Intragap States Research Articles

Tailoring Energy Structure of Low‐Toxic Ternary Ag−Bi−S Quantum Dots through Solution‐Phase Synthesis for Quantum‐Dot‐Sensitized Solar Cells

AbstractLow‐toxic multinary semiconductor quantum dots (QDs) showing a photoresponse in a wide wavelength range from visible to near‐IR wavelength regions have been intensively investigated for fabricating efficient solar light conversion systems. Recently, AgBiS2 QDs have attracted much attention for their application to improve the performance of QD solar cells because they have a large absorption coefficient in the visible and near‐IR regions. In this report, we describe solution‐phase preparation of ternary Ag−Bi−S QDs with different sizes and with different Ag/Bi ratios. The average size of resulting spherical Ag−Bi−S QDs was controllable from 2.7 to 8.1 nm by adjusting the reaction temperature from 373 to 473 K, while the Ag fraction of obtained QDs also increased with an increase in particle size. The absorption onset wavelength shifted from 850 to 1200 nm in the near‐IR region as the particle size increased. AgBiS2 QDs with an almost stoichiometric composition, obtained at reaction temperatures of 423 K and 473 K, contained no deep intragap states and exhibited a p‐type semiconductor behavior, while QDs prepared at a reaction temperature of 393 K or lower had non‐stoichiometric Ag‐deficient compositions producing intragap defect states. Sensitized solar cells fabricated with stoichiometric AgBiS2 QDs exhibited a photoresponse in visible and near‐IR wavelength regions, the optimal PCE being 0.74% with AgBiS2 QDs of 6.2 nm in diameter that were prepared at 423 K.

Role of Intragap States in Sensitized Sb-Doped Tin Oxide Photoanodes for Solar Fuels Production.

In view of developing photoelectrosynthetic cells which are able to store solar energy in chemical bonds, water splitting is usually the reaction of choice when targeting hydrogen production. However, alternative approaches can be considered, aimed at substituting the anodic reaction of water oxidation with more commercially capitalizable oxidations. Among them, the production of bromine from bromide ions was investigated long back in the 1980s by Texas Instruments. Herein we present optimized perylene-diimide (PDI)-sensitized antimony-doped tin oxide (ATO) photoanodes enabling the photoinduced HBr splitting with >4 mA/cm2 photocurrent densities under 0.1 W/cm2 AM1.5G illumination and 91 ± 3% faradaic efficiencies for bromine production. These remarkable results, among the best currently reported for the photoelectrochemical Br- oxidation by dye sensitized photoanodes, are strongly related to the occupancy extent of ATO's intragap (IG) states, generated upon Sb-doping, as demonstrated by comparing their performances with PDI-sensitized analogues on both undoped SnO2- and TiO2-passivated ATO scaffolds by means of (spectro)electrochemistry and electrochemical impedance spectroscopy. The architecture of the ATO-PDI photoanodic assembly was further modified via the introduction of a molecular iridium-based water oxidation catalyst, thus proving the versatility of the proposed hybrid interfaces as photoanodic platforms for photoinduced oxidations in PEC devices.

High‐Efficiency Single‐Photon Upconversion Photoluminescence of Perovskite Quantum Dots via Intragap State Regulation

AbstractLead halide perovskite quantum dots (PQDs) have shown remarkable single‐photon upconversion photoluminescence (SPUC‐PL) bringing them a brilliant perspective as the active media for biological imaging, optiag, and upconversion photovoltaics. However, the mechanism of SPUC in PQDs is still in dispute, and the specific strategy for optimizing PQDs toward a higher SPUC performance has yet to be established, which impedes the application of PQDs‐based SPUC‐PL in practice. In this work it is revealed that the PL quantum yield is declined by surface trap states, while the SPUC efficiency is promoted by Urbach tail states. These two types of intragap states can be chemically manipulated by engineering the surface ligand and the growth kinetics of perovskite nanocrystals, bringing on the improvement of light emission efficiency and the promotion of subgap low‐energy photon absorption, respectively. As a proof of concept, utilizing the synergistic effect of the proposed chemical manipulation method, the SPUC‐PL efficiency of PQDs is boosted by more than 40%, which gives rise to a spectral window of optical refrigeration gain as broad as ≈130 meV.

