Absorption In Semiconductors Research Articles

Hybrids of Deep HOMO Organic Cyanoacrylic Acid Dyes and Graphene Nanomaterials for Water Splitting Photoanodes.

Dye-sensitization is a promising strategy to improve the light absorption and photoactivity abilities of wide-bandgap semiconductors, like TiO2. For effective water-splitting photoanodes with no sacrificial agents, the electrochemical potential of the dye must exceed the thermodynamic threshold needed for the oxygen evolution reaction. This study investigates two promising organic cyanoacrylic dyes, designed to meet that criterion by means of theoretical calculations. Both yellow-colored dyes were synthesized and characterized by optical and photoelectrochemical techniques, demonstrating strong light absorption in the visible region, suitable experimental reduction potentials, and adsorption from the organic solvent onto mesoporous TiO2 layers. In addition, to promote immobilization in aqueous electrolytes, the dyes were hybridized with graphene oxide or multi-walled carbon nanotubes. Photoelectrochemical analysis of the dye-sensitized photoelectrodes demonstrated efficient charge transfer from the dyes to the TiO2 photoanode under simulated solar light. While the starting photocurrent notably surpassed the blank TiO2, a subsequent decay points to kinetic obstacles that still need to be overcome.

Characterizing ultrashort pulses with photon energies above 1.12 eV based on transient absorption in silicon thin films

Abstract Frequency-resolved optical switching (FROSt) is a phase-matching-free characterization technique for ultrashort pulses based on transient absorption in semiconductors. So far, this technique has been limited to characterizing pulses with photon energies smaller than the bandgap of the semiconductors used. In this work, we extend the method to characterize pulses of photon energy greater than the bandgap of the semiconductor used for characterization. We demonstrate this by characterizing ultrashort visible pulses and supercontinuum (SC) using silicon (Si) thin films deposited on a sapphire substrate. We also demonstrate that visible light sources up to a repetition rate of 250 kHz can be characterized using these samples. Therefore, this study highlights the potential of FROSt as a suitable technique for the temporal characterization of weak visible to infrared (IR) pulses, including high harmonics generated in solids.

Constructing a Z-scheme heterojunction of oxygen-deficient WO3-x and g-C3N4 for superior photocatalytic evolution of H2

Semiconductor-based photocatalytic water splitting enables the conversion of abundant solar energy to green and renewable hydrogen energy. Graphitic carbon nitride (g-C3N4) is synthesized using a straightforward method, demonstrating stable physicochemical properties and possessing an optimal bandgap, thus positioning it as a promising photocatalyst in the realm of environmental sustainability. Oxygen vacancies are extensively employed to modulate light absorption and surface properties of metal-oxide semiconductors. In this study, g-C3N4 nanosheets were coupled with oxygen-deficient tungsten trioxide (WO3-x) to form heterojunction photocatalysts (X-WOCN). Comprehensive material characterization results demonstrated that the constructed heterojunction extended the visible light absorption range, improved photogenerated electron-hole separation efficiency, and thus augmented photocatalytic activity. Notably, the optimum hydrogen evolution rate of 6 %-WOCN was enhanced by 5.4-fold compared to that of g-C3N4. Furthermore, we propose a Z-scheme heterojunction charge separation mechanism mediated by oxygen defects and support this mechanism through detection of surface-active substances •O2− and •OH. This study offers novel propositions into the function of oxygen defects in facilitating charge separation within Z-scheme heterojunction.

Two-photon absorption in silicon using the real density matrix approach.

Two-photon absorption in indirect gap semiconductors is a frequently encountered, but not well-understood phenomenon. To address this, the real-density matrix approach is applied to describe two-photon absorption in silicon through the excitonic response to the interacting fields. This approach produces an analytical expression for the dispersion of the two-photon absorption coefficient for indirect-gap materials and can be used to explain trends in reported experimental data for bulk silicon both old and new with minimal fitting.

SESAM-assisted Kerr-lens mode-locked Cr:ZnS laser.

