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Steric augmentation of three-coordinate Cu( I ) β-diketiminate isocyanide chromophores to achieve microsecond excited-state lifetime

Copper(I) complexes are promising alternatives to noble metal-based photosensitizers. A recently developed class of three-coordinate copper(I) charge-transfer chromophores, pairing β-diketiminate ligands with aryl isocyanides, exhibits excited-state lifetimes that are responsive to the steric profile of the isocyanide, reaching a value of nearly 300 nanoseconds when a substituted m-terphenyl isocyanide was used. In this work, we show that extreme steric augmentation of the β-diketiminate and m-terphenyl isocyanide ligands can lead to further improvements in excited-state lifetime, with one example surpassing 1 µs. This study includes a series of eight compounds of the general formula Cu(RNacNac)(CN-Ar X2 ), where RNacNac is the substituted β-diketiminate and CN-Ar X2 is the substituted m-terphenyl isocyanide. All eight compounds are crystallographically characterized, and their excited-state properties are thoroughly evaluated by a combination of steady-state and time-resolved photoluminescence studies. This combined structural/photophysical approach unveils a correlation between common steric parameters, derived from buried volume (%V bur ) and solid angle analysis, and the excited-state lifetime. Our investigation reveals that the steric profile of the β-diketiminate has a much larger impact on the steric profile and lifetime, whereas the m-terphenyl isocyanide substituents have an unsystematic and subtle influence on these two correlated parameters. Nevertheless, judicious pairing of the two ligands is critical for achieving long excited-state lifetimes.

Kumar, Ashish [University of Houston, TX (United S↗

350 ps Ultrafast room-temperature scintillation realized on CsPbBr 3 -based single crystals via Br 2 over-doping

Ultrafast scintillators are essential for next-generation radiation detection, positron emission tomography, and high-speed medical imaging. All-inorganic CsPbBr 3 perovskites are attractive candidates because of their high stopping power, and excellent optical quality, yet their long carrier lifetimes result in slow scintillation responses on the order of hundreds of nanoseconds. Here, we demonstrate that controlled over-doping with Br 2 produces CsPbBr 3.03 single crystals with sub-nanosecond scintillation at room temperature while preserving crystal quality. Single crystals grown by the Bridgman method exhibit high transparency and maintain the orthorhombic perovskite structure. Br 2 over-doping induces a slight lattice expansion (about 0.42% increase in unit-cell volume) while maintaining the orthorhombic perovskite phase and high optical transparency. Optical absorption reveals a slight redshift of the absorption edge after Br 2 introduction, indicating a modified defect landscape. Time-resolved photoluminescence and radioluminescence measurements show that Br 2 doping creates dense and efficient recombination centers that reduce the scintillation decay time from more than 100 ns in undoped crystals to 350 ps under 5.486 MeV α-particle excitation, and the scintillation decay time decreases by two orders of magnitude. The doped crystals also achieve a spatial resolution of 12 lp mm −1 in X-ray imaging. These results reveal a defect-engineering route for achieving ultrafast scintillation in halide perovskites and highlight the potential of Br 2 -modified CsPbBr 3 for fast timing applications.

Li, Zongxiao [Chinese Academy of Sciences (CAS), N↗

Characterization of n-Type Iodine-Doped and Indium-Doped CdTe/Cd-Se-Te Thin Films Fabricated by Close-Spaced Sublimation Epitaxy

In this study, n-type CdTe thin films, specifically iodine-doped CdTe (CdTe:I), indium-doped CdTe (CdTe:In), and indium-doped Cd-Se-Te (CST:In), were synthesized using close-spaced sublimation epitaxy (CSSE). Characterization techniques secondary ion mass spectrometry (SIMS), electron backscatter diffraction (EBSD), Hall-effect measurements, and time-resolved photoluminescence (TRPL) were employed to analyze the chemical, structural, and electronic properties of these materials. The results indicated epitaxial single crystal CSSE films grew on the single crystal substrates, with carrier density ranging from 10^14 - 10^16 cm -3 , and after post-annealing, the minority-carrier lifetimes reach near the radiative limit. Additionally, a preliminary exploration of homojunction structures with an n- type (CdTe:In /CST:In /CdTe:I) /CdTe:P /Cu /Mo configuration was performed. The best device performance was achieved with CdTe:I including CdS aiding in band alignment, resulting in a power conversion efficiency (..eta..) of 2.61% with open circuit voltage (Voc) of 850 mV, fill factor (FF) of 47.8%, and short-circuit current (Jsc) of 6.44 mA/cm 2 . The observed low Jsc and efficiency may be attributed to a buried junction and a poor interface, due to dopant interdiffusion. Consequently, further investigations focusing on interface optimization, diffusion blocking, and reduced recombination through passivation, are crucial to enhancing the efficiency of CSSE CdTe homojunction devices in the future.