Concepts behind the Redox Photocatalysis with Quantum Dots

AbstractIn this conceptual review, we present the optical and electronic characteristics of quantum dots for the designing of organic synthesis experiments through the photocatalysis. We discuss the control parameters associated to the charge recombination processes on the semiconductor interface. The positioning of bands and control of intragap states, such as charge donors and acceptors, can define the performance of faradaic processes. Electrochemical strategies, such as voltammetry, can be used as a powerful tool for the determining of the electronic band edges with good precision.

Probing Intra-Gap States Mediated Charge Dynamics of Rh-Doped Rutile TiO2 Photocatalyst by Light-Modulated Photocurrent Spectroscopies.

The intra-gap states that are introduced into a semiconducting photocatalyst via dopants and other defects have significant implications on the transport dynamics of photoexcited electrons and holes during an aqueous light-driven reaction. In this work, mechanistic understanding of Rh-doped rutile, a promising photocatalyst for hydrogen production from water, is gained by systematic assessment combining intensity-modulated photocurrent spectroscopy with sub-gap excitations and alternating-current photocurrent spectroscopy. These operando techniques not only help in discovering a new electronic transport path in Rh-rutile via surface Rh4+ species and elucidating complex interaction between electrolyte molecules and semiconductors, but also underscore the potential of utilizing multiple sub-gap excitations synergistically. This combination offers a powerful tool for acquiring insight into photo-physical and photo-chemical behaviors of photo(electro)catalysts with intra-gap states.

Charge carrier recombination processes, intragap defect states, and photoluminescence mechanisms in stoichiometric and reduced TiO2 brookite nanorods: an interpretation scheme through in situ photoluminescence excitation spectroscopy in controlled environment.

The study of titanium dioxide (TiO2) in the brookite phase is gaining popularity as evidence has shown the efficient photocatalytic performance of this less investigated polymorph. It has been recently reported that defective anisotropic brookite TiO2 nanorods display remarkable substrate-specific reactivity towards alcohol photoreforming, with rates of hydrogen production significantly (18-fold) higher than those exhibited by anatase TiO2 nanoparticles. To elucidate the basic photo-physical mechanisms and peculiarities leading to such an improvement in the photoactive efficiency, we investigated the recombination processes of photoexcited charge carriers in both stoichiometric and reduced brookite nanorods via photoluminescence excitation spectroscopy in controlled environment. Through an investigation procedure employing both supragap and subgap excitation during successive exposure to oxidizing and reducing gaseous agents, we firstly obtained an interpretation scheme describing the main photoluminescence and charge recombination pathways in stoichiometric and reduced brookite, which includes information about the spatial and energetic position of the intragap states involved in photoluminescence mechanisms, and secondly identified a specific photoluminescence enhancement process occurring in only reduced brookite nanorods, which indicates the injection of a conduction band electron during ethanol photo-oxidation. The latter finding may shed light on the empirical evidence about the exceptional reactivity of reduced brookite nanorods toward the photo-oxidation of alcohols and the concomitant efficiency of photocatalytic hydrogen generation.

