Self-assembled Quantum Wells Research Articles

Effect of phase distribution and defect passivation on amplified spontaneous emission of quasi-2D Dion–Jacobson perovskite

Quasi-2D Dion–Jacobson (DJ) halide perovskites with large exciton binding energy, self-assembled quantum wells, and high quantum yield attract growing attention in light-emitting diodes and solar devices. DJ-layered perovskites have the eliminated van der Waals gap and show improved photophysical features. However, there are a variety of defects and complex phase distributions produced during the solution procedure and the fast crystal development. In this paper, we reveal the effect of phase distribution and defect passivation on amplified spontaneous emission of quasi-2D perovskite (PDMA)(MA)2Pb3Br10 thin films through solvent engineering and additive methods, by establishing the correlation between the precursor compositions and the photophysical performance of the layered DJ perovskites. The energy transfer rate and the photoluminescence quantum yield increase due to the spatially homogeneous domain distribution and the reduced defect density after the addition of KBr in the DMSO:DMF. More importantly, we realize green amplified spontaneous emission and single-mode vertical-cavity surface-emitting lasing with low thresholds of 8.8 and 10.5 μJ cm−2, respectively. This work provides a guideline to achieve low-threshold multicolor lasers based on DJ perovskites.

Phase Engineering Reinforced Energy Transfer for High-Performance Blue Perovskite Light-Emitting Diodes.

Layered metal-halide perovskites, a category of self-assembled quantum wells, are of paramount importance in emerging photonic sources, such as lasers and light-emitting diodes (LEDs). Despite high trap density in two-dimensional (2D)perovskites, efficient non-radiative energy funneling from wide- to narrow-bandgap components, sustained by the Förster resonance energy transfer (FRET) mechanism, contributes to efficient luminescence by light or electrical injection. Herein, it is demonstrated that bandgap extension of layered perovskites to the blue-emitting regime will cause sluggish and inefficient FRET, stemming from the tiny spectral overlap between different phases. Motivated by the importance of blue LEDs and inefficient energy transfer in materials with phase polydispersity, wide-bandgap quasi-2D perovskites with narrow phase distribution, improved crystallinity, and the pure crystal orientation perpendicular to the charge transport layer are developed. Based on this emitter, high-performance blue perovskite LEDs with improved electroluminescence (EL) external quantum efficiency (EQE) of 7.9% at 478nm, a narrow full width at half-maximum (FWHM) of 22nm and a more stable EL spectra are achieved. These results provide an important insight into spectrally stable and efficient blue emitters and EL devices based on perovskites.

Highly Efficient Light-Emitting Diodes based on Self-Assembled Colloidal Quantum Wells.

Nanocrystal-based light-emitting diodes (Nc-LEDs) have immense potential for next-generation high-definition displays and lighting applications. They offer numerous advantages, such as low cost, high luminous efficiency, narrow emission, and long lifetime. However, the external quantum efficiency (EQE) of Nc-LEDs, typically employing isotropic nanocrystals, has been limited by the out-coupling factor. Here we demonstrate efficient, bright, and long lifetime red Nc-LEDs based on anisotropic nanocrystals of colloidal quantum wells (CQWs). Through modification of the substrate's surface properties and control of the interactions among CQWs, we successfully spin-coated a self-assembled layer with an exceptionally high distribution of in-plane transitions dipole moment (TDM) of 95%, resulting in an out-coupling factor of 37%. Our devices exhibit a remarkable peak external quantum efficiency (EQE) of 26.9%, accompanied by a maximum brightness of 55,754cd m-2 and a long operational lifetime (T95 @100cd m-2 ) over 15,000h. These achievements represent a significant advancement compared to previous studies on Nc-LEDs incorporating anisotropic nanocrystals. We expect our work to provide a general self-assembly strategy for enhancing the light extraction efficiency of Nc-LEDs based on anisotropic nanocrystals. This article is protected by copyright. All rights reserved.

