Host Semiconductor Research Articles

A Charged Particle with Anisotropic Mass in a Perpendicular Magnetic Field–Landau Gauge

The loss of any symmetry in a system leads to quantum problems that are typically very difficult to solve. Such a situation arises for particles with anisotropic mass, like electrons in various semiconductor host materials, where it is known that they may have an anisotropic effective mass. In this work, we consider the quantum problem of a spinless charged particle with anisotropic mass in two dimensions and study the resulting energy and eigenstate spectrum in a uniform constant perpendicular magnetic field when a Landau gauge is adopted. The exact analytic solution to the problem is obtained for arbitrary values of the anisotropic mass using a mathematical technique that relies on the scaling of the original coordinates. The characteristic features of the energy spectrum and corresponding eigenstate wave functions are analyzed. The results of this study are expected to be of interest to quantum Hall effect theory.

Low disorder and high valley splitting in silicon

The electrical characterisation of classical and quantum devices is a critical step in the development cycle of heterogeneous material stacks for semiconductor spin qubits. In the case of silicon, properties such as disorder and energy separation of conduction band valleys are commonly investigated individually upon modifications in selected parameters of the material stack. However, this reductionist approach fails to consider the interdependence between different structural and electronic properties at the danger of optimising one metric at the expense of the others. Here, we achieve a significant improvement in both disorder and valley splitting by taking a co-design approach to the material stack. We demonstrate isotopically purified, strained quantum wells with high mobility of 3.14(8) × 105 cm2 V−1 s−1 and low percolation density of 6.9(1) × 1010 cm−2. These low disorder quantum wells support quantum dots with low charge noise of 0.9(3) μeV Hz−1/2 and large mean valley splitting energy of 0.24(7) meV, measured in qubit devices. By striking the delicate balance between disorder, charge noise, and valley splitting, these findings provide a benchmark for silicon as a host semiconductor for quantum dot qubits. We foresee the application of these heterostructures in larger, high-performance quantum processors.

Ligand-Directed Self-Assembly of Organic-Semiconductor/Quantum-Dot Blend Films Enables Efficient Triplet Exciton-Photon Conversion.

Blends comprising organic semiconductors and inorganic quantum dots (QDs) are relevant for many optoelectronic applications and devices. However, the individual components in organic-QD blends have a strong tendency to aggregate and phase-separate during film processing, compromising both their structural and electronic properties. Here, we demonstrate a QD surface engineering approach using electronically active, highly soluble semiconductor ligands that are matched to the organic semiconductor host material to achieve well-dispersed inorganic-organic blend films, as characterized by X-ray and neutron scattering, and electron microscopies. This approach preserves the electronic properties of the organic and QD phases and also creates an optimized interface between them. We exemplify this in two emerging applications, singlet-fission-based photon multiplication (SF-PM) and triplet-triplet annihilation-based photon upconversion (TTA-UC). Steady-state and time-resolved optical spectroscopy shows that triplet excitons can be transferred with near unity efficiently across the organic-inorganic interface, while the organic films maintain efficient SF (190% yield) in the organic phase. By changing the relative energy between organic and inorganic components, yellow upconverted emission is observed upon 790 nm NIR excitation. Overall, we provide a highly versatile approach to overcome longstanding challenges in the blending of organic semiconductors with QDs that have relevance for many optical and optoelectronic applications.

Enhanced room-temperature magnetic field effect on spin-polarized excitons of cesium lead bromine-magnetite nanocomposites

The generation and manipulation of spin-polarized electrons are the basis of spintronic applications. Spin injection from a ferromagnetic surface or heterojunction to a semiconductor adjacent layer is often used to create spin-polarized carriers; however, for halide perovskites, due to the mismatch of lattice parameters with most ferromagnets at room temperature, this spin injection is challenging. In this study, we synthesize all-inorganic perovskite CsPbBr3 surrounded by Fe3O4 magnetic nanoparticles. It is found that this nanocomposite shows both magnetization and magnetic field-induced circularly polarized photoluminescence at room temperature. Specifically, with the attachment of Fe3O4 nanoparticles closely on the surface of CsPbBr3 nanocrystals, both the degree of circular polarization and g-factor enhanced by 3.5 times compared with that of pure CsPbBr3. The phenomenon should be due to the formation of exciton magnetic polaron through the coupling of the magnetic aligned nanoparticles with the excitonic state of the host semiconductor in the external magnetic field. The effective spin injection provides a method of controlling the excitonic spin polarization of all-inorganic halide perovskites for spintronic applications.