cadmium compounds↗

Collaborative R&D with REEL Solar Inc (REEL) to Understand and Overcome Performance Limitations in CdTe Solar Cells: Cooperative Research and Development (Final Report)

This CRADA will focus on processing, advanced characterization, and testing of photovoltaic materials and devices to understand and improve REEL CdTe solar technology. This will include examining process variations and different buffer, absorber, and contact layers from REEL and NLR to maximize performance. The unique and diverse advanced characterization tools at NLR, such as time-resolved photoluminescence, capacitance-voltage measurements, electron beam scattered diffraction, cathodoluminescence, electron microscopy, TOF-SIMS, and other measurements will be applied to characterize REEL processing to improve understanding and guide experimental directions. Accelerated stability and potential induced degradation tests will be used to analyze metastability, short-and-long term degradation, and improve bankability. A second and major thrust this period will be joint development of Si/CdTe tandem solar cells to overcome industry wide terrestrial solar efficiency limits with the two lowest cost and manufacturable solar materials today. This will include developing novel transparent back contacts that can be incorporated into tandem structures and other novel solar applications, detailed analysis of designs and configurations for CdTe/Si tandem modules, and prototyping REEL CdTe Technology with Si bottom cells in tandem structures.

14 SOLAR ENERGY↗

Isolation of Single Donors in ZnO

The shallow donor in zinc oxide (ZnO) is a promising semiconductor spin qubit with optical access. Single indium donors are isolated in a commercial ZnO substrate using plasma focused ion beam (PFIB) milling. Quantum emitters are identified optically by spatial and frequency filtering. The indium donor assignment is based on the optical bound exciton transition energy and magnetic dependence. The emission stability of these single donors in terms of both intensity and frequency, alongside their transition linewidths less than twice the lifetime limit, highlight the promise of single In donors as optically accessible spin qubits. Here, the optical stability of single donors after FIB fabrication is promising for optical device integration required for scalable quantum technologies based on single donors in direct band gap semiconductors.

42 ENGINEERING↗

Effect of ground-state charge transfer on photoexcited charge transfer in transition metal dichalcogenide heterostructures

We report an experimental investigation on the effect of ground-state charge transfer and its induced electric field on photoexcited charge transfer in van der Waals heterostructures. Two heterostructure samples were fabricated by stacking an undoped WSe 2 monolayer with either a Nb-doped or undoped MoSe 2 monolayer. While no ground-state charge transfer is expected in the MoSe 2 /WSe 2 heterostructure, the doped holes in the MoSe 2 :Nb/WSe 2 heterostructure can transfer to WSe 2 , creating a space-charge electric field. By comparing the photoluminescence and time-resolved differential reflectance of the two heterostructures, we find that photoexcited hole transfer from MoSe 2 to WSe 2 is largely blocked by this field, whereas photoexcited electron transfer from WSe 2 to MoSe 2 is less affected. Furthermore, these results provide insight into the impact of doping on the charge-transfer performance of van der Waals heterostructures.

2D materials↗

Radiative Defects in Chloride-Activated CdSe Thin Films

Defect recombination limits wide-gap Se-based chalcogenide devices, yet how chloride activation reshapes radiative pathways remains unclear. Here we show that a 40 min CdCl 2 anneal converts evaporated CdSe from porous nanograins into dense micrometer-scale polycrystals and sharpens the optical band edge, reducing the Urbach energy from 85 to 17 meV at 300 K. Combining temperature- and fluence-dependent photoluminescence (PL), time-resolved PL, hyperspectral mapping, and hybrid-DFT, we resolve three emissive channels and identify their mechanisms. The near-edge band is excitonic at low temperature and evolves into free-carrier emission at elevated temperature. A sub-gap band at E g −0.45 eV requires above-gap carriers and thermally quenches with a 0.16 eV activation energy. A broad ∼1.05 eV infrared band is excited by above- and below-gap photons and retains microsecond lifetimes at room temperature; patial mapping links it to edge-rich microstructure. Calculations suggest selenium-vacancy and cadmium-vacancy−chlorine complexes, pointing to routes to suppress defect-related losses in wide-gap chalcogenide devices.

