Silicon in a cubic diamond structure currently plays a significant role in the photovoltaic industry. However, the intrinsic band structures of crystalline silicon restrict its sunlight conversion efficiency. Recently, a clathrate-like Si-24 has been successfully synthesized, which has a quasi-direct bandgap and sheds light on silicon-based photovoltaics. Here, we proposed a two-step crystal structure search method based on first-principles calculations and explored silicon clathrate structures extensively. First, the guest-host compounds were searched at high pressure, and then, the porous guest-free silicon clathrates were obtained by removing the guest atoms. Using potassium as the guest atom, we identified four metastable silicon clathrate structures, and some of them have bandgaps close to the optimal range of the Shockley-Queisser limit and have a better absorption rate than the cubic diamond silicon. These silicon clathrates may have promising value in photovoltaic applications.
We propose an atomistic model for the pressure-induced isostructural phase transition of metal-doped silicon clathrates, Ba8Si46 and K8Si46, that has been observed at 14 GPa and 23 GPa, respectively. The model explains successfully the equation of state, transition pressure, change of Raman spectra and dependence on the doped cations as well as the effects of substituting Si(6c) atoms with noble metals.
The lattice thermal conductivities of silicon clathrate frameworks II and VIII are investigated by using ab initio lattice dynamics and iterative solution of the linearized Boltzmann transport equation(BTE) for phonons. Within the temperature range 100-350 K, the clathrate structures II and VIII were found to have lower lattice thermal conductivity values than silicon diamond structure (d-Si) by factors of 1/2 and 1/5, respectively. The main reason for the lower lattice thermal conductivity of the clathrate structure II in comparison to d-Si was found to be the harmonic phonon spectra, while i…
The thermal and lattice dynamical properties of seven silicon clathrate framework structures are investigated with ab initio density functional methods (frameworks I, II, IV, V, VII, VIII, and H). The negative thermal expansion (NTE) phenomenon is investigated by means of quasiharmonic approximation and applying it to equal time displacement correlation functions. The thermal properties of the studied clathrate frameworks, excluding the VII framework, resemble those of the crystalline silicon diamond structure. The clathrate framework VII was found to have anomalous NTE temperature range up to…
Silicon materials play a key role in many technologically relevant fields, ranging from the electronic to the photovoltaic industry. A systematic search for silicon allotropes was performed by employing a modified ab initio minima hopping crystal structure prediction method. The algorithm was optimized to specifically investigate the hitherto barely explored low-density regime of the silicon phase diagram by imitating the guest-host concept of clathrate compounds. In total 44 metastable phases are presented, of which 11 exhibit direct or quasi-direct band-gaps in the range of $\approx$1.0-1.8 …
Understanding the covalent clathrate formation is a crucial point for the design of new superhard materials with intrinsic coupling of superhardness and metallic conductivity. Silicon clathrates have the archetype structures that can serve an existant model compounds for superhard clathrate frameworks "Si-B", "Si-C", "B-C" and "C" with intercalated atoms (e.g. alkali metals or even halogenes) that can assure the metalic properties. Here we report the in situ and ex situ studies of high-pressure formation and stability of clathrates Na8Si46 (structure I) and Na24+xSi136 (structure II). Experime…
We present state-of-the-art first-principle calculations of the electronic and optical properties of silicon allotropes with interesting characteristics for applications in thin-film solar cells. These new phases consist of distorted sp$^3$ silicon networks and have a lower formation energy than other experimentally produced silicon phases. Some of these structures turned out to have quasi-direct and dipole-allowed band gaps in the range 0.8--1.5\,eV, and to display absorption coefficients comparable with those of chalcopyrites used in thin-film record solar cells.