Room temperature optically detected magnetic resonance of single spins in GaN.

High-contrast optically detected magnetic resonance is a valuable property for reading out the spin of isolated defect colour centres at room temperature. Spin-active single defect centres have been studied in wide bandgap materials including diamond, SiC and hexagonal boron nitride, each with associated advantages for applications. We report the discovery of optically detected magnetic resonance in two distinct species of bright, isolated defect centres hosted in GaN. In one group, we find negative optically detected magnetic resonance of a few percent associated with a metastable electronic state, whereas in the other, we find positive optically detected magnetic resonance of up to 30% associated with the ground and optically excited electronic states. We examine the spin symmetry axis of each defect species and establish coherent control over a single defect's ground-state spin. Given the maturity of the semiconductor host, these results are promising for scalable and integrated quantum sensing applications.

Understanding the suitable alloying conditions for highly efficient Cu- and Mn-doped Zn1-xCdxS/ZnS core-shell quantum dots

Doping of alloyed colloidal quantum dots (QDs) has garnered significant attention for providing tunable and Stokes-shifted emission. By alloying the host semiconductor nanocrystals (NCs), their band gap can be tuned. With the specific addition of dopant ions, these NCs can emit tunable emissions within the visible spectrum. However, while doped and alloyed quantum dots (QDs) have shown promise for tunable emissions, their emission qualities have not been consistent across the spectrum. Here, we report the synthesis of high-quality Cu- and Mn-doped ZnxCd1-xS (x = 0–1) alloyed QDs by a colloidal non-injection method. In this study, we examined the effect of different dopant ions on the optical properties of similar alloyed nanocrystals. The deposition of a ZnS shell on these doped QDs significantly improves their quantum yield (QY), increasing it from 7.0 % to 50.0 % for Cu-doped QDs and from 30.0 % to 80.0 % for Mn-doped QDs. The Cu-doped QDs exhibit tunable emission from green to red across the visible spectrum by varying the Zn/Cd ratio, whereas the Mn-doped QDs show a fixed orange emission. Interestingly, the Cu-doped alloyed QDs show a contrasting trend in quantum yield (QY) compared to those of Mn-doped QDs when the amount of Cd in ZnCdS alloyed QDs is systematically changed. As the amount of Cd increases in the ZnCdS alloyed QDs, the Cu-doped QDs show both an increase in average lifetime and an increase in QY. In contrast, for the Mn-doped QDs, the decay lifetime values remain fairly constant for different amounts of Cd in the ZnCdS alloyed QDs, but the QY decreases as the amount of Cd increases. The results of this study may facilitate the design of optimal alloying combinations for Cu/Mn-doped QDs in optoelectronic applications.

Defect Engineering of Ta3N5 Photoanodes: Enhancing Charge Transport and Photoconversion Efficiencies via Ti Doping