Periodical Ultra-Modulation of Broadened Laser Spectra in Dielectrics at Variable Ultrashort Laser Pulsewidths: Ultrafast Plasma, Plasmonic and Nanoscale Structural Effects

Self-phase modulation (SPM) broadening of prompt laser spectra was studied in a transmission mode in natural and synthetic diamonds at variable laser wavelengths (515 and 1030 nm), pulse energies and widths (0.3–12 ps, positively chirped pulses), providing their filamentary propagation. Besides the monotonous SPM broadening of the laser spectra versus pulse energy, which was more pronounced for the (sub)picosecond pulsewidths and more nitrogen-doped natural diamond with its intra-gap impurity states, periodical low-frequency modulation was observed in the spectra at the shorter laser pulsewidths, indicating dynamic Bragg filtering of the supercontinuum due to ultrafast plasma and nanoplasmonic effects. Damping of broadening and ultra-modulation for the longer picosecond pulsewidths was related to the thermalized electron-hole plasma regime established for the laser pulsewidths longer, than 2 ps. Unexpectedly, at higher pulse energies and corresponding longer, well-developed microfilaments, the number of low-intensity, low-frequency sideband spectral modulation features counterintuitively increases, thus indicating dynamic variation of the periods in the longitudinal plasma Bragg gratings along the filaments due to prompt secondary laser–plasmon interactions. The underlying sub- and/or near-wavelength longitudinal nanoscale Bragg gratings produced by femtosecond laser pulses in this regime could be visualized in less hard lithium niobate by atomic force microscopy cross-sectional analysis in the correlation with the corresponding sideband spectral components, supporting the anticipated Bragg filtering mechanism and envisioning the corresponding grating periods.

Regulating intragap states in colloidal quantum dots for universal photocatalytic hydrogen evolution

Understanding and manipulating intragap states in semiconductors may enable superior solar-to-hydrogen energy conversion. The effect of intragap states on photocatalysis usually remains unclear and is sometimes contradictory. Quantum-confined colloidal quantum dots (QDs) provide a unique platform to tune the density and distribution of intragap states due to their discrete energy levels. Herein, intragap active domains, composed of Cu vacancies (VCu′) and high-valent Cu (Cu*) defect states, are constructed in copper-deficient Zn-doped CuInS2 QDs. Note that these intragap states mainly exist at in-facet and on-edge defects in QDs, being away from the valence band maximum and close to Fermi level. Steady and transient optical spectra indicate that photoactivated Cu* states serving as photoinduced absorption centers can facilitate the generation of long-lived hot electrons (ca. 85 ps) as a manifestation of phonon bottleneck. Synergistically, the VCu′ states enable the holes capture and electron-hole pairs decoupling to suppress ultrafast Auger-like hot carrier cooling (ca. 178 fs). Moreover, the on-edge defects are demonstrated to play an active role in mediating proton reduction kinetics through density functional calculation. As a result, the QDs exhibit an outstanding hydrogen generation rate of 50.4 mmol g−1 h−1 without any noble metal, meanwhile, various molecule oxidation and polymer degradation can be integrated with the hydrogen generation process.

Enhancing Photocatalysis: Understanding the Mechanistic Diversity in Photocatalysts Modified with Single-Atom Catalytic Sites.

Surface modification of heterogeneous photocatalysts with single-atom catalysts (SACs) is an attractive approach for achieving enhanced photocatalytic performance. However, there is limited knowledge of the mechanism of photocatalytic enhancement in SAC-modified photocatalysts, which makes the rational design of high-performance SAC-based photocatalysts challenging. Herein, a series of photocatalysts for the aerobic degradation of pollutants based on anatase TiO2 modified with various low-cost, non-noble SACs (vanadate, Cu, and Fe ions) is reported. The most active SAC-modified photocatalysts outperform TiO2 modified with the corresponding metal oxide nanoparticles and state-of-the-art benchmark photocatalysts such as platinized TiO2 and commercial P25 powders. A combination of in situ electron paramagnetic resonance spectroscopy and theoretical calculations reveal that the best-performing photocatalysts modified with Cu(II) and vanadate SACs exhibit significant differences in the mechanism of activity enhancement, particularly with respect to the rate of oxygen reduction. The superior performance of vanadate SAC-modified TiO2 is found to be related to the shallow character of the SAC-induced intragap states, which allows for both the effective extraction of photogenerated electrons and fast catalytic turnover in the reduction of dioxygen, which translates directly into diminished recombination. These results provide essential guidelines for developing efficient SAC-based photocatalysts.