Being a source of clean and renewable energy, the possibility to convert solar radiation in electric current with high efficiency is one of the most important topics of modern scientific research. Currently the exploitation of interaction between nanocrystals seems to be a promising route to foster the establishment of third generation photovoltaics. Here we adopt a fully ab-initio scheme to estimate the role of nanoparticle interplay on the carrier multiplication dynamics of interacting silicon nanocrystals. Energy and charge transfer-based carrier multiplication events are studied as a funct…
Computational searching and screening of new functional materials exploiting earth abundant elements can accelerate developments of their energy applications. Based on a state-of-the-art materials search algorithm and ab initio calculations, we demonstrate a recently suggested stable silicon oxide with a layered structure (Si$_{3}$O) as an ideal photovoltaic material. With many-body first-principles approaches, the monolayer and layered bulk of Si$_{3}$O show direct quasiparticle gaps of 1.85 eV and 1.25 eV, respectively, while an optical gap of about 1.2 eV is nearly independent of the number…
There is a renewed interest in photovoltaic solar thermal (PVT) hybrid systems, which harvest solar energy for heat and electricity. Typically, a main focus of a PVT system is to cool the photovoltaic (PV) cells to improve the electrical performance, however, this causes the thermal component to under-perform compared to a solar thermal collector. The low temperature coefficients of amorphous silicon (a-Si:H) allow for the PV cells to be operated at higher temperatures and are a potential candidate for a more symbiotic PVT system. The fundamental challenge of a-Si:H PV is light-induced degrada…
Historically, the design of hybrid solar photovoltaic thermal (PVT) systems has focused on cooling crystalline silicon (c-Si)-based photovoltaic (PV) devices to avoid temperature-related losses. This approach neglects the associated performance losses in the thermal system and leads to a decrease in the overall exergy of the system. Consequently, this paper explores the use of hydrogenated amorphous silicon (a-Si:H) as an absorber material for PVT in an effort to maintain higher and more favourable operating temperatures for the thermal system. Amorphous silicon not only has a smaller temperat…
Solar cells have generated a lot of interest as a potential source of clean renewable energy for the future. However a big bottleneck in wide scale deployment of these energy sources remain the low efficiency of these conversion devices. Recently the use of nanostructures and the strategy of quantum confinement have been as a general approach towards better charge carrier generation and capture. In this article we have presented calculations on the optical characteristics of nanowires made out of Silicon. Our calculations show these nanowires form excellent optoelectronic materials and may yie…
Antireflection with broadband and wide angle properties is important for a wide range of applications on photovoltaic cells and display. The SiOx shell layer provides a natural antireflection from air to the Si core absorption layer. In this work, we have demonstrated the random core-shell silicon nanowires with both broadband (from 400nm to 900nm) and wide angle (from normal incidence to 60\degree) antireflection characteristics within AM1.5 solar spectrum. The graded index structure from the randomly oriented core-shell (Air/SiOx/Si) nanowires may provide a potential avenue to realize a broa…
All electronic, optoelectronic or photovoltaic applications of silicon depend on controlling majority charge carriers via doping with impurity atoms. Nanoscale silicon is omnipresent in fundamental research (quantum dots, nanowires) but also approached in future technology nodes of the microelectronics industry. In general, silicon nanovolumes, irrespective of their intended purpose, suffer from effects that impede conventional doping due to fundamental physical principles such as out-diffusion, statistics of small numbers, quantum- or dielectric confinement. In analogy to the concept of modul…
Chalcopyrite semiconductors are of considerable interest for application as absorber layers in thin-film photovoltaic cells. When growing films of these compounds, however, they are often found to contain CuAu- like domains, a metastable phase of chalcopyrite. It has been reported that for CuInS2, the presence of the CuAu-like phase improves the short circuit current of the chalcopyrite-based photovoltaic cell. We investigate the thermodynamic stability of both phases for a selected list of I-III-VI2 materials using a first-principles density functional theory approach. For the CuIn-VI2 compou…
We report on very high enhancement of thin layer's absorption through band-engineering of a photonic crystal structure. We realized amorphous silicon (aSi) photonic crystals, where slow light modes improve absorption efficiency. We show through simulation that an increase of the absorption by a factor of 1.5 is expected for a film of aSi. The proposal is then validated by an experimental demonstration, showing an important increase of the absorption of a layer of aSi over a spectral range of 0.32-0.76 microns.