Mode-locking in Cr:ZnS/Se lasers typically rely on Kerr-lensing (KLM) or a semiconductor saturable absorber mirror (SESAM). The former allows generation of shorter pulses, but, unlike the latter, does not support self-starting mode-locking. Here, we combine the advantages of these two techniques and demonstrate the SESAM-assisted KLM Cr:ZnS laser. Our self-starting oscillator generates up to 1 W of average power with 54 fs pulses at a central wavelength of 2360 nm. We identify a general limitation for further pulse shortening in SESAM mode-locked Cr:ZnS/Se lasers, which is related to the finite operation bandwidth of the semiconductor absorbers. In our experiment, we fully exploit the potential of commercially available GaSb SESAMs and fill their entire reflection bands. Furthermore, we compare the performance of a SESAM-assisted KLM laser with a pure KLM oscillator producing broadband, yet not self-starting, 33 fs pulses with 780 mW power. We also show that the choice of saturable absorbers has a negligible impact on the laser intensity noise, which is exceptionally low with sub-0.005% integrated noise.

Evaluating Photovoltaic Conversion Performance under Artificial Indoor Lighting

Several photovoltaic technologies, based on different semiconductor absorbers with band-gap energy in the range Eg = 1.0–1.5 eV are currently sharing the market for outdoor applications. These photovoltaic cells are designed to achieve an optimal photovoltaic conversion under solar illumination (represented by the standard AM1.5 global spectrum), but their performance changes under different artificial indoor lights. Here, the detailed balance principle that was first applied for an ideal photovoltaic absorber under solar radiation is now used by considering the actual spectra of four typical indoor lamps: incandescent, halogen, metal halide and white LED. For each particular illumination source, the theoretical maximum for short-circuit current, open-circuit voltage and maximum power point have been calculated and represented as a function of the absorber band-gap energy. Furthermore, the optical absorption spectra of some semiconductors with optimal solar conversion efficiencies are used to estimate their comparative performance under the various artificial light sources. It has been found that wide band-gap absorbers (Eg~1.9 eV) are needed to achieve a light-to-electricity conversion efficiency of 60% under LED illumination or 31% with metal halide bulbs, while a lowest band-gap energy of about 0.8 eV is required to obtain a maximum efficiency of 24% with incandescent and halogen lamps.

PyArc: A python package for computing absorption and radiative coefficients from first principles

Light absorption and radiative recombination are two critical processes in optoelectronic materials that characterize the energy conversion efficiency. The absorption and radiative coefficients are thus key properties for device optimization and design. Here, we develop a python package named pyArc that allows rigorous computation of absorption and radiative coefficients from first principles. By integrating several interpolation strategies to augment k-point sampling in reciprocal space, our code is accurate yet highly efficient. In addition to evaluation of the coefficients, our code is capable of intuitive analysis of carrier distribution, facilitating a deeper understanding of the microscopic mechanisms underlying the radiative coefficients. Utilizing GaAs as a prototypical example, we demonstrate how to employ our package to compute absorption and radiative coefficients and to investigate the key features in the electronic structure that give rise to these coefficients. Program SummaryProgram title: PyArcCPC Library link to program files:https://doi.org/10.17632/5x9g9bvhcv.1Licensing provisions: MIT licenseProgramming language: Python 3Nature of problem: Light absorption and radiative recombination processes in semiconductors critically impact the energy conversion efficiency of optoelectronic devices. Developing a method to calculate coefficients of the two processes based on first-principles theory is essential, which not only can help to obtain the key properties of those semiconductor materials and guide the device design, but also can unveil the underlying microscopic mechanisms.Solution method: PyArc, written in the Python language, implements first-principles methodologies for the computation of absorption and radiative coefficients of semiconductors based on Fermi's golden rule. This package takes the electronic eigenvalues and dipole matrix elements of a material computed from first-principles codes such as VASP as input. Dense k-point sampling for the Brillouin zone is achieved through efficient interpolation schemes implemented in our code to acquire well converged results. The functionality of cross-sectional visualization of carrier distribution in our code provides intuitive insights into the fundamental mechanism beneath the charge-carrier radiative recombination process.