Abudulimu, Abasi [Univ. of Toledo, OH (United Stat↗

Solvent-mediated carboxylic acid diammonium spacer for synthesizing FA-based 2D Dion–Jacobson perovskites toward efficient solar cells

Two-dimensional (2D) perovskites are promising for photovoltaic applications due to their outstanding optical properties and better environmental stability compared to three-dimensional (3D) perovskites. Unlike 2D Ruddlesden–Popper (RP) perovskites, which use monovalent ammonium spacers, Dion–Jacobson (DJ) perovskites employ divalent organic spacers that enhance structural stability by mitigating weak van der Waals interactions. However, the random phase distribution and disorder crystal orientation in 2D DJ perovskites create deep quantum wells, hindering charge transfer and reducing short-circuit current density (J SC ) and overall photovoltaic performance. This study introduces an organic diammonium, 1,4-butanediamine diacetate (BDAAc 2 ), to replace the traditional halide spacer 1,4-butanediamine iodide (BDADI 2 ). This substitution regulates perovskites crystallization dynamics, reducing compositional disorder and random phase distribution, thus improving the quality of the perovskite films. The robust coordination interactions between BDAAc 2 and the perovskite inorganic framework lead to an ordered [PbX 6 ] 4− arrangement, suppressing the formation of complex intermediate phases and significantly enhancing δ phase crystallinity in the intermediate film. This results in a high yield of high-quality α phase. Consequently, the resulting 2D DJ perovskite solar cells based on BDAFA 3 Pb 4 (I 0.9 Br 0.1 ) 13 achieve a higher power conversion efficiency of 16.41% and an elevated J SC of 20.46 mA cm −2 .

14 SOLAR ENERGY↗

CdSeTe solar-cell performance with different dopant types

Four doping conditions were explored for CdTe-based solar cells: p-type As and P, n-type Al, and no intentional doping. In each case, the CdTe absorber was alloyed with Se, but only near the normal front-side, light entry for the cells, while the dopants were added from the back. Cells with p-dopants showed efficiencies up to 20% with front-side illumination, but the n-doped and undoped ones were close to zero. With back-side illumination, this was reversed with undoped up to 8% and p-doped ones only about 2%. These results are explained by Kelvin-probe measurements of electric-field profiles, which showed that the diode field was near the front for the higher-efficiency p-doping, but near the back for undoped and n-doped.

14 SOLAR ENERGY↗

Electron-Deficient Phenazines: Synthesis, Structures, Redox, and Optoelectronic Properties in the Gas Phase, in Solution, and in the Solid State

High-temperature gas-phase reactions of 1,4-C4F8I2 with phenazine (PHNZ) afforded new thermally- and air-stable derivatives with cyclo-C4F8 substituents, viz. 1,2-PHNZ(C4F8), 2,3-PHNZ(C4F8), 1,2:6,7-PHNZ(C4F8)2, 1,2:7,8-PHNZ(C4F8)2, and 1,2:8,9-PHNZ(C4F8)2. Reactions in the presence of Cu powder resulted in reductive-defluorination/aromatization of some of the cyclo-C4F8 substituents to produce 2,3-PHNZ(C4F4), 2,3-PHNZ(C4HF3), and 1,2:6,7-PHNZ(C4F8)(C4F4), which are formally tri- or tetrafluoro derivatives of benzo[a]phenazine. Single-crystal X-ray diffraction structures of these compounds demonstrate the planarity of 2,3-PHNZ(C4F4) and 2,3-PHNZ(C4HF3) and ordered p-stacking in 1,2-PHNZ(C4HF3), 1,2-PHNZ(C4F4), 1,2-PHNZ(C4F8), and 2,3-PHNZ(C4F8). Low-temperature gas-phase photoelectron spectra of the PHNZ(C4F8)1,2 compounds show that they are strong electron acceptors, with the three PHNZ(C4F8)2 isomers having electron affinities exceeding that of C60. Cyclic voltammetry in acetonitrile show that the five PHNZ(C4F8)1,2 compounds exhibit reversible one-electron reductions with large positive shifts in their reduction potentials relative to unsubstituted PHNZ. Spectroelectrochemical absorption and EPR spectra of PHNZ(C4F8)1,2- • anion radicals and extensive DFT calculations revealed the significant role that the different substitution patterns have on determining the optoelectronic properties of the PHNZ(C4F8)1,2 derivatives and PHNZ(C4F8)1,2- • anion radicals. Time-resolved microwave conductivity measurements and photoluminescence spectra of blends of the PHNZ(C4F8)1,2 derivatives with the donor poly(3-hexylthiophene) (P3HT) were recorded to assess the possible use of the new compounds in optoelectronic devices.

