Mid-Infrared, Optically Active Black Phosphorus Thin Films on Centimeter Scale.

Black phosphorus (BP) is a narrow bandgap (∼0.3 eV) semiconductor with a great potential for optoelectronic devices in the mid-infrared wavelength. However, it has been challenging to achieve a high-quality scalable BP thin film. Here we present the successful synthesis of optically active BP films on a centimeter scale. We utilize the pulsed laser deposition of amorphous red phosphorus, another allotrope of phosphorus, followed by a high-pressure treatment at ∼8 GPa to induce a phase conversion into BP crystals. The crystalline quality was improved through thermal annealing, resulting in the observation of photoluminescence emission at mid-infrared wavelengths. We demonstrate high-pressure conversion on a centimeter scale with a continuous film with a thickness of ∼18 nm using a flat-belt-type high-pressure apparatus. This synthesis procedure presents a promising route to obtain optical-quality BP films, enabling the exploration of integrated optoelectronic device applications such as light-emitting devices and mid-infrared cameras on a chip scale.

Gate Controlled Excitonic Emission in Quantum Dot Thin Films.

Formation of charged trions is detrimental to the luminescence quantum efficiency of colloidal quantum dot (QD) thin films as they predominantly undergo nonradiative recombination. In this regard, control of charged trion formation is of interest for both fundamental characterization of the quasi-particles and performance optimization. Using CdSe/CdS QDs as a prototypical material system, here we demonstrate a metal-oxide-semiconductor capacitor based on QD thin films for studying the background charge effect on the luminescence efficiency and lifetime. The concentration ratio of the charged and neutral quasiparticles in the QDs is reversibly controlled by applying a gate voltage, while simultaneous steady-state and time-resolved photoluminescence measurements are performed. Notably, the photoluminescence intensity is modulated by up to 2 orders of magnitude with a corresponding change in the effective lifetime. In addition, chip-scale modulation of brightness is demonstrated, where the photoluminescence is effectively turned on and off by the gate, highlighting potential applications in voltage-controlled electrochromics.

Large-area epitaxial growth of InAs nanowires and thin films on hexagonal boron nitride by metal organic chemical vapor deposition.

Large-area epitaxial growth of III-V nanowires and thin films on van der Waals substrates is key to developing flexible optoelectronic devices. In our study, large-area InAs nanowires and planar structures are grown on hexagonal boron nitride templates using metal organic chemical vapor deposition method without any catalyst or pre-treatments. The effect of basic growth parameters on nanowire yield and thin film morphology is investigated. Under optimised growth conditions, a high nanowire density of 2.1×109cm-2is achieved. A novel growth strategy to achieve uniform InAs thin film on h-BN/SiO2/Si substrate is introduced. The approach involves controlling the growth process to suppress the nucleation and growth of InAs nanowires, while promoting the radial growth of nano-islands formed on the h-BN surface. A uniform polycrystalline InAs thin film is thus obtained over a large area with a dominant zinc-blende phase. The film exhibits near-band-edge emission at room temperature and a relatively high Hall mobility of 399 cm-2/(Vs). This work suggests a promising path for the direct growth of large-area, low-temperature III-V thin films on van der Waals substrates.

Efficiency Roll-Off Free Electroluminescence from Monolayer WSe2.

Exciton-exciton annihilation (EEA) is a nonradiative process commonly observed in excitonic materials at high exciton densities. Like Auger recombination, EEA degrades luminescence efficiency at high exciton densities and causes efficiency roll-off in light-emitting devices. Near-unity photoluminescence quantum yield has been demonstrated in transition metal dichalcogenides (TMDCs) at all exciton densities with optimal band structure modification mediated by strain. Although the recombination pathways in TMDCs are well understood, the practical application of light-emitting devices has been challenging. Here, we demonstrate a roll-off free electroluminescence (EL) device composed of TMDC monolayers tunable by strain. We show a 2 orders of magnitude EL enhancement from the WSe2 monolayer by applying a small strain of 0.5%. We attain an internal quantum efficiency of 8% at all injection rates. Finally, we demonstrate transient EL turn-on voltages as small as the band gap. Our approach will contribute to practical applications of roll-off free optoelectronic devices based on excitonic materials.

Enhanced direct-gap light emission from Si-capped n+-Ge epitaxial layers on Si after post-growth rapid cyclic annealing: impact of non-radiative interface recombination toward Ge/Si double heterostructure lasers: erratum.