Graphene-silicon Schottky junction (GSJ) which has the potential for large-scale manufacturing and integration can bring new opportunities to Schottky solar cells for photovoltaic (PV) power conversion. However, the essential power conversion limitation for these devices lies in the small open-circuit voltage ($V_{oc}$), which depends on the Schottky barrier height (SBH). In this study, we introduce an electromechanical method based on the flexoelectric effect to enhance the PV efficiency in GSJ. By atomic force microscope (AFM) tip-based indentation and in situ current measurement, the curren…
A method of scanning mid-IR-laser microscopy has recently been proposed for the investigation of large-scale electrically and recombination-active defects in semiconductors and non-destructive inspection of semiconductor materials and structures in the industries of microelectronics and photovoltaics. The basis for this development was laid with a wide cycle of investigations on low-angle mid-IR-light scattering in semiconductors. The essence of the technical idea was to apply the dark-field method for spatial filtering of the scattered light in the scanning mid-IR-laser microscope together wi…
Amorphous hydrogenated silicon (a-Si:H) is an important material for surface defect passivation of photovoltaic silicon (Si) wafers in order to reduce their recombination losses. The material is however unstable with regards to hydrogen (H) desorption at elevated temperatures, which can be an issue during processing and device manufacturing. In this work we determine the temperature stability of a-Si:H by structural characterization of a-Si:H/Si bilayers with neutron- (NR) and X-ray reflectometry (XRR) combined with photoconductance measurements yielding the minority carrer lifetime. The neutr…
Here we report the development of high-efficiency microscale GaAs laser power converters, and their successful transfer printing onto silicon substrates, presenting a unique, high power, low-cost and integrated power supply solution for implantable electronics, autonomous systems and internet of things applications. We present 300 μm diameter single-junction GaAs laser power converters and successfully demonstrate the transfer printing of these devices to silicon using a PDMS stamp, achieving optical power conversion efficiencies of 48% and 49% under 35 and 71 W/cm2 808 nm laser illumination r…
The theoretical analysis of photovoltaic conversion efficiency of highly effective silicon solar cells (SC) is performed for n-type and p-type bases. The case is considered when the Shockley-Read-Hall recombination in the silicon bulk is determined by the deep level of Fe. It is shown that due to the asymmetry of the recombination parameters of this level the photovoltaic conversion efficiency is increasing in the SC with the n-type base and decreasing in the SC with the p-type base with the increase in doping. Two approximations for the band-to-band Auger recombination lifetime dependence on …
High density and uniformity sub-100nm surface oxidized silicon nanocone forest structure is created and integrated onto the existing texturization microstructures on photovoltaic device surface by a one-step high throughput plasma enhanced texturization method. We suppressed the broadband optical reflection on chemically textured grade-B silicon solar cells for up to 70.25% through this nanomanufacturing method. The performance of the solar cell is improved with the short circuit current increased by 7.1%, fill factor increased by 7.0%, conversion efficiency increased by 14.66%. Our method dem…
Upconversion of sub-band-gap photons constitutes a promising way for improving the efficiency of silicon-based solar cells beyond the Shockley-Queisser limit. 1500 to 980 nm upconversion by trivalent erbium ions is well-suited for this purpose, but the small absorption cross section hinders real-world applications. We employ tailored gold nanostructures to vastly improve the upconversion efficiency in erbium-doped TiO$_2$ thin films. The nanostructures are found using topology optimization and parameter optimization and fabricated by electron beam lithography. In qualitative agreement with a t…
Spectral converters have been proposed as a tool to achieve high efficiencies from Silicon photovoltaics(PV). Even though from the scientifical point of view it could be interesting to acomplish that, scientists should concentrate effort to invest in materials that can provide more return: in the case of spectral converters, they are very unlikely to have a place in flat-panel PV's. However, concentrated photovoltaics (CPV) technology may get a boost from such devices, an more attention should be driven to this goal.
Moisture in the form of humidity has a significant impact on the operation of photovoltaic (PV) cells and panels. Moisture is often diffuse through the encapsulant film (Ethylene Vynil Acetate (EVA), PVB, PVF, PMMA) or the breathable back-sheet. Moisture is known to accelerate the degradation and reduce the performance of a PV while operating in a wet environment. SCAPS 1 D is widely used to simulate and estimate the operation of PV. In this work, we showed the effect of moisture on the operation and performance of a PV, made from monocrystalline silicon. Namely, the influence of defects and i…
Conventional photovoltaic machinery, including traditional silicone panels, fails to address efficiency problems. Recent technological advances suggest less metal-specific reliance, but plastic substrates are bound by cost-inefficiency. Photovoltaic paint effectively dissociates from metal dependency and relies on a combination p-n junction diode principle/thermoelectric effect to generate electrical energy from solar exposure. Replicating the junction is accomplished via multi-polymer layers of crystalline-silica water-based paint with ionic solution concentration gradient overlap, reconstruc…
The effect of chemical doping of graphene films on the photovoltaic properties of the graphene/silicon Schottky junction solar cells was investigated. Thionyl chloride modification greatly enhanced the conductivity of graphene film, resulting in a significant improvement in cell performance with a 3-fold increase in conversion efficiency (up to 3.9%) and good short-term stability.