Ultrasensitive Photodetectors Based on Strongly Interacted Layered-Perovskite Nanowires.

Metal-halide layered perovskites, self-assembled quantum wells with alternating insulating interlayer organic cations, and conductive perovskite layers boost the incorporation of multiple functionalities into a single-phase material. Optoelectronic performances in layered perovskites are more sensitive to crystallinity than their 3D counterparts due to the traps and insulating barriers introduced by interlayer cations. Here, we combine the capillary-bridge lithography method for the fabrication of single-crystalline nanowire arrays with strongly interacted layered perovskites for the enhancement of crystallinity and crystallographic orientation purity. Due to regulated nucleation and growth of layered perovskites in capillary bridges and the sulfur-sulfur interaction between interlayer cations, nanowires with pure (101) orientation are realized for underpinning insulating crystal interiors and photoconductive layer edges. Based on these nanowires, ultrasensitive photodetectors are reached with an ultralow dark current of below 10-12 A, an average responsivity of 7.3 × 103 A W-1, an average specific detectivity of 3.9 × 1015 Jones, and a 3 dB bandwidth of 10.3 kHz.

Kinetic Molecular Cationic Control of Defect-Induced Broadband Light Emission in 2D Hybrid Lead Iodide Perovskites.

In this study, we examine the effects of changing organic cation concentrations on the efficiency and photophysical implications of exciton trapping in two-dimensional hybrid lead iodide self-assembled quantum wells (SAQWs). We show that increasing the concentration of alkyl and aryl ammonium cations causes the formation of SAQWs at a liquid-liquid interface to possess intense, broadband subgap photoluminescence (PL) spectra. Electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopic studies suggest that materials formed under these cation concentrations possess morphologies consistent with inhibited crystallization kinetics but exhibit qualitatively similar bulk chemical bonding to nonluminescent materials stabilized in the same structure from precursor solutions containing lower cation concentrations. Temperature- and power-dependent PL spectra suggest that the broadband subgap light emission stems from excitons self-trapped at defect sites, which we assign as edge-like, collective I vacancies using a simple model of the chemical equilibrium driving material self-assembly. These results suggest that changes to the availability of molecular cations can suitably control the light emission properties of self-assembled hybrid organic-inorganic materials in ways central to their applicability in lighting technologies.

Anharmonic Molecular Vibrational Probes of Dynamical Organic–Inorganic Interactions in Two-Dimensional Hybrid Lead Iodide Perovskites

There remains a gap in our knowledge of the fundamental physical determinants of dynamical interactions between the constituents of two-dimensional hybrid perovskites, sometimes called self-assembled quantum wells (SAQWs). In this study, we use the anharmonic properties of vibrations localized on the molecular cations of two separate SAQW samples to characterize their coupling to low-frequency phonons in these materials. For the case of an aromatic molecular cation, benzyl ammonium, we use analysis of Raman spectra to propose that the quartic anharmonic coupling to phonons spread over both the organic and inorganic sublattices explains the spectral position of its ammonium bending vibration as a function of temperature. In contrast, we find that the cubic anharmonic coupling to phonons of the inorganic octahedral layers qualitatively explains the temperature-dependent peak position of this vibration for an alkyl molecular cation, hexyl ammonium. Furthermore, we use density functional theory calculations to construct the two-vibration density of states and characterize how cubic anharmonic coupling explains the shape of the ammonium bending vibrational peak in each material. Using this method, we explain the asymmetric shape of the NH3+ bending peak in hexyl ammonium lead iodide when measured at room temperature. Our results provide fundamental physical insights into the dynamical interactions between the organic and inorganic constituents of hybrid SAQWs necessary to further develop their use in thermal, mechanical, and electronic technologies.