We report an error in Fig. 13(a) of our article [Opt. Express25, 21286 (2017)], and the correction is presented. Typographical errors in the text are also corrected.

Germanium vertically light-emitting micro-gears generating orbital angular momentum.

Germanium (Ge) is capturing researchers' interest as a possible optical gain medium implementable on complementary metal-oxide-semiconductor (CMOS) chips. Band-gap engineering techniques, relying mainly on tensile strain, are required to overcome the indirect band-gap nature of bulk Ge and promote electron injection into the direct-gap valley. We used Ge on silicon on insulator (Ge-on-SOI) wafers with a high-crystalline-quality Ge layer to fabricate Ge micro-gears on silicon (Si) pillars. Micro-gears are created by etching a periodic grating-like pattern on the circumference of a conventional micro-disk, resulting in a gear shape. Thermal built-in stresses within the SiO2 layers that encapsulate the micro-gears were used to impose tensile strain on Ge. Biaxial tensile strain values ranging from 0.3-0.5% are estimated based on Raman spectroscopy measurements and finite-element method (FEM) simulations. Multiple sharp-peak resonances within the Ge direct-gap were detected at room temperature by photo-luminescence (PL) measurements. By investigating the micro-gears spectrum using finite-difference time-domain (FDTD) simulations, we identified vertically emitted optical modes with non-zero orbital angular momentum (OAM). To our best knowledge, this is the first demonstration of OAM generation within a Ge light source.

Enhanced direct-gap light emission from Si-capped n+-Ge epitaxial layers on Si after post-growth rapid cyclic annealing: impact of non-radiative interface recombination toward Ge/Si double heterostructure lasers.

Enhanced direct-gap light emission is reported for Si-capped n+-Ge layers on Si after post-growth rapid cyclic annealing (RCA), and impact of non-radiative recombination (NRR) at the Ge/Si interface is discussed toward Ge/Si double heterostructure (DH) lasers. P-doped n+-Ge layer (1 × 1019 cm-3, 400 nm) is grown on Si by ultra-high vacuum chemical vapor deposition, followed by a growth of Si capping layer (5 nm) to form a Si/Ge/Si DH structure. Post-growth RCA to eliminate defects in Ge is performed in N2 at temperatures between 900°C and 780°C, where the annealing time is minimized to be 5 s in each RCA cycle to prevent an out-diffusion of P dopants from the Ge surface. Direct-gap photoluminescence (PL) intensity at 1.6 µm increases with the RCA cycles up to 40, although the threading dislocation density in Ge is not reduced after 3 cycles in the present condition. The PL enhancement is ascribed to the suppression of NRR at the Ge/Si interface, where an intermixed SiGe alloy is formed. For Ge/Si DH lasers, NRR at the Ge/Si interface is found to have a significant impact on the threshold current density Jth. In order to achieve Jth on the order of 1 kA/cm2, similar to III-V lasers, the interface recombination velocity S is required below 103 cm/s in spite of S as large as 105 cm/s at the ordinary defect-rich Ge/Si interface.

Enhanced light emission from improved homogeneity in biaxially suspended Germanium membranes from curvature optimization.

A silicon compatible light source is crucial to develop a fully monolithic silicon photonics platform. Strain engineering in suspended Germanium membranes has offered a potential route for such a light source. However, biaxial structures have suffered from poor optical properties due to unfavorable strain distributions. Using a novel geometric approach and finite element modelling (FEM) structures with improved strain homogeneity were designed and fabricated. Micro-Raman (µ-Raman) spectroscopy was used to determine central strain values. Micro-photoluminescence (µ-PL) was used to study the effects of the strain profiles on light emission; we report a PL enhancement of up to 3x by optimizing curvature at a strain value of 0.5% biaxial strain. This geometric approach offers opportunity for enhancing the light emission in Germanium towards developing a practical on chip light source.

Quantitative Mid-infrared Photoluminescence Characterization of Black Phosphorus-Arsenic Alloys.