Balser, Sebastian↗

Self-Trapped-Exciton Radiative Recombination in β–Ga 2 O 3 : Impact of Two Concurrent Nonradiative Auger Processes

The peculiarities of radiative and nonradiative processes associated with self-trapped intrinsic eXcitons in the excited β-Ga 2 O 3 crystals are studied via time-resolved techniques of induced absorption, transient grating, and photoluminescence (PL) at room temperature. The excitation above the bandgap is produced by laser pulses with linear light polarization parallel and orthogonal in the (–201) and (001) planes. We elucidate that the nonradiative recombination rate occurring in the eXciton prevails over its radiative emission rate in a wide range of free carrier concentration composed of excited and equilibrium electrons. Hence, the nonradiative recombination has no effect on the strong anisotropy and the shape of the eXciton emission band. However, we find out that the conventional ABC model of electron effective lifetime is insufficient for explanation of the excitation dependences. Inclusion of two nonradiative Auger mechanisms in a modified ABC formula provides excellent agreement of these dependences. We conclude that the trap-assisted Auger process is in proportion to the free electron density with coefficient B = 1.1 × 10 –11 cm 3 /s and appears at low/intermediate excitation, while the triple-particle Auger process is in proportion to Δn 2 with coefficient C = 8 × 10 –30 cm 6 /s and appears at high excitation conditions. The transition between two Auger mechanisms is accompanied by a rise of the eXciton diffusivity in preferred crystallographic directions where the radiative PL intensity is maximal. The diffusion length LD in these directions can reach values ~300 nm, but, at high excitations, LD becomes limited by Auger lifetimes. These findings pave the way for the implementation of self-trapped eXcitons into specific optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring Cs 2 AgIn x Bi 1− x Cl 6 double perovskites for optoelectronics: insights from theoretical and photophysical approaches

Lead-free halide double perovskites (HDPs) have become attractive materials for optoelectronic applications owing to their nontoxicity, structural stability, and germane photoelectric properties. In this work, we report the synthesis of high-quality In-alloyed Cs 2 AgIn x Bi (1−x) Cl 6 nanocrystals (NCs) using the antisolvent recrystallization method and comprehensively investigate the effects of In alloying on the structural, morphological, optoelectronic, and temperature-dependent photoluminescence (TDPL) properties using the state-of-the-art experimental and computational tools. Both XRD and Raman spectroscopy analyses confirmed the synthesis of highly crystalline Cs 2 AgIn x Bi (1−x) Cl 6 materials, which exhibited cubic morphology, as confirmed by TEM analysis. Room-temperature photoluminescence (PL) measurements revealed a drastic increase in the intensity above 75% In concentration with dual emission, whereas the time-resolved PL (TR-PL) results show an increase in the average lifetime values with an increase in In content, suggesting that the materials have excellent optical properties and hence are suitable candidates for optoelectronics. The TDPL measurements revealed the smallest Huang–Rhys factor (18.6) for the Cs 2 AgIn x Bi (1−x) Cl 6 (x = 0.9) sample, indicating weak exciton–phonon coupling in this composition. When deployed in the fabrication of a photodetector device, the Cs 2 AgIn x Bi (1−x) Cl 6 (x = 0.9) sample exhibited significantly enhanced photoresponsivity and a faster response time, confirming its potential for photodetector applications. Complementary DFT calculations showed that In alloying modifies the band structure of Cs 2 AgIn x Bi (1−x) Cl 6 . Our results provide valuable insights for designing multifunctional Cs 2 AgIn x Bi (1−x) Cl 6 -based materials for next-generation energy and optoelectronic devices.