AbstractWhile Ta3N5 shows excellent potential as a semiconductor photoanode for solar water splitting, its performance is hindered by poor charge carrier transport and trapping due to native defects that introduce electronic states deep within its bandgap. Here, it is demonstrated that controlled Ti doping of Ta3N5 can dramatically reduce the concentration of deep‐level defects and enhance its photoelectrochemical performance, yielding a sevenfold increase in photocurrent density and a 300 mV cathodic shift in photocurrent onset potential compared to undoped material. Comprehensive characterization reveals that Ti4+ ions substitute Ta5+ lattice sites, thereby introducing compensating acceptor states, reducing the concentrations of deleterious nitrogen vacancies and reducing Ta3+ states, and thereby suppressing trapping and recombination. Owing to the similar ionic radii of Ti4+ and Ta5+, substitutional doping does not introduce lattice strain or significantly affect the underlying electronic structure of the host semiconductor. Furthermore, Ti can be incorporated without increasing the oxygen donor content, thereby enabling the electrical conductivity to be tuned by over seven orders of magnitude. Thus, Ti doping of Ta3N5 provides a powerful basis for precisely engineering its optoelectronic characteristics and to substantially improve its functional characteristics as an advanced photoelectrode for solar fuels applications.

High-throughput identification of spin-photon interfaces in silicon.

Color centers in host semiconductors are prime candidates as spin-photon interfaces for quantum applications. Finding an optimal spin-photon interface in silicon would move quantum information technologies toward a mature semiconducting host. However, the space of possible charged defects is vast, making the identification of candidates from experiments alone extremely challenging. Here, we use high-throughput first-principles computational screening to identify spin-photon interfaces among more than 1000 charged defects in silicon. The use of a single-shot hybrid functional approach is critical in enabling the screening of many quantum defects with a reasonable accuracy. We identify three promising spin-photon interfaces as potential bright emitters in the telecom band: [Formula: see text], [Formula: see text], and [Formula: see text]. These candidates are excited through defect-bound excitons, stressing the importance of such defects in silicon for telecom band operations. Our work paves the way to further large-scale computational screening for quantum defects in semiconductors.

Additive GaN Solid Immersion Lenses for Enhanced Photon Extraction Efficiency from Diamond Color Centers.

Effective light extraction from optically active solid-state spin centers inside high-index semiconductor host crystals is an important factor in integrating these pseudo-atomic centers in wider quantum systems. Here, we report increased fluorescent light collection efficiency from laser-written nitrogen-vacancy (NV) centers in bulk diamond facilitated by micro-transfer printed GaN solid immersion lenses. Both laser-writing of NV centers and transfer printing of micro-lens structures are compatible with high spatial resolution, enabling deterministic fabrication routes toward future scalable systems development. The micro-lenses are integrated in a noninvasive manner, as they are added on top of the unstructured diamond surface and bonded by van der Waals forces. For emitters at 5 μm depth, we find approximately 2× improvement of fluorescent light collection using an air objective with a numerical aperture of NA = 0.95 in good agreement with simulations. Similarly, the solid immersion lenses strongly enhance light collection when using an objective with NA = 0.5, significantly improving the signal-to-noise ratio of the NV center emission while maintaining the NV's quantum properties after integration.

Optically detected magnetic resonance spectroscopic analyses on the role of magnetic ions in colloidal nanocrystals.

Incorporating magnetic ions into semiconductor nanocrystals has emerged as a prominent research field for manipulating spin-related properties. The magnetic ions within the host semiconductor experience spin-exchange interactions with photogenerated carriers and are often involved in the recombination routes, stimulating special magneto-optical effects. The current account presents a comparative study, emphasizing the impact of engineering nanostructures and selecting magnetic ions in shaping carrier-magnetic ion interactions. Various host materials, including the II-VI group, halide perovskites, and I-III-VI2 in diverse structural configurations such as core/shell quantum dots, seeded nanorods, and nanoplatelets, incorporated with magnetic ions such as Mn2+, Ni2+, and Cu1+/2+ are highlighted. These materials have recently been investigated by us using state-of-the-art steady-state and transient optically detected magnetic resonance (ODMR) spectroscopy to explore individual spin-dynamics between the photogenerated carriers and magnetic ions and their dependence on morphology, location, crystal composition, and type of the magnetic ion. The information extracted from the analyses of the ODMR spectra in those studies exposes fundamental physical parameters, such as g-factors, exchange coupling constants, and hyperfine interactions, together providing insights into the nature of the carrier (electron, hole, dopant), its local surroundings (isotropic/anisotropic), and spin dynamics. The findings illuminate the importance of ODMR spectroscopy in advancing our understanding of the role of magnetic ions in semiconductor nanocrystals and offer valuable knowledge for designing magnetic materials intended for various spin-related technologies.