Controlled bunching approach for achieving high efficiency active region in AlGaN-based deep ultraviolet light-emitting devices with dual-band emission

Developing efficient active region structures with low sensitivity to threading dislocation density (TDD) is of great technical significance for AlGaN-based deep ultraviolet (DUV) light-emitting devices. Here, we propose an active region strategy by introducing bunching effect to form self-assembled sidewall quantum wells (SQWs) with much stronger carrier confinement, resulting in a significant enhancement of internal quantum efficiency (from 46% to 59%) compared to the commonly adopted multiple quantum wells (MQWs) due to the lower sensitivity to TDD. As a demo, an AlGaN-based DUV light-emitting diode (LED) with the proposed active region involving both SQWs and MQWs presents dual-band emission and a consequent 68% enhancement in light output power compared to the DUV-LED with only MQWs as the active region, suggesting that the proposed architecture is fully suitable for the development of high performance DUV light-emitting devices even based on poor or medium quality materials.

Efficient Energy Funneling in Quasi-2D Perovskites: From Light Emission to Lasing.

Quasi-2D Ruddlesden-Popper halide perovskites with a large exciton binding energy, self-assembled quantum wells, and high quantum yield draw attention for optoelectronic device applications. Thin films of these quasi-2D perovskites consist of a mixture of domains having different dimensionality, allowing energy funneling from lower-dimensional nanosheets (high-bandgap domains) to 3D nanocrystals (low-bandgap domains). High-quality quasi-2D perovskite (PEA)2 (FA)3 Pb4 Br13 films are fabricated by solution engineering. Grazing-incidence wide-angle X-ray scattering measurements are conducted to study the crystal orientation, and transient absorption spectroscopy measurements are conducted to study the charge-carrier dynamics. These data show that highly oriented 2D crystal films have a faster energy transfer from the high-bandgap domains to the low-bandgap domains (<0.5 ps) compared to the randomly oriented films. High-performance light-emitting diodes can be realized with these highly oriented 2D films. Finally, amplified spontaneous emission with a low threshold 4.16 µJ cm-2 is achieved and distributed feedback lasers are also demonstrated. These results show that it is important to control the morphology of the quasi-2D films to achieve efficient energy transfer, which is a critical requirement for light-emitting devices.

The quantum-confined Stark effect in layered hybrid perovskites mediated by orientational polarizability of confined dipoles

The quantum-confined Stark effect (QCSE) is an established optical modulation mechanism, yet top-performing modulators harnessing it rely on costly fabrication processes. Here, we present large modulation amplitudes for solution-processed layered hybrid perovskites and a modulation mechanism related to the orientational polarizability of dipolar cations confined within these self-assembled quantum wells. We report an anomalous (blue-shifting) QCSE for layers that contain methylammonium cations, in contrast with cesium-containing layers that show normal (red-shifting) behavior. We attribute the blue-shifts to an extraordinary diminution in the exciton binding energy that arises from an augmented separation of the electron and hole wavefunctions caused by the orientational response of the dipolar cations. The absorption coefficient changes, realized by either the red- or blue-shifts, are the strongest among solution-processed materials at room temperature and are comparable to those exhibited in the highest-performing epitaxial compound semiconductor heterostructures.

Synthesis, structure, lattice energy and enthalpy of 2D hybrid perovskite [NH3(CH2)4NH3]CoCl4, compared to [NH3(CH2)nNH3]CoCl4, n=3–9

A new organic–inorganic 2D hybrid perovskite [NH3(CH2)4NH3]CoCl4,1,4butane diammonium tetra-chlorocobaltate, has been synthesized. Blue prismatic single crystals were grown from ethanolic solution in 1:1 stoichiometric ratio (organic/inorganic) by gradual cooling to room temperature after heating at 70°C for 1h. The hybrid crystallizes in a triclinic phase with the centrosymetric space group P 1¯. Its unit cell parameters are a=7.2869 (2)Å, b=8.1506 (2)Å, c=10.4127 (3)Å, α=77.2950 (12)°, β=80.0588 (11)°, γ=82.8373 (12)° and Z=2. The final R factor is 0.064. The structure consists of organic dications [NH3(CH2)4NH3]2+ which act as spacer between layers of inorganic dianions [CoCl4]2− in which CoII ions are coordinated by four Cl atoms in an isolated tetrahedral structure. The organic and inorganic layers form infinite 2D sheets which are parallel to the ac plane, stacking alternatively along the b-axis, and are connected via N–H…. Cl hydrogen bonds. The lamellar structure of the 1,4 butane diammonium tetrachlorocobaltate hybrid is typically considered as naturally self-assembled multiple quantum wells (MQW). The calculated lattice potential energy Upot (kJ/mol) and lattice enthalpy ΔHL (kJ/mol) are inversely proportional to the molecular volume Vm (nm3) of perovskite hybrid of the formula [NH3(CH2)nNH3]CoCl4, n=3–9.

