Deconvoluting Energy Transport Mechanisms in Metal Halide Perovskites Using CsPbBr3 Nanowires as a Model System

Understanding energy transport in metal halide perovskites is essential to effectively guide further optimization of materials and device designs. However, difficulties to disentangle charge carrier diffusion, photon recycling, and photon transport have led to contradicting reports and uncertainty regarding which mechanism dominates. In this study, monocrystalline CsPbBr₃ nanowires serve as 1D model systems to help unravel the respective contribution of energy transport processes in metal-halide perovskites. Spatially, temporally, and spectrally resolved photoluminescence (PL) microscopy reveals characteristic signatures of each transport mechanism from which a robust model describing the PL signal accounting for carrier diffusion, photon propagation, and photon recycling is developed. For the investigated CsPbBr₃ nanowires, an ambipolar carrier mobility of μ = 35 cm² V⁻¹ s⁻¹ is determined, and is found that charge carrier diffusion dominates the energy transport process over photon recycling. Moreover, the general applicability of the developed model is demonstrated on different perovskite compounds by applying it to data provided in previous related reports, from which clarity is gained as to why conflicting reports exist. These findings, therefore, serve as a useful tool to assist future studies aimed at characterizing energy transport mechanisms in semiconductor nanowires using PL.     

Far-red-emitting YAl3(BO3)4:Cr3+ phosphors with excellent thermal stability and high luminescent yield for plant growth LEDs

Phosphors-converted LEDs (pc-LEDs) are excellent artificial light sources for indoor plant cultivation, in which the far-red-emitting component (700−780 nm) plays an important role in regulating the photomorphogenesis of plants. Accordingly, highly efficient and thermally stable far-red-emitting phosphors are indispensable for developing high-performance plant cultivation pc-LEDs. Herein, far-red-emitting YAl₃(BO₃)₄:Cr³⁺ (YAB:Cr³⁺) phosphors were synthesized by solid-state reaction, and their photoluminescence characteristics, thermal quenching, quantum yield (QY), and application in pc-LEDs were systematically investigated. The YAB:Cr³⁺ phosphor has an intense broadband absorption to the blue light, simultaneously exhibiting the sharp-line ²E emission and the broadband ⁴ T₂ emission of Cr³⁺ with a QY of ~86.7%. The far-red broadband emissions of YAB:Cr³⁺ centered at ~735 nm show a high resemblance to the active-state (P_FR) absorption of plant phytochrome. Moreover, the YAB:Cr³⁺ phosphor shows the thermally enhanced luminescence at temperatures of 303−393 K and the near-zero thermal quenching up to 423 K. The anomalous thermal enhancement is attributed to the temperature-dependent repopulation between ²E and ⁴ T₂ states. Finally, a pc-LED device was fabricated with the YAB:Cr³⁺ phosphor and blue chip, exhibiting the light out power of ~50.6 mW and energy conversion efficiency of ~17.4% at 100 mA drive current, respectively. The exceptional PL features including suitable excitation/emission wavelengths, suppressed thermal quenching and high QY make YAB:Cr³⁺ phosphors very promising for applications in plant growth pc-LEDs.     

Y4.67Si3O13-based phosphors: Structure,morphology and upconversion luminescence for optical thermometry

How to improve the sensitivity of the temperature-sensing luminescent materials is one of the most important objects currently. In this work, to obtain high sensitivity and learn the corresponding mechanism, the rare earth (RE) ions doped Y_4.67Si₃O₁₃ (YS) phosphors were developed by solid-state reaction. The phase purity, structure, morphology and luminescence characteristics were evaluated by XRD, TEM, emission spectra, etc. The change of the optical bandgaps between the host and RE-doped phosphors was found, agreeing with the calculation results based on density-functional theory. The temperature-dependence of the upconversion (UC) luminescence revealed that a linear relationship exists between the fluorescence intensity ratio of Ho³⁺ and temperature. The theoretical resolution was evaluated. High absolute (0.083 K⁻¹) and relative (3.53% K⁻¹ at 293 K) sensitivities have been gained in the YS:1%Ho³⁺, 10%Yb³⁺. The effect of the Yb³⁺ doping concentration and pump power on the sensitivities was discussed. The pump-power–dependence of the UC luminescence indicated the main mechanism for high sensitivities in the YS:1%Ho³⁺, 10%Yb³⁺. Moreover, the decay-lifetime based temperature sensing was also evaluated. The above results imply that the present phosphors could be promising candidates for temperature sensors, and the proposed strategies are instructive in exploring other new temperature sensing luminescent materials.     

Intense broadband photoemission from Bi-doped ZrO2 embedded in vitreous aluminoborate via direct melt-quenching

Tuning the optical properties of active species embedded within a glass matrix by modifying the ligand environment is of interest for luminescence-based technologies, for example, in optical sensing, data transmission, or spectral conversion. Here, we discuss a facile synthesis procedure for a glass-crystal composite material comprising of bismuth (Bi)-doped zirconia within an aluminoborate glass phase. The approach offers tunable and broad photoemission characteristics in the visible spectral region from 400 to 750 nm. Incorporation of Bi ions into the crystal phase enhances the photoemission intensity by two orders of magnitude, with an external quantum efficiency of about 29%. At higher ZrO₂ dopant concentration, we observe a red-shift of both the excitation and the emission bands to match commodity ultra-violet light emitting diodes as excitation sources. Encapsulation within the aluminoborate glass phase provides advantageous thermal behavior, with the emission intensity remaining at >80 % of its initial value up to a temperature of 400 K.     