(Invited) Techno-Economics of Photoelectrochemical Water Splitting and Progress in Cost Reduction of High-Efficiency III-V Photoabsorbers

Photoelectrochemical (PEC) water splitting is a potentially promising route to direct solar-driven hydrogen production. Challenging targets for solar-to-hydrogen (STH) efficiency, durability, and semiconductor absorber costs must be realized for this approach to be economically competitive with other hydrogen production pathways. The first part of this talk will focus on the cost and performance metrics that go into techno-economic analysis and their status.Research on PEC hydrogen production at the National Renewable Energy Laboratory (NREL) has focused on III-V semiconductor absorber materials because their tunable bandgaps, high photon conversion efficiencies, and ability to make multi-junction structures that have resulted in the highest STH efficiencies yet demonstrated. However, to achieve the U.S. DOE’s hydrogen production target of $2/kg, in addition to high STH efficiency, the semiconductor absorber synthesis cost must come down 1-2 orders of magnitude from the current metal organic vapor phase epitaxial route. Hydride vapor phase epitaxy (HVPE) is a technique that has the potential to lower tandem III-V synthesis costs. The second part of this talk will describe experimental photoelectrochemical characterizations of HVPE-grown GaInP/GaAs tandem photoelectrodes with 1.85/1.38 eV bandgaps. Their incident photon-to-current efficiency, photocurrent vs. circuit bias, and unbiased chronoamperometry will be presented and discussed. Upon illumination, the HVPE-grown structures were able to drive water electrolysis spontaneously (e.g., without an external bias) at STH efficiencies up to 10%. The durability of III-V photoelectrodes remains an unresolved challenge for cost effective hydrogen production via photoelectrolysis.

Kretschmann configuration as a method to enhance optical absorption in two-dimensional graphene-like semiconductors

Objectives. The optical properties of two-dimensional semiconductor materials, specifically monolayered transition metal dichalcogenides, present new horizons in the field of nano- and optoelectronics. However, their practical application is hindered by the issue of low light absorption. When working with such thin structures, it is essential to consider numerous complex factors, such as resonance and plasmonic effects which can influence absorption efficiency. The aim of this study is the optimization of light absorption in a two-dimensional semiconductor in the Kretschmann configuration for future use in optoelectronic devices, considering the aforementioned phenomena. Methods. A numerical modeling method was applied using the finite element method for solving Maxwell’s equations. A parametric analysis was conducted focusing on three parameters: angle of light incidence, metallic layer thickness, and semiconductor layer thickness.Results. Parameters were identified at which the maximum area of absorption peak was observed, including the metallic layer thickness and angle of light incidence. Based on the resulting graphs, optimal parameters were determined, in order to achieve the highest absorption percentages in the two-dimensional semiconductor film.Conclusions. Based on numerical studies, it can be asserted that the optimal parameters for maximum absorption in the monolayer film are: Ag thickness <20 nm and angle of light incidence between 55° and 85°. The maximum absorption in the two-dimensional film was found only to account for a portion of the total absorption of the entire structure. Thus, a customized approach to parameter selection is necessary, in order to achieve maximum efficiency in certain optoelectronic applications.

Charge transport and extrinsic absorption of two-dimensional defect-rich ZnIn2S4 semiconductor for below-bandgap photodetection

As a rediscovered ternary two-dimensional (2D) material, defect-rich Znln2S4 has great potential for energy-harvesting applications. However, the effect of defects on its physical properties and device performance remains elusive. Herein, we explored the influence of defects (S vacancies and In–Zn substitutions) in few-layer Znln2S4 on the charge transport and photoelectric performance. It is demonstrated that the defect-rich Znln2S4 device exhibits two-dimensional variable range hopping transport mechanism, with uniform charge transport along the channel and low contact resistance at the electrical contacts of Znln2S4/Au. Importantly, due to the contribution of the donor and acceptor energy levels inside the bandgap, the flake exhibits pronounced extrinsic absorption, leading to the competitive photodetector performance under sub-bandgap photo-excitation. Explicitly, the device exhibits a maximum responsivity of 4.08 × 104 A W−1, a photo-gain of >108 electrons per photon, and a specific detectivity of ∼1015 Jones under 532 nm laser excitation, with detection wavelength extending from 400 to 980 nm. Our findings underscore the significant potential of defect-engineering to enrich the functionalities of 2D semiconductors.