14 SOLAR ENERGY↗

(NH 3 (CH 2 ) 7 NH 3 ) 2 Sn 3 I 10 , a Vacancy-Ordered Three-Dimensional Tin(II) Perovskite-Derived Semiconductor

Ordering vacancies in hybrid Sn(II) halide semiconductors provides a strategy for preventing uncontrolled oxidation and formation of mobile holes. In this study, we report the structure and optical and electronic properties of (NH 3 (CH 2 ) 7 NH 3 ) 2 Sn 3 I 10 , a vacancy-ordered perovskite derivative with three-dimensional inorganic connectivity. The crystal structure resembles that of a Dion–Jacobson layered perovskite derivative, but with [SnI 5 ] square pyramids bridging the layers. UV–vis diffuse reflectance spectroscopy reveals a sharp onset of light absorption at 1.86(1) eV with the photoluminescence emission maximum at 1.90(1) eV. However, the maximum excitation occurs from 3.42 to 3.81 eV (325 to 370 nm), revealing a significant Stokes shift of 1.3 eV. The electronic properties determined from dark and time-resolved microwave conductivity measurements reveal a minimum carrier mobility of 4.3 × 10 –2 cm 2 V –1 s –1 and a maximum carrier density of 5.96 × 10 16 cm –3 , a uniquely low value for a hybrid Sn(II) halide semiconductor. The transport behavior in combination with first-principles calculations of the electronic band structure and dielectric permittivity suggest polaron-mediated electronic transport, yet the photogenerated carriers have a fast and fluence-dependent nonradiative recombination rate, suggestive of localized “defect-like” states at the band edge. The observed photoluminescence is most consistent with single-ion-like behavior of an asymmetric Sn(II) environment. Together, these results suggest that defect ordering presents a strategy for the reduction of mobile charge carriers at equilibrium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient up-conversion in CsPbBr 3 nanocrystals via phonon-driven exciton-polaron formation

Lead halide perovskite nanocrystals demonstrate efficient up-conversion, although the precise mechanism remains a subject of active research. This study utilizes steady-state and time-resolved spectroscopy methods to unravel the mechanism driving the up-conversion process in CsPbBr 3 nanocrystals. Employing above- and below-gap photoluminescence measurements, we extract a distinct phonon mode with an energy of ~7 meV and identify the Pb-Br-Pb bending mode as the phonon involved in the up-conversion process. This result was corroborated by Raman spectroscopy. We confirm an up-conversion efficiency reaching up to 75%. Transient absorption measurements under conditions of sub-gap excitation also unexpectedly reveal coherent phonons for the subset of nanocrystals undergoing up-conversion. This coherence implies that the up-conversion and subsequent relaxation is accompanied by a synchronized and phased lattice motion. This study reveals that efficient up-conversion in CsPbBr 3 nanocrystals is powered by a unique interplay between the soft lattice structure, phonons, and excited states dynamics.

Anti-Stokes Photoluminescence↗

Photophysical and Time‐resolved Infrared Properties of Long‐Lived Rhenium(I) 4,5‐Diazafluorene Tricarbonyl Chromophores

This report investigates the synthesis, structural characterization, fundamental molecular photophysics, electrochemistry, UV-Vis spectroelectrochemistry, and time-resolved infrared spectroscopic properties of eight [fac-Re(dafR)(CO) 3 L] 0/+ complexes, where R=ethyl [(dedaf); 1, 3, 5, 7] or H [(dafH); 2, 4, 6, 8] and L=Cl− (1, 2), imidazole [(Im); 3, 4], 4-ethylpyridine [(4-Etpy); 5, 6], or pyridine [(py); 7, 8]. Universally, 1–8 yield higher energy photoluminescence (PL) emission bands and higher PL quantum yields (up to 53 %) than the classic 2,2’-bipyridine (bpy) and 1,10-phenanthroline (phen) ligated Re(I) tricarbonyl complexes. The excited state lifetimes of 1–8 lie between those corresponding to the bpy and phen derivatives, ranging from 120 and 1300 ns at room temperature. Combinations of reductive UV-Vis spectroelectrochemistry, transient absorption spectroscopy, and time-resolved infrared spectroscopy consistently assigned the lowest excited states in 1–8 being of metal-to-ligand charge transfer (MLCT) character. These new ReI MLCT chromophores follow classic energy gap law behavior and possess the characteristics necessary for serving as valuable photosensitizers suitable to energize excited state electron and energy transfer photochemistry.