Photoluminescence and thermal expansion of zirconium vanadate

The optical property and phase transition of ZrV₂O₇ were investigated by temperature-dependent X-ray diffraction, photoluminescence (PL), and Raman spectra. It was found that the material exhibited PL emission in the visible region. The temperature-dependent PL emission showed that the peak energy for emission (at red wavelength) presented a red shift from 10 to 80 K, and then a blue shift with the increase in temperature. The PL emission bands of ZrV₂O₇ shifted with change in temperature relating to its phase transition (80-100 K), which could be confirmed by temperature-dependent Raman spectra.     

Excitonic Properties of Chemically Synthesized 2D Organic–Inorganic Hybrid Perovskite Nanosheets

2D organic–inorganic hybrid perovskites (OIHPs) represent a unique class of materials with a natural quantum‐well structure and quasi‐2D electronic properties. Here, a versatile direct solution‐based synthesis of mono‐ and few‐layer OIHP nanosheets and a systematic study of their electronic structure as a function of the number of monolayers by photoluminescence and absorption spectroscopy are reported. The monolayers of various OIHPs are found to exhibit high electronic quality as evidenced by high quantum yield and negligible Stokes shift. It is shown that the ground exciton peak blueshifts by ≈40 meV when the layer thickness reduces from bulk to monolayer. It is also shown that the exciton binding energy remains effectively unchanged for (C₆H₅(CH₂)₂NH₃)₂PbI₄ with the number of layers. Similar trends are observed for (C₄H₉NH₃)₂PbI₄ in contrast to the previous report. Further, the photoluminescence lifetime is found to decrease with the number of monolayers, indicating the dominant role of surface trap states in nonradiative recombination of the electron–hole pairs.     

光伏用电致发光缺陷检测仪空间分辨率的量化评估

针对光伏用电致发光缺陷检测仪空间分辨率目视判定重复性、准确性差,并且难以量化等问题,提出一套基于卷积神经网络模型的空间分辨率量化评估方法。参照相关标准JJF(闽)1088-2018,采取不同的拍摄条件拍摄并切割出空间分辨率线对图像,对图像进行人工分类。设计卷积神经网络结构,采用卷积层、池化层和全连接层结构,并使用已分类完成的空间分辨率线对图像对模型进行训练。最终使用测试集对模型进行评估,结果表明,模型在测试集上的判别正确率达到99.2%。该方法满足使用要求,可取代目视判别,提高了光伏用电致发光缺陷检测仪空间分辨率判定的准确性与重复性,并为其量化提出了新的解决思路。由于太阳电池片用光致发光缺陷检测仪与光伏用电致发光缺陷检测仪的成像方式类似,该方法可兼容太阳电池片光致发光检测仪的性能评估。     

Dynamic Passivation in Perovskite Quantum Dots for Specific Ammonia Detection at Room Temperature

Perovskite structured CsPbX₃ (X = Cl, Br, or I) quantum dots (QDs) have attracted considerable interest in the past few years due to their excellent optoelectronic properties. Surface passivation is one of the main pathways to optimize the optoelectrical performance of perovskite QDs, in which the amino group plays an important role for the corresponding interaction between lead and halide. In this work, it is found that ammonia gas could dramatically increase photoluminescence of purified QDs and effectively passivate surface defects of perovskite QDs introduced during purification, which is a reversible process. This phenomenon makes perovskite QDs a kind of ideal candidate for detection of ammonia gas at room temperature. This QD film sensor displays specific recognition behavior toward ammonia gas due to its significant fluorescence enhancement, while depressed luminescence in case of other gases. The sensor, in turn‐on mode, shows a wide detection range from 25 to 350 ppm with a limit of detection as low as 8.85 ppm. Meanwhile, a fast response time of ≈10 s is achieved, and the recovery time is ≈30 s. The fully reversible, high sensitivity and selectivity characteristics make CsPbBr₃ QDs ideal active materials for room‐temperature ammonia sensing.     

Two‐Photon Up‐Conversion Photoluminescence Realized through Spatially Extended Gap States in Quasi‐2D Perovskite Films

A new approach to generate a two‐photon up‐conversion photoluminescence (PL) by directly exciting the gap states with continuous‐wave (CW) infrared photoexcitation in solution‐processing quasi‐2D perovskite films [(PEA)₂(MA)₄Pb₅Br₁₆ with n = 5] is reported. Specifically, a visible PL peaked at 520 nm is observed with the quadratic power dependence by exciting the gap states with CW 980 nm laser excitation, indicating a two‐photon up‐conversion PL occurring in quasi‐2D perovskite films. Decreasing the gap states by reducing the n value leads to a dramatic decrease in the two‐photon up‐conversion PL signal. This confirms that the gap states are indeed responsible for generating the two‐photon up‐conversion PL in quasi‐2D perovskites. Furthermore, mechanical scratching indicates that the different‐n‐value nanoplates are essentially uniformly formed in the quasi‐2D perovskite films toward generating multi‐photon up‐conversion light emission. More importantly, the two‐photon up‐conversion PL is found to be sensitive to an external magnetic field, indicating that the gap states are essentially formed as spatially extended states ready for multi‐photon excitation. Polarization‐dependent up‐conversion PL studies reveal that the gap states experience the orbit–orbit interaction through Coulomb polarization to form spatially extended states toward developing multi‐photon up‐conversion light emission in quasi‐2D perovskites.