C–V AND AS STUDY OF SELF-ASSEMBLED GE ISLANDS IN SI P-N JUNCTION

The electrical properties of self-assembled Ge quantum dots (QDs) and Ge quantum wells (QWs) embedded in Si p-i-n diodes were studied using capacitance-voltage(C-V) measurements and admittance spectroscopy(AS). The investigated samples were grown on Si(001) substrates by an ultra high vacuum chemical vapour deposition (UHV-CVD) system. A linear increase of the thermal activation energy observed in voltage-dependent admittance spectroscopy(from 250meV up to 380meV) for the sample with quantum dots shows that the ensemble of Ge islands has a low, continuous averaged density of states. For the sample without Boron pretreatment we found two levels with activation energies about 132meV and 202meV which were about constant in some reverse bias region.

Structural tunability and switchable exciton emission in inorganic-organic hybrids with mixed halides

Room-temperature tunable excitonic photoluminescence is demonstrated in alloy-tuned layered Inorganic-Organic (IO) hybrids, (C12H25NH3)2PbI4(1−y)Br4y (y = 0 to 1). These perovskite IO hybrids adopt structures with alternating stacks of low-dimensional inorganic and organic layers, considered to be naturally self-assembled multiple quantum wells. These systems resemble stacked monolayer 2D semiconductors since no interlayer coupling exists. Thin films of IO hybrids exhibit sharp and strong photoluminescence (PL) at room-temperature due to stable excitons formed within the low-dimensional inorganic layers. Systematic variation in the observed exciton PL from 510 nm to 350 nm as the alloy composition is changed, is attributed to the structural readjustment of crystal packing upon increase of the Br content in the Pb-I inorganic network. The energy separation between exciton absorption and PL is attributed to the modified exciton density of states and diffusion of excitons from relatively higher energy states corresponding to bromine rich sites towards the lower energy iodine sites. Apart from compositional fluctuations, these excitons show remarkable reversible flips at temperature-induced phase transitions. All the results are successfully correlated with thermal and structural studies. Such structural engineering flexibility in these hybrids allows selective tuning of desirable exciton properties within suitable operating temperature ranges. Such wide-range PL tunability and reversible exciton switching in these novel IO hybrids paves the way to potential applications in new generation of optoelectronic devices.

Exciton switching and Peierls transitions in hybrid inorganic-organic self-assembled quantum wells

The switching behavior of exciton absorption and photoluminescence is systematically explored in hybrid inorganic-organic multiple quantum well structures, based on (C12H25NH3)2PbI4 thin films and single crystals. Two structural phases found between 15 and 75 °C, based on orthorhombic and monoclinic unit cells, show different optical excitons which are demonstrated to arise from the reversible crumpling of the quantum well layers. Structural flips can be controlled by annealing or film thickness, with different thermal hysteresis behavior observed for single crystals and thin films.