Black phosphorus (bP) is a promising material for mid-infrared (mid-IR) optoelectronic applications, exhibiting high performance light emission and detection. Alloying bP with arsenic extends its operation toward longer wavelengths from 3.7 µm (bP) to 5 µm (bP3As7), which is of great practical interest. Quantitative optical characterizations are performed to establish black phosphorus-arsenic (bPAs) alloys optoelectronic quality. Anisotropic optical constants (refractive index, extinction coefficient, and absorption coefficient) of bPAs alloys from near-infrared to mid-IR (0.2-0.9 eV) are extracted with reflection measurements, which helps optical device design. Quantitative photoluminescence (PL) of bPAs alloys with different As concentrations are measured from room temperature to 77 K. PL quantum yield measurements reveal a 2 orders of magnitude decrease in radiative efficiency with increasing As concentration. An optical cavity is designed for bP3As7, which allows for up to an order of magnitude enhancement in the quantum yield due to the Purcell effect. Our comprehensive optical characterization provides the foundation for high performance mid-IR optical device design using bPAs alloys.

Transient Nanoscopy of Exciton Dynamics in 2D Transition Metal Dichalcogenides.

The electronic and optical properties of 2D transition metal dichalcogenides are dominated by strong excitonic resonances. Exciton dynamics plays a critical role in the functionality and performance of many miniaturized 2D optoelectronic devices; however, the measurement of nanoscale excitonic behaviors remains challenging. Here, a near-field transient nanoscopy is reported to probe exciton dynamics beyond the diffraction limit. Exciton recombination and exciton-exciton annihilation processes in monolayer and bilayer MoS2 are studied as the proof-of-concept demonstration. Moreover, with the capability to access local sites, intriguing exciton dynamics near the monolayer-bilayer interface and at the MoS2 nano-wrinkles are resolved. Such nanoscale resolution highlights the potential of this transient nanoscopy for fundamental investigation of exciton physics and further optimization of functional devices.

Multicolor Inks of Black Phosphorus for Midwave-Infrared Optoelectronics.

Black phosphorus (bP) based ink with a bulk bandgap of 0.33 eV (λ = 3.7 µm) has recently been shown to be promising for large-area, high performance mid-wave infrared (MWIR) optoelectronics. However, the development of multicolor bP inks expanding across the MWIR wavelength range has been challenging. Here a multicolor ink process based on bP with spectral emission tuned from 0.28 eV (λ = 4.4 µm) to 0.8 eV (λ = 1.5 µm) is demonstrated. Specifically, through the reduction of bP particle size distribution (i.e., lateral dimension and thickness), the optical bandgap systematically blueshifts, reaching up to 0.8 eV. Conversely, alloying bP with arsenic (bP1- xAsx) induces a redshift in the bandgap to 0.28 eV. The ink processed films are passivated with an infrared-transparent epoxy for stable infrared emission in ambient air. Utilizing these multicolor bP-based inks as an infrared light source, a gas sensing system is demonstrated that selectively detects gases, such as CO2 and CH4 whose absorption band varies around 4.3 and 3.3 µm, respectively. The presented ink formulation sets the stage for the advancement of multiplex MWIR optoelectronics, including spectrometers and spectral imaging using a low-cost material processing platform.

Long operating lifetime mid-infrared LEDs based on black phosphorus.

Black phosphorus (BP) is a narrow bandgap layered semiconductor promising for mid-infrared optoelectronic applications. BP-based devices have been shown to surpass state-of-the-art mid-infrared detectors and light-emitting diodes (LEDs) in terms of performance. Despite their device advantages, the material's inherent instability in the air could hinder its use in practical optoelectronic applications. Here, we investigated the impact of passivation on the device lifetime of BP LEDs, which deteriorate in a matter of seconds without using passivation. The lifetime is significantly extended with an Al2O3 passivation layer and nitrogen packaging via atomic layer deposition and ultra-violet curable resin sealing. The operational lifetime (half-life) at room temperature is extrapolated to be ~15,000 h with an initial power density of 340 mW/cm2 based on accelerated life testing. The present results indicate that efficient BP optoelectronics can be highly robust through simple and scalable packaging technologies, with important practical implications for mid-infrared applications.

Large-scale efficient mid-wave infrared optoelectronics based on black phosphorus ink.

