near‐infrared‐emitting electroluminescent (EL) devices using blue‐light‐emitting polymers blended with the Yb complexes Yb(DBM)₃phen (DBM = dibenzoylmethane), Yb(DNM)₃phen (DNM = dinaphthoylmethane), and Yb(TPP)L(OEt) (L(OEt) = [(C₅H₅)Co{P(O)Et₂}₃]^–) have been studied. EL devices composed of Yb(DNM)₃phen blended with PPP‐OR11 showed enhanced near‐IR output at 977 nm when compared to those fabricated with Yb(DBM)₃phen/PPP‐OR11 blends. The maximum near‐IR external efficiencies of the devices with Yb(DBM)₃phen and Yb(DNM)₃phen are, respectively, 7 × 10^–5 (at 6 V and at 0.81 mA mm^–2) and 4 × 10^–4 (at 7 V, and 0.74 mA mm^–2). The optimal blend composition for EL device performance consisted of PPP‐OR11 blended with 10–20 mol‐% Yb(DNM)₃phen. A device fabricated using Yb‐(TPP)L(OEt)/PPP‐OR11 showed significantly enhanced near‐IR output efficiency, and future efforts will focus on devices fabricated using porphyrin‐based materials.     

Highly Emissive Nd3+‐Sensitized Multilayered Upconversion Nanoparticles for Efficient 795 nm Operated Photodynamic Therapy

Photodynamic therapy (PDT) is a noninvasive and site‐specific therapeutic technique for the clinical treatment of various of superficial diseases. In order to tuning the operation wavelength and improve the tissue penetration of PDT, rare‐earth doped upconversion nanoparticles (UCNPs) with strong anti‐stokes emission are introduced in PDT recently. However, the conventional Yb³⁺‐sensitized UCNPs are excited at 980 nm which is overlapped with the absorption of water, thus resulting in strong overheating effect. Herein, a convenient but effective design to obtain highly emissive 795 nm excited Nd³⁺‐sensitized UCNPs (NaYF₄:Yb,Er@NaYF₄:Yb_0.1Nd_0.4@NaYF₄) is reported, which provides about six times enhanced upconversion luminescence, comparing with traditional UCNPs (NaYF₄:Yb,Er@NaYF₄). A colloidal stable and non‐leaking PDT nanoplatform is fabricated later through a highly PEGylated mesoporous silica layer with covalently linked photosensitizer (Rose Bengal derivative). With as‐prepared Nd³⁺‐sensitized UCNPs, the nanoplatform can produce singlet oxygen more effective than traditional UCNPs. Significant higher penetration depth and lower overheating are demonstrated as well. All these features make as‐prepared nanocomposites excellent platform for PDT treatment. In addition, the nanoplatform with uniform size, high surface area, and excellent colloidal stability can be extended for other biomedical applications, such as imaging probes, biosensors, and drug delivery vehicles.     

Unveiling the Nanoparticle‐Seeded Catalytic Nucleation Kinetics of Perovskite Solar Cells by Time‐Resolved GIXS

Recently, a new seeding growth approach for perovskite thin films is reported to significantly enhance the device performance of perovskite solar cells. This work unveils the intermediate structures and the corresponding growth kinetics during conversion to perovskite crystal thin films assisted by seeding PbS nanocrystals (NCs), using time‐resolved grazing‐incidence X‐ray scattering. Through analyses of time‐resolved crystal formation kinetics obtained from synchrotron X‐rays with a fast subsecond probing time resolution, an important “catalytic” role of the seed‐like PbS NCs is clearly elucidated. The perovskite precursor‐capped PbS NCs are found to not only accelerate the nucleation of a highly oriented intermediate phase, but also catalyze the conversion of the intermediate phase into perovskite crystals with a reduced activation energy E_a = 47 (±5) kJ mol^?1, compared to 145 (±38) kJ mol^?1 for the pristine perovskite thin film. The reduced E_a is attributed to a designated crystal lattice alignment of the perovskite nanocrystals with perovskite cubic crystals; the pivotal heterointerface alignment of the perovskite crystals coordinated by the Pb NCs leads to an improved film surface morphology with less pinholes and enhanced crystal texture and thermal stability. These together contribute to the significantly improved photovoltaic performance of the corresponding devices.     

All‐Inorganic Perovskite Nanocrystals for High‐Efficiency Light Emitting Diodes: Dual‐Phase CsPbBr3‐CsPb2Br5 Composites

A dual‐phase all‐inorganic composite CsPbBr₃‐CsPb₂Br₅ is developed and applied as the emitting layer in LEDs, which exhibited a maximum luminance of 3853 cd m^–2, with current density (CE) of ≈8.98 cd A^–1 and external quantum efficiency (EQE) of ≈2.21%, respectively. The parasite of secondary phase CsPb₂Br₅ nanoparticles on the cubic CsPbBr₃ nanocrystals could enhance the current efficiency by reducing diffusion length of excitons on one side, and decrease the trap density in the band gap on the other side. In addition, the introduction of CsPb₂Br₅ nanoparticles could increase the ionic conductivity by reducing the barrier against the electronic and ionic transport, and improve emission lifetime by decreasing nonradiative energy transfer to the trap states via controlling the trap density. The dual‐phase all‐inorganic CsPbBr₃‐CsPb₂Br₅ composite nanocrystals present a new route of perovskite material for advanced light emission applications.     

Textured Tubular Nanoparticle Structures: Precursor‐Templated Synthesis of GaN Sub‐micrometer Sized Tubes

Porous and sub‐micrometer tubes made of textured GaN nanoparticles have been synthesized by an in situ chemical reaction and characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence (PL) and Raman spectroscopies. The in situ reaction involves thermal decomposition and nitridation of 1D gallium oxyhydroxide (GaOOH) at temperatures in the range of 700–900 °C. The 1D shape of the precursor GaOOH is maintained in the resultant GaN tubes. The GaN nanocrystals (estimated to be about 15 nm in size) are found to be highly oriented with respect to each other in the tube structure, with the [110] GaN direction parallel to the tube axis. The growth mechanism of the tube structure has also been studied. β‐Ga₂O₃ is found to be an intermediate phase between the starting GaOOH precursor and the final GaN product. The growth mechanism involves decomposition of GaOOH, which produces β‐Ga₂O₃ tubes with hollow interiors, and nitridation of β‐Ga₂O₃, which leads to growth of textured GaN nanocrystals. Based on the growth mechanism, tubular structures with either quasi‐circular or rectangular cross section are selectively synthesized by controlling the heating rate and calcination temperature. This in situ chemical reaction method provides a new route for synthesizing 1D hollow nanostructures.