ODMR of impurity centers embedded in silicon microcavities

We present the findings of high efficient light absorption in self-assembled quantum wells (SQW) incorporated in silicon microcavities that exhibit a distributed feedback identified by the FIR transmission spectra. The excitonic normal-mode coupling (NMC) is found to result in high efficient bound exciton photoluminescence in the range of the Rabi splitting. The bound excitons at the iron–boron pair and the erbium-related centers inserted in SQW are shown to cause giant exchange splitting of the center multiplets as a result of the strong sp–d and sp–f mixing in the absence of the external magnetic field. The NMC regime is observed to reveal this exchange splitting in the angular dependencies of the transmission spectra measured in the range of the Rabi splitting that are evidence of the ODMR of the trigonal iron–boron pairs and trigonal erbium-related centers.

Spin interference in silicon one-dimensional rings

We present the first findings of the spin transistor effect in the Rashba gate-controlled ring embedded in the p-type self-assembled silicon quantum well that is prepared on the n-type Si (100) surface. The coherence and phase sensitivity of the spin-dependent transport of holes are studied by varying the value of the external magnetic field and the top gate voltage that are applied perpendicularly to the plane of the double-slit ring and revealed by the Aharonov-Bohm (AB) and Aharonov-Casher (AC) conductance oscillations, respectively. Firstly, the amplitude and phase sensitivity of the 0.7.(2e2/h) feature of the hole quantum conductance staircase revealed by the quantum point contact inserted in the one of the arms of the double-slit ring are found to result from the interplay of the spontaneous spin polarization and the Rashba spin-orbit interaction (SOI). Secondly, the values of the AC conductance oscillations caused by the Rashba SOI are found to take the fractional form with both the plateaus and steps as a function of the top gate voltage.

Spin interference in silicon one-dimensional rings

We present the first findings of the spin transistor effect caused by the Rashba gate-controlled ring embedded in the p-type self-assembled silicon quantum well that is prepared on the Si (1 0 0) surface using the planar diffusion CVD technology. The coherence and phase sensitivity of spin-dependent transport of holes are studied by varying the value of external magnetic field and gate voltage that are perpendicular to the plane of the double-slit ring. Firstly, quantum scatterers connected to two one-dimensional leads and quantum point contact inserted in the one of the arms of the double-slit ring are shown to define the amplitude and the phase of the Aharonov–Bohm and the Aharonov–Casher conductance oscillations. Secondly, the amplitude and phase sensitivity of the 0.7 (2e 2/h) feature of hole quantum conductance staircase revealed by the quantum point contact inserted are found to result from the interplay of spontaneous spin polarization and Rashba spin-orbit interaction.

Compositional modulation in [formula omitted

Transmission electron microscopy and X-ray diffraction were used to study compositional modulation in In x Ga 1 - x N layers grown with compositions close to the miscibility gap. The samples ( 0.34 < x < 0.8 ) were deposited by molecular beam epitaxy using either a 200-nm-thick AlN or GaN buffer layer grown on a sapphire substrate. In the TEM imaging mode this modulation is seen as black/white fringes which can be considered as self-assembled thin quantum wells. Periodic compositional modulation leads to extra electron diffraction spots and satellite reflections in X-ray diffraction in the θ – 2 θ coupled geometry. The modulation period was determined using both methods. Larger modulation periods were observed for layers with higher In content and for those having larger mismatch with the underlying AlN buffer layer. Compositional modulation was not observed for a sample with x = 0.34 grown on a GaN buffer layer. Modulated films tend to have large “Stokes shifts” between their absorption edge and photoluminescence peak.

Superconductivity in silicon nanostructures

We present the findings of single-hole and pair-hole tunneling into the negative-U centres at the quantum well—δ-barrier interfaces that seems to give rise to the superconductivity observed in the silicon nanostructures prepared by short time diffusion of boron on the n-type Si(100) surface. These Si-based nanostructures represent the p-type ultra-narrow self-assembled silicon quantum wells, 2nm, confined by the δ-barriers heavily doped with boron, 3nm. The EPR and the thermo-emf studies show that the δ-barriers appear to consist of the trigonal dipole centres, B+–B−, which are caused by the negative-U reconstruction of the shallow boron acceptors, 2B0→B++B−. Using the CV and thermo-emf techniques, the transport of two-dimensional holes inside SQW is demonstrated to be accompanied by single-hole tunneling through these negative-U centres that results in the superconductivity of the δ-barriers, which seems to be in frameworks of the mechanism suggested by E. Simanek and C.S. Ting (Sol. St. Commun. 32 (1979) 731; Phys. Rev. Lett. 45 (1980) 1213). The values of the correlation gaps obtained from these measurements are in a good agreement with the data derived from the temperature and magnetic field dependencies of the magnetic susceptibility, which reveal a strong diamagnetism and additionally identify the superconductor gap value.