Charge transfer↗

Data for "Gold-Induced Chemical Perturbations in CdTe-Based Photovoltaic Cells"

Back contacting p-type CdTe has been identified as one of the major areas of loss in CdTe photovoltaic (PV) power conversion efficiency (PCE). In research settings, Au is a common contact material due to its ease of use and decent performance. This work provides a detailed investigation into using gold for back contacting As-doped, CdCl2 treated, polycrystalline CdTe that has been exposed to air after absorber processing, another routine practice. First, X-ray photoemission spectroscopy (XPS) is used to determine the native oxide to be 1.6 nm of CdTeO3 using a combination of angle-resolved XPS and the cadmium modified Auger parameter. During gold metallization of CdTe, oxygen and oxidized tellurium are eliminated from the thin CdTeO3 native oxide. The fate of the released oxygen and possibly cadmium and tellurium are not known, but these reaction byproducts can enter the absorber bulk or grain boundaries, stay at the interface, or dissolve in the Au. Interfacial hole barriers between CdTe and Au are measured for samples with and without the native oxide present prior to metallization. Results show that the thin CdTeO3 alleviates the downward band bending by 40 meV from 470 meV to 430 meV even though it is consumed during interface formation. The implications of these chemical reactions on the device are assessed through photoluminescence (PL) spectroscopy which shows losses in internal open circuit voltage (iVoc) from 820 meV to 795 meV, carrier lifetime from 123 ns to 45 ns, and PL quantum yield from 2.9x10-5 to 1.2x10-5. Modeling time-resolved PL lifetimes demonstrates the back surface recombination velocity due to metallization reduces minority carrier lifetimes. These results identify the native oxide and show that it plays an important role in mediating downward band bending along with how the back interface reaction can negatively impact device-scale parameters and reduce PV PCE.

14 SOLAR ENERGY↗

Dynamic Behavior of Bound Interlayer Excitons in Interlayer-Doped Cs 3 Bi 2 Br 9 Vacancy-Ordered Perovskite

Interlayer doping of the vacancy-ordered 2D perovskite Cs 3 Bi 2 Br 9 (CBB) enables the formation of bound interlayer excitons (BIEs), a unique charge-transfer excited state within the layered solid. BIEs previously reported with silver (Ag + ) as an interlayer dopant exhibited bright broadband photoluminescence (PL) with prolonged lifetime at room temperature, offering potential applications in efficient white light emission, photocatalysis, and optoelectronics. However, the dynamic behavior of radiation and excited carriers remains poorly understood due to the limitations of ensemble spectroscopic measurements. Here, we investigate the temperature-dependent dynamics of Ag-doped Cs 3 Bi 2 Br 9 (Ag-CBB) using single-particle time-resolved PL spectroscopy and ultrafast transient absorption imaging. Single-particle PL measurements reveal three distinct emission regimes across temperature: (i) BIE-dominant emission at high temperatures, (ii) a mixture of radiation from BIEs and self-trapped excitons (STEs) at intermediate temperatures, and (iii) STE-dominant emission below 100 K. Rapid transient absorption mapping using Parallel Rapid Imaging with Spectroscopic Mapping (PRISM) reveals subpicosecond STE formation in pristine CBB and long-lived photoinduced absorption by BIEs, consistent with electron–hole separation and suppressed STE transfer. The spatial uniformity of these signals confirms homogeneous Ag doping across single crystals. These findings highlight the role of Ag interlayer dopants in governing the BIE dynamics.

bound interlayer exciton↗

Au 76 (SC 6 H 4 - p -CH 3 ) 42 Square Quantum Platelet: One-Dimensional Growth of Quantum Rods Turns 90 Degrees

The growth pattern of atomically precise nanoclusters (NCs) is of fundamental interest, and the structural effect on their photoluminescence (PL) is important owing to their PL in the second near-infrared (NIR-II) range (900–1700 nm optoelectronically or 1000–1700 nm biologically) that holds great promise for optoelectronic and biomedical applications. Because of the small energy gaps required for NIR-II emission, the PL performance of NIR-II luminophores is largely limited by nonradiative processes. In this work, we discovered a Au 76 (p-MBT) 42 (Au 76 ) (p-MBTH = p-methylbenzenethiol) nanocluster featuring a face-centered cubic (fcc) core in a square shape (edge length: 1 nm). This square quantum platelet can be viewed as a side-facet (010) growth of the Au 52 (p-MBT) 32 (Au 52 ) rod, as opposed to the (001) facet growth. We found that Au 76 exhibits bright emission centered at 970 nm with a PL quantum yield (PLQY) of 30% in solution under ambient conditions, which can be further enhanced to 40% when the solution is deaerated. X-ray crystallography analysis coupled with time-resolved spectroscopy revealed that the nearly doubled PLQY compared to Au 52 (18.3%) was resulted from shorter Au–Au bond lengths in Au 76 (average 2.835 Å) than that in Au 52 (3.04 Å). This work provides important insights into the design of highly luminescent NCs, which are promising for photovoltaics, photocatalysis, and optoelectronic applications.

36 MATERIALS SCIENCE↗