Investigation of LSPR Coupling Effects toward the Rational Design of CsxWO3–δ Based Solar NIR Filtering Coatings

AbstractThe optical range of localized surface plasmon resonance (LSPR) is extended into the infrared region, thanks to the development of highly doped semiconductor nanocrystals. Particularly, the near‐infrared (NIR) range holds a significant interest in managing solar radiation. However, practical applications necessitate the arrangement of particles, which is known to possibly impact their optical properties through LSPR coupling effects. How such coupling modifies the LSPR response in semiconductor hosts remains largely unexplored. In this study, a protocol for producing composite coatings composed of cesium‐doped tungsten bronze nanocrystals embedded in a silica matrix is presented. Achieving individual dispersion of nanocrystals is made possible through careful selection of a surface polyglycerol ligand exchange. This allows to tune the interparticle distance by adjusting the nanocrystal volume fraction in the composite. The findings demonstrate that LSPR coupling effects significantly influence the LSPR intensity of nanocrystals in the composite when the nanocrystal‐to‐nanocrystal distance matches their size. Beyond elucidating the LSPR coupling effect, this study provides insights into the potential use of Cs‐HTB nanocrystals for solar control applications. Through the optimization of morphology and film structure, remarkable selectivity is obtained in terms of maintaining good transparency in the visible range while achieving high absorption in the NIR.

P‐Type Doping of PM6:Y6‐Based Photoactive Layer with Formic Acid

The introduction of molecular doping process is necessary to enhance the optic and electronic properties of organic semiconductors for facilitating charge transport. In particular, since the doping process has a positive influence on the charge transfer interaction between host semiconductor and dopant, improved mobility has been efficiently achieved. Despite its advantages, doping technologies in organic solar cells (OSCs) are emphasized to the development of n‐type dopants used for balancing the electron and hole. In addition, since the bulk‐heterojunction microstructure in OSCs has randomly blended phases of the donor and acceptor, it is important to optimize charge extraction without loss by controlling the morphology. Herein, OSCs by p‐type doping with formic acid (FA) into a photoactive layer is reported. The champion device yields a significantly improved power conversion efficiency from 14.3% to 15.3% with a high fill factor of 71.7%. It is found that the p‐doped photoactive layer exhibits enhanced conductivity, improved carrier mobilities, suppressed charge recombination, and lowered leakage current. The FA simultaneously acts as a film morphology controller of the photoactive layer with enhanced phase separation to transport the charge efficiently. Thus, the doping process with FA can maintain the device performance in stability tests (95.6% remaining).

Sterically‐Hindered Molecular p‐Dopants Promote Integer Charge Transfer in Organic Semiconductors

AbstractMolecular p‐dopants designed to undergo electron transfer with organic semiconductors are typically planar molecules with high electron affinity. However, their planarity can promote the formation of ground‐state charge transfer complexes with the semiconductor host and results in fractional instead of integer charge transfer, which is highly detrimental to doping efficiency. Here, we show this process can be readily overcome by targeted dopant design exploiting steric hindrance. To this end, we synthesize and characterize the remarkably stable p‐dopant 2,2′,2′′‐(cyclopropane‐1,2,3‐triylidene)tris(2‐(perfluorophenyl)acetonitrile) comprising pendant functional groups that sterically shield its central core while retaining high electron affinity. Finally, we demonstrate it outperforms a planar dopant of identical electron affinity and increases the thin film conductivity by up to an order of magnitude. We believe exploiting steric hindrance represents a promising design strategy towards molecular dopants of enhanced doping efficiency.

Sterically-Hindered Molecular p-Dopants Promote Integer Charge Transfer in Organic Semiconductors.