Does the Traditional Band Picture Describe the Electronic Structure of Doped Conjugated Polymers? TD-DFT and Natural Transition Orbital Study of Doped P3HT.

Polarons and bipolarons are created when one or two electrons are removed from the π-system of a p-type conjugated polymer, respectively. In the traditional band picture, the creation of a polaron causes two electronic energy levels to move into the band gap. The removal of a second electron to form a bipolaron causes the two intragap states to move further into the gap. Several groups, however, who looked at the energies of the Kohn-Sham orbitals from DFT calculations, have recently argued that the traditional band picture is incorrect for explaining the spectroscopy of doped conjugated polymers. Instead, the DFT calculations suggest that polaron creation causes only one unoccupied state to move into the band gap near the valence band edge while half-filled state in the valence band and the conduction band bend downward in energy. To understand the discrepancy, we performed TD-DFT calculations of polarons and bipolarons on poly(3-hexylthiophene) (P3HT). Not only do the TD-DFT-calculated absorption spectra match the experimental absorption spectra, but an analysis using natural transitional orbitals (NTOs), which provides an approximate one-electron picture from the many-electron TD-DFT results, supports the traditional band picture. Our TD-DFT/NTO analysis indicates that the traditional band picture also works for bipolarons, a system for which DFT calculations were unable to determine the electronic structure.

Phase transition of polarons in bilayer graphene nanoribbons

Stacking graphene nanoribbons (GNRs) is the natural path to obtain semiconductors with exotic quantum phenomena by manipulating the interlayer coupling. Recently, a report demonstrated that, during charge transport, interlayer coupling significantly affects the phonon breathing modes. Therefore, a reliable physical description of charged carriers must explicitly address the coupling nature of the electronic and lattice phenomena. In this work, we gauge the influence of interlayer coupling (t ⊥) on the formation of charged carriers in a bilayer of an armchair graphene nanoribbon using a model Hamiltonian with electron-phonon coupling. We find different quasiparticle solutions depending on the t ⊥ magnitude. As it increases, the carrier’s charge progressively delocalizes along the layers, resulting in two interlayer polaron morphologies: the non-symmetric (0 meV <t ⊥ ≤ 45 meV) and the symmetric (t ⊥> 45 meV). These solutions also manifest in the band structure through first-order electronic phase transitions in the intragap states with a significant energy shift of about 0.3 eV. Consequently, the carrier’s mobility and effective mass are expected to be highly sensitive to t ⊥, suggesting that mechanical stress can regulate the mechanism. The findings extend to other GNR bilayers, potentially inspiring the development of novel nanoelectronics based on highly confined stacked systems.

Investigating the Mechanism by Which Intragap States Tailor Light Emission: Case of Copper Deficient and Zn Doped Cu−In−Se Quantum Dots**

AbstractThe large structural tolerance of I–III–VI group quantum dots (QDs) to off‐stoichiometry allows their photoluminescence properties to be adjusted via doping, thereby enabling application in different fields. However, the photophysical processes underlying their photoluminescence mechanism remain significantly unknown. In particular, the transition channels of CuInSe2 QDs, which are altered by intrinsic and extrinsic intragap states, remain poorly reported. Herein, we investigated the photophysical processes associated with intragap states via electrochemical and optical techniques by using copper deficient Cu−In−Se QDs as well as Zn doped Cu−In−Se QDs. When the Cu/In molar ratios of Cu−In−Se QDs increased from 0.3 : 1 to 0.9 : 1, the photoluminescence spectra displayed a red‐shift from 700 nm to 1050 nm. Although there was a blue‐shift after the introduction of Zn2+ dopants in Cu−In−Se QDs, a significant red‐shift occurred (from 660 nm to 760 nm) when the Zn/Cu molar ratios decreased from 0.7 : 0.3 to 0.3 : 0.7. The Gaussian deconvolution results of the photoluminescence spectra and the band gap derived from absorption spectra by fitting supported the fact that the optical transition channels are dependent on the Cu/In and Zn/Cu molar ratios. After the introduction of the Zn2+ ions, the alloyed‐resultant blue‐shift of the emission spectra was observed, primarily due to the enlarged band gap; however, the radiative recombination of prominent intrinsic intragap states is still observed; and only a small proportion of the band‐edge exciton undergoes recombination for the sample with low Zn content. Cyclic voltammetry measurements revealed well‐defined extrinsic ZnCu intragap states (Zn substitution on Cu sites) and intrinsic Cux (x= 1+/2+) states in the band gap. The results presented here provide a better understanding of the varying effects of dopant on photoluminescence in terms of I–III–VI group QDs.