Molecularly Thin 2D Organic Single Crystals: A New Platform for High-Performance Polarization-Sensitive Phototransistors.

The inherent linear dichroism (LD), high absorption, and solution processability of organic semiconductors hold immense potential to revolutionize polarized light detection. However, the disordered molecular packing inherent to polycrystalline thin films obscures their intrinsic diattenuation, resulting in diminished polarization sensitivity. In this study, we develop filter-free organic polarization-sensitive phototransistors (PSPs) with both a high linear dichroic ratio (LDR) and exceptional photosensitivity utilizing molecularly thin dithieno[3,2-b:2',3'-d]thiophene derivatives (DTT-8) two-dimensional molecular crystals (2DMCs) as the active layer. The orderly molecular packing in 2DMCs amplifies the inherent LD, and their molecular-scale thickness enables complete channel depletion, significantly reducing the dark current. As a result, PSPs with an impressive LDR of 3.15 and a photosensitivity reaching 3.02 × 106 are obtained. These findings present a practical demonstration of using the polarization angle as an encryption key in optical communication, showcasing the potential of 2DMCs as a viable and promising category of semiconductors for filter-free, polarization-sensitive photodetectors.

Integration of Multijunction Absorbers and Catalysts for Efficient Solar‐Driven Artificial Leaf Structures: A Physical and Materials Science Perspective

Artificial leaves could be the breakthrough technology to overcome the limitations of storage and mobility through the synthesis of chemical fuels from sunlight, which will be an essential component of a sustainable future energy system. However, the realization of efficient solar‐driven artificial leaf structures requires integrated specialized materials such as semiconductor absorbers, catalysts, interfacial passivation, and contact layers. To date, no competitive system has emerged due to a lack of scientific understanding, knowledge‐based design rules, and scalable engineering strategies. Herein, competitive artificial leaf devices for water splitting, focusing on multiabsorber structures to achieve solar‐to‐hydrogen conversion efficiencies exceeding 15%, are discussed. A key challenge is integrating photovoltaic and electrochemical functionalities in a single device. Additionally, optimal electrocatalysts for intermittent operation at photocurrent densities of 10–20 mA cm−2 must be immobilized on the absorbers with specifically designed interfacial passivation and contact layers, so‐called buried junctions. This minimizes voltage and current losses and prevents corrosive side reactions. Key challenges include understanding elementary steps, identifying suitable materials, and developing synthesis and processing techniques for all integrated components. This is crucial for efficient, robust, and scalable devices. Herein, corresponding research efforts to produce green hydrogen with unassisted solar‐driven (photo‐)electrochemical devices are discussed and reported.

Prediction of highly stable 2D carbon allotropes based on azulenoid kekulene

Despite enormous interest in two-dimensional (2D) carbon allotropes, discovering stable 2D carbon structures with practically useful electronic properties presents a significant challenge. Computational modeling in this work shows that fusing azulene-derived macrocycles – azulenoid kekulenes (AK) – into graphene leads to the most stable 2D carbon allotropes reported to date, excluding graphene. Density functional theory predicts that placing the AK units in appropriate relative positions in the graphene lattice opens the 0.54 eV electronic bandgap and leads to the appearance of the remarkable 0.80 eV secondary gap between conduction bands – a feature that is rare in 2D carbon allotropes but is known to enhance light absorption and emission in 3D semiconductors. Among porous AK structures, one material stands out as a stable narrow-multigap (0.36 and 0.56 eV) semiconductor with light charge carriers (me = 0.17 m0, mh = 0.19 m0), whereas its boron nitride analog is a wide-multigap (1.51 and 0.82 eV) semiconductor with light carriers (me = 0.39 m0, mh = 0.32 m0). The multigap engineering strategy proposed here can be applied to other carbon nanostructures creating novel 2D materials for electronic and optoelectronic applications.