The mid-wave infrared (MWIR), ranging from 2 to 5 micrometers, is of substantial interest for chemical sensing, imaging, and spectroscopy. Black phosphorus (bP)-based MWIR light emitters and detectors have been shown to outperform the state-of-the-art for commercial devices due to the low Auger recombination coefficient of bP. However, the scalability of these devices remains a challenge. Here, we report a bP ink formula that preserves the exceptional MWIR optoelectronic properties of bP to deposit centimeter-scale, uniform, and pinhole free films with a photoluminescence quantum yield higher than competing III-V and II-VI semiconductors with similar bandgaps at high excitation regime. As a proof of concept, we use bP ink as a "phosphor" on a red commercial light-emitting diode to demonstrate bright MWIR light emission. We also show that these films can be integrated into heterostructure device architectures with electron and hole selective contacts for direct-injected light emission and detection in MWIR.

Anomalous thickness dependence of photoluminescence quantum yield in black phosphorous.

Black phosphorus has emerged as a unique optoelectronic material, exhibiting tunable and high device performance from mid-infrared to visible wavelengths. Understanding the photophysics of this system is of interest to further advance device technologies based on it. Here we report the thickness dependence of the photoluminescence quantum yield at room temperature in black phosphorus while measuring the various radiative and non-radiative recombination rates. As the thickness decreases from bulk to ~4 nm, a drop in the photoluminescence quantum yield is initially observed due to enhanced surface carrier recombination, followed by an unexpectedly sharp increase in photoluminescence quantum yield with further thickness scaling, with an average value of ~30% for monolayers. This trend arises from the free-carrier to excitonic transition in black phosphorus thin films, and differs from the behaviour of conventional semiconductors, where photoluminescence quantum yield monotonically deteriorates with decreasing thickness. Furthermore, we find that the surface carrier recombination velocity of black phosphorus is two orders of magnitude lower than the lowest value reported in the literature for any semiconductor with or without passivation; this is due to the presence of self-terminated surface bonds in black phosphorus.

Engineering Exciton Recombination Pathways in Bilayer WSe2 for Bright Luminescence.

Exciton-exciton annihilation (EEA) in counterdoped monolayer transition metal dichalcogenides (TMDCs) can be suppressed by favorably changing the band structure with strain. The photoluminescence (PL) quantum yield (QY) monotonically approaches unity with strain at all generation rates. In contrast, here in bilayers (2L) of tungsten diselenide (WSe2) we observe a nonmonotonic change in EEA rate at high generation rates accompanied by a drastic enhancement in their PL QY at low generation rates. EEA is suppressed at both 0% and 1% strain, but activated at intermediate strains. We explain our observation through the indirect to direct transition in 2L WSe2 under uniaxial tensile strain. By strain and electrostatic counterdoping, we attain ∼50% PL QY at all generation rates in 2L WSe2, originally an indirect semiconductor. We demonstrate transient electroluminescence from 2L WSe2 with ∼1.5% internal quantum efficiency for a broad range of carrier densities by applying strain, which is ∼50 times higher than without strain. The present results elucidate the complete optoelectronic photophysics where indirect and direct excitons are simultaneously present and expedite exciton engineering in a TMDC multilayer beyond indirect-direct bandgap transition.

Chiral germanium micro-gears for tuning orbital angular momentum.

Group IV light sources with vertical emission and non-zero orbital-angular momentum (OAM) promise to unlock many novel applications. In this report, we demonstrate cylindrically symmetrical germanium micro-gear cavities, fabricated by etching a grating around the circumference of standard micro-disks, with periods ranging from 14 to 22. Photoluminescence (PL) measurements were done to identify the confined whispering-gallery modes (WGM). Finite-difference time-domain (FDTD) simulations were conducted to map the resonant modes to their modal profiles and characteristics. Vertical emission of WGMs with non-zero OAM was demonstrated, with a clear dependence of the OAM order ([Formula: see text]) on the WGM azimuthal order and the number of micro-gear grating periods. As the chirality, or the direction of rotation, is not controlled in a symmetrical cavity, we propose introducing staircase or triangular-shaped gear periods resulting in an asymmetry. By choosing the diameter, number of periods, and the asymmetrical direction of the gear-teeth, it is possible to generate OAM signals with certain wavelength, OAM order and chirality.

Enhanced Neutral Exciton Diffusion in Monolayer WS2 by Exciton-Exciton Annihilation.