A method based on the particle swarm optimization (PSO) algorithm is presented to design quasi-two-dimensional (Q2D) materials. With this development, various single-layer and bi-layer materials in C, Si, Ge, Sn, and Pb were predicted. A new Si bi-layer structure is found to have a much-favored energy than the previously widely accepted configuration. Both single-layer and bi-layer Si materials have small band gaps, limiting their usages in optoelectronic applications. Hydrogenation has therefore been used to tune the electronic and optical properties of Si layers. We discover two hydrogenated…
Based on first-principles calculation we predict two new thermodynamically stable layered-phases of silicon, named as silicites, which exhibit strong directionality in the electronic and structural properties. As compared to silicon crystal, they have wider indirect band gaps but also increased absorption in the visible range making them more interesting for photovoltaic applications. These stable phases consist of intriguing stacking of dumbbell patterned silicene layers having trigonal structure with $\sqrt{3} \times \sqrt{3}$ periodicity of silicene and have cohesive energies smaller but co…
Si nanocrystals have been extensively studied because of their novel properties and their potential applications in electronic, optoelectronic, photovoltaic, thermoelectric and biological devices. These new properties are achieved through the combination of the quantum confinement of carriers and the strong influence of surface chemistry. As in the case of bulk Si the tuning of the electronic, optical and transport properties is related to the possibility of doping, in a controlled way, the nanocrystals. This is a big challenge since several studies have revealed that doping in Si nanocrystals…
We discuss the key principles of artificial photosynthesis for photovoltaic energy conversion. We demonstrate these principles by examining the operation of the so-called "dye sensitized solar cell" (DSSC) - a photoelectrochemical device which simulates the charge separation process across a nano-structured membrane that is characteristic of natural systems. These type of devices have great potential to challenge silicon semiconductor technology in the low cost, medium efficiency segment of the PV market. Ruthenium charge transfer complexes are currently used as the photon harvesting component…
Lead-halide perovskites have demonstrated astonishing increases in power conversion efficiency in photovoltaics over the last decade. The most efficient perovskite devices now outperform industry-standard multi-crystalline silicon solar cells, despite the fact that perovskites are typically grown at low temperature using simple solution-based methods. However, the toxicity of lead and its ready solubility in water are concerns for widespread implementation. These challenges, alongside the many successes of the perovskites, have motivated significant efforts across multiple disciplines to find …
Frequently, trends in record AM1.5 power-conversion efficiencies versus time, such as the NREL efficiency chart, are used to analyze the relative merits of different photovoltaic material technologies. However, this approach belies the effort expended in achieving these levels of performance. We introduce cumulative publications as a proxy for total R&D efforts and find surprisingly that silicon, Cu(In,Ga)Se2 (CIGSe), CdTe, and halide perovskite technologies have each followed essentially the same learning curve of 20-24% efficiency within 10,000 publications and a consistent marginal rate of …
Thin film of silicon is an interesting material for many technological applications in electronic industry and in energy harvesting technologies, but requires a method for controlled growth of thin films. The purpose of this study is to screen a wide variety of Si content precursors for Si ALD reactions using state-of-the-art density-functional calculations. Among the studied 85 Si content precursors we found that C7H12OSi(Methoxy-trivinyl-silane) and C7H9NSi (Benzyliminosilane) show positive indications for ALD reactivity for Si deposition. We believe that this finding will be helpful to deve…
Searches for low-energy tetrahedral polymorphs of carbon and silicon have been performed using density functional theory computations and the ab initio random structure searching (AIRSS) ap- proach. Several of the hypothetical phases obtained in our searches have enthalpies that are lower or comparable to those of other polymorphs of group 14 elements that have either been experimentally synthesized or recently proposed as the structure of unknown phases obtained in experiments, and should thus be considered as particularly interesting candidates. A structure of P bam symmetry with 24 atoms in…