Molecular p-dopants designed to undergo electron transfer with organic semiconductors are typically planar molecules with high electron affinity. However, their planarity can promote the formation of ground-state charge transfer complexes with the semiconductor host and results in fractional instead of integer charge transfer, which is highly detrimental to doping efficiency. Here, we show this process can be readily overcome by targeted dopant design exploiting steric hindrance. To this end, we synthesize and characterize the remarkably stable p-dopant 2,2',2''-(cyclopropane-1,2,3-triylidene)tris(2-(perfluorophenyl)acetonitrile) comprising pendant functional groups that sterically shield its central core while retaining high electron affinity. Finally, we demonstrate it outperforms a planar dopant of identical electron affinity and increases the thin film conductivity by up to an order of magnitude. We believe exploiting steric hindrance represents a promising design strategy towards molecular dopants of enhanced doping efficiency.

Pseudo-spin order of Wigner crystals in multi-valley electron gases

We study multi-valley electron gases in the low density (rs ≫ 1) limit. Here the ground-state is always a Wigner crystal (WC), with additional pseudo-spin order where the pseudo-spins are related to valley occupancies. Depending on the symmetries of the host semiconductor and the values of the parameters such as the anisotropy of the effective mass tensors, we find a striped or chiral pseudo-spin antiferromagnet, or a time-reversal symmetry breaking orbital loop-current ordered pseudo-spin ferromagnet. Our theory applies to the recently-discovered WC states in AlAs and in mono and bilayer transition metal dichalcogenides. We identify a set of interesting electronic liquid crystalline phases that could arise by continuous quantum melting of such WCs.

Mn Doping in Low-Dimensional Perovskites: A Switch for Controlling Dopant and Host Emission

The growth of solid-state photonics relies on the design of highly efficient devices with tunable photoluminescence (PL) based on thermally stable phosphors. In this study, a room-temperature, all-ambient synthesis of Mn-doped hybrid lead halide perovskite phosphors is presented. By applying temperature-dependent (4.2–300 K) steady-state and transient PL measurements, the photophysical pathways of the hybrid system were identified and the carrier recombination processes at play were defined. At higher Mn-doping concentrations (>4%), the excitonic white light host emission nearly disappears, and a bright Mn transition appears at ∼650 nm with a record PL quantum yield of ∼87.4%. The intense sensitized Mn luminescence results from rapid and efficient exciton-to-dopant energy transfer, as evidenced by time-gated and femtosecond fluorescence upconversion measurements. A millisecond PL decay time attributed to the Mn dopant and a microsecond PL decay time associated with the excitonic emission of the host were found, indicating energy and reverse energy transfer in the system. These findings provide unique insights into the chemical tailoring of the Mn-dopant emission by investigating the coupling between the host semiconductor and the dopant ion, a stepping stone toward the development of high-performance solid-state light-emitting diodes and scintillators.

Doped nanomaterials: Application in hydrogen production via photocatalytic water splitting

A green and sustainable energy resource is needed to meet global energy demand and minimize environmental pollution. Hydrogen (H2) is a clean and renewable energy that can be generated via photocatalytic splitting of water. Recent studies on the application of doped photocatalysts in water splitting are numerous. Here, metal and non-metal ion doped photocatalysts with their H2 production capacity has been reviewed. Firstly, the influence of metal/non-metal dopants on the properties of host semiconductors were deduced. Then, metal (alkaline earth, transition and inner-transition metal ions) and non-metal ions doped photocatalysts with their water splitting capacity were discussed. Different metal compounds and carbon nitride materials were used as host photocatalysts. The experimental conditions which influence the efficiency of the doped photocatalysts in H2 generation were highlighted. Strategies such as multi-ionic doping process, composite construction and defect creation for the enhancement of activity of doped photocatalysts in water splitting were also summarized. At last, the challenges, future directions and conclusions derived from this literature review were outlined.