Surface Engineering of Metal and Semiconductor Nanocrystal Assemblies and Their Optical and Electronic Devices.

ConspectusColloidal nanocrystals (NCs) are composed of inorganic cores and organic or inorganic ligand shells and serve as building blocks of NC assemblies. Metal and semiconductor NCs are well known for the size-dependent physical properties of their cores. The large NC surface-to-volume ratio and the space between NCs in assemblies places significant importance on the composition of the NC surface and ligand shell. Nonaqueous colloidal NC syntheses use relatively long organic ligands to control NC size and uniformity during growth and to prepare stable NC dispersions. However, these ligands create large interparticle distances that dilute the metal and semiconductor NC properties of their assemblies. In this Account, we describe postsynthesis chemical treatments to engineer the NC surface and design the optical and electronic properties of NC assemblies. In metal NC assemblies, compact ligand exchange reduces the interparticle distance and drives an insulator-to-metal transition tuning the dc resistivity over a 1010 range and the real part of the optical dielectric function from positive to negative across the visible-to-IR region. Juxtaposing NC and bulk metal thin films in bilayers allows the differential chemical and thermal addressability of the NC surface to be exploited in device fabrication. Ligand exchange and thermal annealing densifies the NC layer, creating interfacial misfit strain that triggers folding of the bilayers and is used to fabricate, with only one lithography step, large-area 3D chiral metamaterials. In semiconductor NC assemblies, chemical treatments such as ligand exchange, doping, and cation exchange control the interparticle distance and composition to add impurities, tailor stoichiometry, or make entirely new compounds. These treatments are employed in longer studied II-VI and IV-VI materials and are being developed as interest in III-V and I-III-VI2 NC materials grows. NC surface engineering is used to design NC assemblies with tailored carrier energy, type, concentration, mobility, and lifetime. Compact ligand exchange increases the coupling between NCs but can introduce intragap states that scatter and reduce the lifetime of carriers. Hybrid ligand exchange with two different chemistries can enhance the mobility-lifetime product. Doping increases carrier concentration, shifts the Fermi energy, and increases carrier mobility, creating n- and p-type building blocks for optoelectronic and electronic devices and circuits. Surface engineering of semiconductor NC assemblies is also important to modify device interfaces to allow the stacking and patterning of NC layers and to realize excellent device performance. It is used to construct NC-integrated circuits, exploiting the library of metal, semiconductor, and insulator NCs, to achieve all-NC, solution-fabricated transistors.

Defect Engineering to Achieve Photostable Wide Bandgap Metal Halide Perovskites.

Bandgap tuning is a crucial characteristic of metal-halide perovskites, with benchmark lead-iodide compounds having a bandgap of 1.6 eV. To increase the bandgap up to 2.0 eV, a straightforward strategy is to partially substitute iodide with bromide in so-called mixed-halide lead perovskites. Such compounds are prone, however, to light-induced halide segregation resulting in bandgap instability, which limits their application in tandem solar cells and a variety of optoelectronic devices. Crystallinity improvement and surface passivation strategies can effectively slow down, but not completely stop, such light-induced instability. Here we identify the defects and the intragap electronic states that trigger the material transformation and bandgap shift. Based on such knowledge, we engineer the perovskite band edge energetics by replacing lead with tin and radically deactivate the photoactivity of such defects. This leads to metal halide perovskites with a photostable bandgap over a wide spectral range and associated solar cells with photostable open circuit voltages.