Dominant recombination pathways in monolayer transition metal dichalcogenides (TMDCs) depend primarily on background carrier concentration, generation rate, and applied strain. Charged excitons formed in the presence of background carriers mainly recombine nonradiatively. Neutral excitons recombine completely radiatively at low generation rates, but experience nonradiative exciton-exciton annihilation (EEA) at high generation rates. Strain can suppress EEA, resulting in near-unity photoluminescence quantum yield (PL QY) at all exciton densities. Although exciton diffusion is the primary channel of energy transport in excitonic materials and a critical optoelectronic design consideration, the combined effects of these factors on exciton diffusion are not clearly understood. In this work, we decouple the diffusion of neutral and charged excitons with chemical counterdoping and explore the effect of strain and generation rate on exciton diffusion. According to the standard semiconductor paradigm, a shorter carrier recombination lifetime should lead to a smaller diffusion length. Surprisingly, we find that increasing generation rate shortens the exciton lifetime but increases the diffusion length in unstrained monolayers of TMDCs. When we suppress EEA by strain, both lifetime and diffusion length become independent of generation rate. During EEA one exciton nonradiatively recombines and kinetically energizes another exciton, which then diffuses fast. Our results probe concentration-dependent diffusion of pure neutral excitons by counterdoping and elucidate how strain controls exciton transport and many-body interactions in TMDC monolayers.

Inhibited nonradiative decay at all exciton densities in monolayer semiconductors.

Most optoelectronic devices operate at high photocarrier densities, where all semiconductors suffer from enhanced nonradiative recombination. Nonradiative processes proportionately reduce photoluminescence (PL) quantum yield (QY), a performance metric that directly dictates the maximum device efficiency. Although transition metal dichalcogenide (TMDC) monolayers exhibit near-unity PL QY at low exciton densities, nonradiative exciton-exciton annihilation (EEA) enhanced by van-Hove singularity (VHS) rapidly degrades their PL QY at high exciton densities and limits their utility in practical applications. Here, by applying small mechanical strain (less than 1%), we circumvented VHS resonance and markedly suppressed EEA in monolayer TMDCs, resulting in near-unity PL QY at all exciton densities despite the presence of a high native defect density. Our findings can enable light-emitting devices that retain high efficiency at all brightness levels.

Purely in-plane ferroelectricity in monolayer SnS at room temperature.

2D van der Waals ferroelectrics have emerged as an attractive building block with immense potential to provide multifunctionality in nanoelectronics. Although several accomplishments have been reported in ferroelectric switching for out-of-plane ferroelectrics down to the monolayer, a purely in-plane ferroelectric has not been experimentally validated at the monolayer thickness. Herein, an in-plane ferroelectricity is demonstrated for micrometer-size monolayer SnS at room temperature. SnS has been commonly regarded to exhibit the odd-even effect, where the centrosymmetry breaks only in the odd-number layers to exhibit ferroelectricity. Remarkably, however, a robust room temperature ferroelectricity exists in SnS below a critical thickness of 15 layers with both an odd and even number of layers, suggesting the possibility of controlling the stacking sequence of multilayer SnS beyond the limit of ferroelectricity in the monolayer. This work will pave the way for nanoscale ferroelectric applications based on SnS as a platform for in-plane ferroelectrics.

Self-passivated ultra-thin SnS layers via mechanical exfoliation and post-oxidation.

Remarkable optical/electrical features are expected in two-dimensional group-IV monochalcogenides (MXs; M = Sn/Ge and X = S/Se) with a uniquely distorted layered structure. The lone pair electrons in the group-IV atoms are the origin of this structural distortion, while they also cause a strong interlayer force and high chemical reactivity. The fabrication of chemically stable few-to-monolayer MX has been a significant challenge. We have observed that, once the SnS surface is oxidized, the SnOx top layer works as a passivation layer for the SnS layer underneath. In this work, the SnOx/SnS hetero-structure is studied structurally, optically, and electrically. When tape-exfoliated bulk SnS is oxygen-annealed under a reduced pressure at 10 Pa, surface oxidation and SnS sublimation proceed simultaneously, resulting in a monolayer-thick SnS layer with the SnOx passivation layer. The field-effect transistor of nine-layer SnS prepared via mechanical exfoliation exhibits a p-type characteristic because of intrinsic Sn vacancies, whereas ambipolar behavior is observed for the monolayer-thick SnS obtained via oxygen annealing probably owing to the additional n-type doping by S vacancies. This work on monolayer-thick SnS fabrication can be applied to other unstable lone pair analogues and can facilitate future research on MXs.