Ferromagnetism by p−d exchange spin-orbit coupling in n -type ferromagnetic semiconductors

The exchange interaction between carrier and localized spin in magnets generates intrinsic spin-orbit coupling induced by the magnetism. Recent studies for the exchange spin-orbit coupling (ESOC) in ferromagnets and antiferromagnets suggest the ESOC and the transport phenomena for spintronics. However, the study on the effects of ESOC on the magnetic phase transition has been still lacking especially for ferromagnets even though the ESOC should be one of the fundamental interactions to stabilize the magnetic phase. In this paper, we study the role of the ferromagnetic properties of the ESOC induced by the $p\text{\ensuremath{-}}d$ exchange interaction of the valence band in $n$-type ferromagnetic semiconductors. Based on the mean-field and $\mathbit{k}\ifmmode\cdot\else\textperiodcentered\fi{}\mathbit{p}$ methods, our theory explains the spin polarization of localized and carrier spin, and the Curie temperature ${T}_{c}$ for the iron concentration, electron density, and host semiconductor dependence. The theoretical ${T}_{c}$ fits experimental values well in low iron concentration and intermediate electron density regions, and the $p\text{\ensuremath{-}}d$ exchange interaction is essential for ${T}_{c}$. Furthermore, the ${T}_{c}$ is higher for narrower gap host semiconductors to provide insights into higher ${T}_{c}$. The theoretical framework of this paper is not limited to the specific materials and will find potential materials for spintronics and the fundamental aspects.

An Iminostilbene Functionalized Benzimidazoline for Enhanced n‐Type Solution Doping of Semiconducting Polymers for Organic Thermoelectrics

AbstractDoped organic semiconductors play a central role in the development of several innovative optoelectronic and energy harvesting applications. Currently, the realization of thermoelectric generators, which require both hole‐ and electron‐transporting materials with high electrical conductivity, is strongly hindered by the scarce availability of stable solution‐processable n‐dopants and their limited efficiency. Herein, the synthesis of 4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzimidazol‐2‐yl)‐dibenzazepine (IStBI), a novel derivative belonging to the well‐known family of the benzimidazoline compounds, is presented. The functionalization with the planarized and rigid iminostilbene substituent allows, without significantly affecting the compound electronic structure, an efficient intercalation of the dopant molecules inside the ordered regions of thin films of the benchmark n‐type polymer poly(N,N′‐bis‐2‐octyldodecylnaphthalene‐1,4,5,8‐bis‐dicarboximide‐2,6‐diyl‐alt‐5,5′‐2,2′‐bithiophene) P(NDI2OD‐T2). Consequently, a maximum electrical conductivity of (1.14 ± 0.13) × 10−2 S cm−1 is recorded, exceeding by one order of magnitude what previously achieved upon solution doping of the reference P(NDI2OD‐T2) with benzimidazoline derivatives. The thermoelectric power factor is also simultaneously increased. The findings confirm that tailoring of the dopant chemical structure to improve structural interactions with the host semiconductors can be employed as a successful strategy to achieve more effective n‐doping, helping to close the performance gap with p‐type materials.

Reducing charge noise in quantum dots by using thin silicon quantum wells

Charge noise in the host semiconductor degrades the performance of spin-qubits and poses an obstacle to control large quantum processors. However, it is challenging to engineer the heterogeneous material stack of gate-defined quantum dots to improve charge noise systematically. Here, we address the semiconductor-dielectric interface and the buried quantum well of a 28Si/SiGe heterostructure and show the connection between charge noise, measured locally in quantum dots, and global disorder in the host semiconductor, measured with macroscopic Hall bars. In 5 nm thick 28Si quantum wells, we find that improvements in the scattering properties and uniformity of the two-dimensional electron gas over a 100 mm wafer correspond to a significant reduction in charge noise, with a minimum value of 0.29 ± 0.02 μeV/Hz½ at 1 Hz averaged over several quantum dots. We extrapolate the measured charge noise to simulated dephasing times to CZ-gate fidelities that improve nearly one order of magnitude. These results point to a clean and quiet crystalline environment for integrating long-lived and high-fidelity spin qubits into a larger system.