Lattice Mn2+ doped CdSe/CdS quantum dots for high-performance photoelectrochemical hydrogen evolution

Colloidal core/shell quantum dots (QDs) have emerged as a promising light absorber for hydrogen (H2) production in photoelectrochemical (PEC) cells due to their attractive optoelectronic properties. However, the unfavorable band alignment and lattice mismatch of core/shell materials lead to the sluggish separation/transfer of interfacial charges, challenging the large-scale utilization of QDs-based PEC systems. Herein, we report a unique synthetic approach that incorporates metal ions (Mn2+) into the lattice of heterostructured QDs in the process of shell growth, which is verified by the combined spectroscopic and electrochemical characterizations. The PEC cell based on the optimized QDs (Mn0.03-CdSe/CdS) exhibits a superior saturated photocurrent density (∼ 18.7 mA cm−2) to that of undoped CdSe/CdS QDs (∼ 9.6 mA cm−2) under one sun illumination. The introduced intragap states (4T1) from Mn2+ ions not only reduce the conduction band offset between CdSe and CdS, but also suppress the non-radiative recombination process of photogenerated charges. This work provides a well-grounded guide to utilize metal ions for improving the transfer dynamics of photogenerated charges of heterostructured QDs in other optoelectronic devices.

Development of Cu-In-Ga-S quantum dots with a narrow emission peak for red electroluminescence.

Narrowing the emission peak width and adjusting the peak position play a key role in the chromaticity and color accuracy of display devices with the use of quantum dot light-emitting diodes (QD-LEDs). In this study, we developed multinary Cu-In-Ga-S (CIGS) QDs showing a narrow photoluminescence (PL) peak by controlling the Cu fraction, i.e., Cu/(In+Ga), and the ratio of In to Ga composing the QDs. The energy gap of CIGS QDs was enlarged from 1.74 to 2.77eV with a decrease in the In/(In+Ga) ratio from 1.0 to 0. The PL intensity was remarkably dependent on the Cu fraction, and the PL peak width was dependent on the In/(In+Ga) ratio. The sharpest PL peak at 668nm with a full width at half maximum (fwhm) of 0.23eV was obtained for CIGS QDs prepared with ratios of Cu/(In+Ga) = 0.3 and In/(In+Ga) = 0.7, being much narrower than those previously reported with CIGS QDs, fwhm of >0.4eV. The PL quantum yield of CIGS QDs, 8.3%, was increased to 27% and 46% without a PL peak broadening by surface coating with GaSx and Ga-Zn-S shells, respectively. Considering a large Stokes shift of >0.5eV and the predominant PL decay component of ∼200-400ns, the narrow PL peak was assignable to the emission from intragap states. QD-LEDs fabricated with CIGS QDs surface-coated with GaSx shells showed a red color with a narrow emission peak at 688nm with a fwhm of 0.24eV.

Electronic Structure of 1D Lepidocrocite TiO2 as Revealed by Optical Absorption and Photoelectron Spectroscopy