Numerical simulation of Cu2Te based thin film solar cell with Cu2O HTL for high efficiency

Copper telluride (Cu2Te) is an attractive semiconductor absorber material for thin film solar cells due to its excellent opto-electronic properties. However, the maximum experimental conversion efficiency of the Cu2Te thin film solar cell remains at about 6%. In the present study, the cuprous oxide (Cu2O) material as the hole transport layer (HTL) has been proposed in the Cu2Te based thin film solar cell. The purpose of this work is to enhance the device performance by inserting widely available Cu2O material as HTL into the basic heterojunction structure. The effects of several material parameters such as thickness, carrier concentration, defect density and back contact metal work function on the device performance of the proposed Cu2Te thin film solar cell consisting of FTO/WS2/Cu2Te/Cu2O/metal have been studied and numerical investigated using the wxAMPS program. Optimized conversion efficiency of the proposed Cu2Te thin film solar cell with Au as back contact metal has been obtained to be 30.32%. These results reveal that the Cu2O material as HTL can be employed to fabricate low cost and highly efficient Cu2Te thin film solar cells.

Excitonic effects in the optical absorption of gapless semiconductor α-tin near the direct bandgap

Most cubic semiconductors have threefold degenerate p-bonding valence bands and nondegenerate s-antibonding conduction bands. This allows strong interband transitions from the valence to the conduction bands. On the other hand, intervalence band transitions within p-bonding orbitals in conventional p-type semiconductors are forbidden at k=0 and, therefore, weak, but observable. In gapless semiconductors, however, the s-antibonding band moves down between the split-off hole band and the valence band maximum due to the Darwin shift. This band arrangement makes them three-dimensional topological insulators. It also allows strong interband transitions from the s-antibonding valence band to the p-bonding bands, which have been observed in α-tin with Fourier-transform infrared spectroscopic ellipsometry [Carrasco et al., Appl. Phys. Lett. 113, 232104 (2018)]. This manuscript presents a theoretical description of such transitions applicable to many gapless semiconductors. This model is based on k→⋅p→ theory, degenerate carrier statistics, the excitonic Sommerfeld enhancement, and screening of the transitions by many-body effects. The impact of nonparabolic bands is approximated within Kane’s 8×8k→⋅p→-model by adjustments of the effective masses. This achieves agreement with experiments.

Enhanced Photogating Gain in Scalable MoS2 Plasmonic Photodetectors via Resonant Plasmonic Metasurfaces.

Absorption of photons in atomically thin materials has become a challenge in the realization of ultrathin, high-performance optoelectronics. While numerous schemes have been used to enhance absorption in 2D semiconductors, such enhanced device performance in scalable monolayer photodetectors remains unattained. Here, we demonstrate wafer-scale integration of monolayer single-crystal MoS2 photodetectors with a nitride-based resonant plasmonic metasurface to achieve a high detectivity of 2.58 × 1012 Jones with a record-low dark current of 8 pA and long-term stability over 40 days. Upon comparison with control devices, we observe an overall enhancement factor of >100; this can be attributed to the local strong EM field enhanced photogating effect by the resonant plasmonic metasurface. Considering the compatibility of 2D semiconductors and hafnium nitride with the Si CMOS process and their scalability across wafer sizes, our results facilitate the smooth incorporation of 2D semiconductor-based photodetectors into the fields of imaging, sensing, and optical communication applications.

High-efficiency decontamination of pharmaceutical wastewater: Synergistic effects from NaGdF4:Tm,Yb@Mn-MOFs composite photocatalysts

Water pollution caused by antibiotics poses a serious threat to human health and ecosystems. Rapid and efficient removal of antibiotic pollution in water by photocatalysts is one of the effective means to protect the environment and public health. Herein, a wide-spectral responsive upconversion NaGdF4:Yb,Tm@Mn-MOFs core-shell nanostructures were built by coating hexagonal NaGdF4:Yb,Tm cores with amino-functionalized manganese carboxylate MOFs (Mn-MOFs) shells, which exhibited good water dispersibility. Mn-MOFs catalysts is mainly concentrated in the ultraviolet region, while NaGdF4:Yb,Tm nanoparticles can transform infrared light into visible light or even higher energy ultraviolet light, which is harvested by the Mn-MOFs. The optimized nanostructures were tested under simulated solar light (After 120 min irradiation) in the degradation of tetracycline, oxytetracycline hydrochloride and tetracycline hydrochloride, while their degradation rates reached 70%, 72% and 75%, respectively. The better photocatalytic mechanism for antibiotics than its individual components was elucidated, which provides a potential strategy to broaden the full spectrum absorption of the wide bandgap semiconductors and apply for the field of environmental remediation.