Electron‐dipole resonance of impurity centres embedded in silicon microcavities

We present the findings of high efficient light absorption by self-assembled quantum well (SQW) embedded in silicon microcavity that exhibits a distributed feedback identified by the FIR transmission spectra. The excitonic normal-mode coupling (NMC) is found to result in high efficient bound exciton photoluminescence in the range of the Rabi splitting. The localisation of this exciton at an iron-boron pair is shown to cause giant exchange splitting created by strong sp-d mixing in the absence of the external magnetic field, which is revealed by the angular dependencies of photoluminescence spectra that are evidence of the electron-dipole resonance of the trigonal iron-boron pairs. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Quantized conductance in silicon quantum wires

The results of studying the quantum-mechanical staircase for the electron and hole conductance of one-dimensional channels obtained by the split-gate method inside self-assembled silicon quantum wells are reported. The characteristics of quantum wells formed spontaneously between the heavily doped δ-shaped barriers at the Si(100) surface as a result of nonequilibrium boron diffusion are analyzed first. To this end, secondary-ion mass spectrometry, and also the detection of angular dependences of the cyclotron resonance and ESR, is used; these methods make it possible to identify both the crystallographic orientation of the self-assembled quantum wells and the ferroelectric properties of heavily doped δ-shaped barriers. Since the obtained silicon quantum wells are ultrathin (∼2 nm) and the confining δ-shaped barriers feature ferroelectric properties, the quantized conductance of one-dimensional channels is first observed at relatively high temperatures (T≥77 K). Further, the current-voltage characteristic of the quantum-mechanical conductance staircase is studied in relation to the kinetic energy of electrons and holes, their concentration in the quantum wells, and the crystallographic orientation and modulation depth of electrostatically induced quantum wires. The results show that the magnitude of quantum steps in electron conductance of crystallographically oriented n-type wires is governed by anisotropy of the Si conduction band and is completely consistent with the valence-valley factor for the [001] (G0=4e2/h and gv=2) and [011] (G0=8e2/h and gv=4) axes in the Si(100) plane. In turn, the quantum staircase of the hole conductance of p-Si quantum wires is caused by independent contributions of the one-dimensional (1D) subbands of the heavy and light holes; these contributions manifest themselves in the study of square-section quantum wires in the doubling of the quantum-step height (G0=4e2/h), except for the first step (G0=2e2/h) due to the absence of degeneracy of the lower 1D subband. An analysis of the heights of the first and second quantum steps indicates that there is a spontaneous spin polarization of the heavy and light holes, which emphasizes the very important role of exchange interaction in the processes of 1D transport of individual charge carriers. In addition, the temperature-and field-related inhibition of the quantum conductance staircase is demonstrated in the situation when kT and the energy of the field-induced heating of the carriers become comparable to the energy gap between the 1D subbands. The use of the split-gate method made it possible to detect the effect of a drastic increase in the height of the quantum conductance steps when the kinetic energy of electrons is increased; this effect is most profound for quantum wires of finite length, which are not described under conditions of a quantum point contact. It is shown in the concluding section of this paper that detection of the quantum-mechanical conductance under the conditions of sweeping the kinetic energy of the charge carriers can act as an experimental test aiding in separating the effects of quantum interference in modulated quantum wires against the background of Coulomb oscillations as a result of the formation of QDs between the delta-shaped barriers.