We recently demonstrated scalable, one-pot syntheses of one-dimensional, titania lepidocrocite microfilaments by reacting Ti-containing water-insoluble, earth-abundant compounds such as TiC, TiB2, TiN, etc., with tetraalkylammonium hydroxide, TMAOH, for a few days at 85 °C under ambient pressure. The resulting one-dimensional lepidocrocite (1DL) titania-based nanofilaments, NFs, tend to self-align along the [100] growth direction to form microfilaments that sometimes self-align into pseudo-two-dimensional (2D) sheets. With sub-square-nanometer cross sections, the resulting band gap energy, Eg, at 4.0 eV is one of the highest ever reported for a titania material. Despite a large band gap, the nanofilaments exhibit significant absorbance throughout the visible spectrum ascribable to intra-gap defect states based on UV–Vis absorbance data and ultraviolet photoelectron spectroscopy (UPS). UP spectra demonstrate work functions of 4.0 ± 0.3 eV vs vacuum and Fermi energies of 3.8 ± 0.1 eV with respect to the valence band edge. Transient absorption (TA) spectroscopy of the 1DL nanofilament thin films with sub-band-gap, visible-light illumination reveals photoexcitations with lifetimes in excess of nanoseconds. In combination with the established oxidative stability, long-lived visible photoexcitations bring forward possible applications of 1DL nanofilaments in photocatalysis and optoelectronics.

Black phosphorus unipolar transistor, memory, and photodetector

We report the fabrication, electrical, and optical characterizations of few-layered black phosphorus (BP)-based field-effect transistor (FET). The fabricated device exhibits a p-type transport with hole mobility up to 175 cm2 V−1 s−1 at Vds = 1 mV. The transfer characteristics show a large hysteresis width that depends linearly on the gate voltage and decreases with the increasing drain bias. The fabricated device also ensures a non-volatile charge-trap memory behaviour, with a stable and long retention time. The material’s photodetection capabilities enhance the functionality of the device making it controllable by light. The photocurrent was observed to be linearly increasing with the light incident power and exposure time. As a photodetector, the transistor reaches a responsivity and detectivity up to 340 mA W−1 and 6.52 × 1011 Jones under white light at 80 mathrm{mW}, respectively. Time-resolved measurements provide evidence of a long single exponential decay process through deep intra-gap states. Our results highlight the potential of a few layers BP as a nanomaterial for field-effect, memory, and optoelectronic devices.Graphical

Changing the Interaction of a Single-Molecule Magnetic Moment with a Superconductor.

The exchange interaction of a brominated Co-porphyrin molecule with the Cooper pair condensate of Pb(111) is modified by reducing the Co-surface separation. The stepwise dehalogenation and dephenylation change the Co adsorption height by a few picometers. Only the residual Co-porphine core exhibits a Yu-Shiba-Rusinov bound state with low binding energy in the Bardeen-Cooper-Schrieffer energy gap. Accompanying density functional calculations reveal that the Co orbital carries the molecular magnetic moment and is responsible for the intragap state. The calculated spatial evolution of the Yu-Shiba-Rusinov wave function is compatible with the experimentally observed oscillatory attenuation of the electron-hole asymmetry with increasing lateral distance from the magnetic porphine center.

The impact of spatially heterogeneous chemical doping on the electronic properties of CdSe quantum dots: insights from ab initio computation.

The introduction of copper (Cu) impurity in semiconductor CdSe quantum dots (QDs) gives rise to unique photoluminescence (PL) bands exhibiting distinctive characteristics, like broad line width, significant Stokes shift, and complex temporal decay. The atomistic origins of these spectral features are yet to be understood comprehensively. We employed multiple computational techniques to systematically study the impact of the spatial heterogeneity of Cu atoms on the stability and photophysical properties, including the emission linewidth of doped QDs under ambient conditions. The Cu substitution introduces a spin-polarized intragap state, the energetic position of which is strongly dependent on the dopant location and causes spectral broadening in QD ensembles. Furthermore, the dopant dynamics under ambient conditions are significantly influenced by the specific arrangement of Cu within the QDs. The dynamic electronic structures of surface-doped CdSe illustrate more pronounced perturbations and vary the mid-gap state position more drastically than those of the core-doped QDs. Vibronic coupling broadens the photoluminescence peaks associated with the conduction band-to-defect level transition for individual QDs. These insights into the dynamic structure-photophysical property relationship suggest viable approaches, such as tuning the operational temperature and selective co-doping, to enhance the functional performances of doped CdSe QDs strategically.