Microscopic origins of radiative performance losses in thin-film solar cells at the example of (Ag,Cu)(In,Ga)Se2 devices

The present work provides an overview of radiative performance losses in thin-film solar cells, focusing on those related to the open-circuit voltage, using (Ag,Cu)(In,Ga)Se2 devices as examples. The microscopic origins of these losses are outlined, highlighting the presence of compositional variations, strain, and inhomogeneously distributed point defects on various length scales as contributors to band-gap and electrostatic potential fluctuations, which both contribute to the broadening of the absorption edge in the absorptance or quantum efficiency spectra of the semiconductor absorber layer or the completed solar-cell device. The relationship between this broadening and Urbach tails is discussed. It is shown that the photovoltaic band-gap energy as well as the broadening can be reliably determined from the arithmetic mean and standard deviation extracted from Gaussian fits to the first derivative of the absorptance or quantum efficiency spectra around the absorption edge. The more enhanced the broadening, the more the local maximum in the luminescence spectrum shifts to smaller energies with respect to the band-gap energy of the absorber layer, as verified for about 30 (Ag,Cu)(In,Ga)Se2 solar cells.

The effect investigates of temperature on the optical and electrical properties of sprayed SnS: experimental and theoretical study

In this study, Tin monosulfide SnS semiconductor absorbers was deposited by chemical spray pyrolysis route on the glass substrate. We examined the impact of substrate temperature on the structural, morphological, linear optical and electrical characteristics of SnS absorber at many substrate temperatures such as 50 °C, 375 °C and 400 °C. The SnS films have been analysed by diverse techniques like X-ray diffraction, Raman spectroscopy, Scanning electron microscopy and UV-Vis spectrophotometer. The X-ray diffraction (XRD) spectra revealed that the SnS crystallize in the orthorhombic crystal system with the apparition of the preferential crystallographic direction oriented along (111) planes. The SEM micrographs indicate a great uniformity and granular morphological surface of SnS films. Linear optical constants such as energy gap (Eg), coefficient of extinction (k), index of refraction (n), optical conductivity (σopt), as well as the electrical properties confirm the suitable application of SnS thin films as absorber layer in the optoelectronic device applications. Additionally, we have applied the density functional theory DFT and GGA generalized gradient approximation to study the electronic characteristics; as a result of the electronic band structure the SnS absorber has a suitable energy gap.

(Invited) Mulitjunction III-V Semiconductors for Photo-Electrochemical Hydrogen Production: Recent Progress in Efficiency, Durability, and Cost

Photo-electrochemical (PEC) hydrogen production is a route to carbon-free fuel that combines light absorption and water electrolysis into one device. Challenging targets for solar-to-hydrogen (STH) efficiency, durability, and semiconductor absorber costs must be realized for this approach to be economically competitive with other hydrogen production pathways. Research on PEC hydrogen production at the National Renewable Energy Laboratory (NREL) has focused on III-V semiconductor absorber materials because their tunable bandgaps, high photon conversion efficiencies, and ability to make multi-junction structures have resulted in the highest STH efficiencies yet demonstrated. This talk will focus on recent NREL results showing progress toward PEC hydrogen production efficiency, durability, and cost targets. Specifically, we have been able to improve theoretically achievable STH efficiency through bandgap engineering in multijunction devices. Photon management strategies to close the gap between theoretical and measured STH efficiency will also be discussed. Durability remains a significant challenge for III-V materials in a PEC environment. We will describe modifications to the semiconductor surface and the electrolyte constitution that can make the photoabsorber less susceptible to photocorrosion during operation. Finally, we will present preliminary results on III-V PEC materials synthesized via hydride vapor phase epitaxy, an alternative route to high-efficiency photoelectrodes that could potentially have much lower costs than the metalorganic vapor phase epitaxy method traditionally used. These improvements have yielded III-V PEC devices that are close to the STH efficiency target (17% vs. 25%) while the demonstrated durability and cost are still considerably far from their target values.