High-low junctions for solar cell applications

A new theoretical model to calculate the effective surface recombination velocity (S_eff) of a high-low junction with an arbitrary impurity distribution is presented. The model is applied to erfc-diffused pp⁺ junctions using experimental data of bandgap narrowing, lifetime and mobility. Bandgap narrowing is shown to degrade the minority carrier reflecting properties of the high-low junction. Computer results are applied for the design of BSF solar cells and to study other solar cells structures based on high-low junctions.     

Effective recombination velocity at the NN+ interface

The effective recombination velocity S_nn⁺ at the nn⁺ interface in buried layer (nn⁺p) and n epi-n⁺ substrate structures has been studied using a model which takes into account the retarding outdiffusion region, recombination and bandgap narrowing. The variation of S_nn⁺ with diffusion length and bandgap narrowing has been estimated taking into consideration their doping-dependence. An attempt has been made to explain the wide range in the reported values for S_nn⁺ using the results of this study.Results indicate clearly the difference between the S_nn⁺ of the two structures. This difference arises from the collection by the p-substrate which accounts for a significant part of the S_nn⁺ of the buried layer structure over a wide range of values of diffusion length. This collection component of S_nn⁺ is sensitive to bandgap narrowing.On the other hand, the S_nn⁺ of the nn⁺ structure is largely determined by the recombination in the outdiffusion region which is sensitive mainly to the value of diffusion length in that region. The component of S_nn⁺ representing recombination in the n⁺ substrate is sensitive to bandgap narrowing. The present study indicates the dependence of S_nn⁺ on the structure and processing of the devices in which the nn⁺ interface occurs.     

Pressure‐Induced Bandgap Optimization in Lead‐Based Perovskites with Prolonged Carrier Lifetime and Ambient Retainability

Bond length and bond angle exhibited by valence electrons is essential to the core of chemistry. Using lead‐based organic–inorganic perovskite compounds as an exploratory platform, it is demonstrated that the modulation of valence electrons by compression can lead to discovery of new properties of known compounds. Yet, despite its unprecedented progress, further efficiency boost of lead‐based organic–inorganic perovskite solar cells is hampered by their wider bandgap than the optimum value according to the Shockley–Queisser limit. By modulating the valence electron wavefunction with modest hydraulic pressure up to 2.1 GPa, the optimized bandgap for single‐junction solar cells in lead‐based perovskites, for the first time, is achieved by narrowing the bandgap of formamidinium lead triiodide (HC(NH₂)₂PbI₃) from 1.489 to 1.337 eV. Strikingly, such bandgap narrowing is partially retained after the release of pressure to ambient, and the bandgap narrowing is also accompanied with double‐prolonged carrier lifetime. With First‐principles simulation, this work opens a new dimension in basic chemical understanding of structural photonics and electronics and paves an alternative pathway toward better photovoltaic materials‐by‐design.     

Influence of the dopant density profile on minority-carrier current in shallow,heavily doped emitters of silicon bipolar devices

Experimental determination of the dependence of recombination current in p⁺ and n⁺ regions on the dopant profile for shallow emitters of ion-implanted silicon solar cells is described. The results are analyzed by extending a previous analytical model for the transport of minority carriers in heavily doped regions. The extension accounts for an effective electric field, defined by heavy-doping effects at the surface, and suggests that the energy-gap narrowing for p⁺ silicon is slightly smaller than that for n⁺ silicon and/or that minority-carrier diffusivities are substantially lower than the majority-carrier ones at comparable dopant densities. The very high dopant densities achieved with the ion implantation/laser annealing technique provide an in situ surface passivation that supresses surface recombination and minimizes the emitter recombination current.     

Interplay of Structural and Optoelectronic Properties in Formamidinium Mixed Tin–Lead Triiodide Perovskites

Mixed lead–tin triiodide perovskites are promising absorber materials for low bandgap bottom cells in all‐perovskite tandem photovoltaic devices. Key structural and electronic properties of the FAPb_1−xSn_xI₃ perovskite are presented here as a function of lead:tin content across the alloy series. Temperature‐dependent photoluminescence and optical absorption measurements are used to identify changes in the bandgap and phase transition temperature. The large bandgap bowing parameter, a crucial element for the attainment of low bandgaps in this system, is shown to depend on the structural phase, reaching a value of 0.84 eV in the low‐temperature phase and 0.73 eV at room temperature. The parabolic nature of the bowing at all temperatures is compatible with a mechanism arising from bond bending to accommodate the random placement of unevenly sized lead and tin ions. Charge‐carrier recombination dynamics are shown to fall into two regimes. Tin‐rich compositions exhibit fast, monoexponential recombination that is almost temperature‐independent, in accordance with high levels of electrical doping. Lead‐rich compositions show slower, stretched‐exponential charge‐carrier recombination that is strongly temperature‐dependent, in accordance with a multiphonon assisted process. These results highlight the importance of structure and composition for control of bandgap bowing and charge‐carrier recombination mechanisms in low bandgap absorbers for all‐perovskite tandem solar cells.     

The emitter efficiency of bipolar transistors: Theory and experiments

A figure of merit (G_e) for the emitter is defined, which takes account of bandgap narrowing caused by high impurity concentrations, a doping-dependent lifetime, the built-in electric field and the recombination velocity at the emitter contact. A simple formula is given for G_e, based on computer simulations, and tested by several experiments.     

Heavy doping effects in silicon

The different mechanisms causing bandgap narrowing in heavily doped silicon are reviewed. A distinction is made between many-body effects and the effects due to random impurity distribution. The values of bandgap narrowing, calculated using a theoretical model, are compared with the experimental results. Recombination in heavily-doped silicon is discussed and the different recombination mechanisms, present at high doping levels, are explained. Experimental values for the minority-carrier lifetime as a function of the doping level are given. Surface recombination at the heavily doped Si/SiO₂ interface is discussed, the trnasport equations in the case of a position dependent bandgap are derived, and finally the influence of heavy-doping effects on the performance of several devices is discussed.     

The physical behaviour of an n+p silicon solar cell in concentrated sunlight

The performance of a simple n⁺p silicon solar cell at various illumination levels is analysed by a modified form of the Gummel and De Mari numerical algorithms. Effects of high doping, such as bandgap narrowing together with the correction to density of states are included. The effective recombination life time of the charge carriers due to both Shockley-Read-Hall recombination via traps and Auger recombination is taken into account. The base acceptor doping concentration is 10¹⁶ cm^?3. The light concentration is varied from 1 to 200 AM1. The physical mechanisms of the device at various levels of illumination are discussed by determining the cell parameters, namely, saturation current density, short circuit current density, ideality factor and fill factor. The ideality factor which is close to 1 at low illumination suggests that the cell is controlled by diffusion-recombination processes. The high value of the ideality factor, which is very much greater than 1 but less than 2, at high-illumination is attributed to high-injection effect. The efficiency reaches a maximum around 100 AM1 and starts falling beyond that. This fall is due to the high-injection and the voltage drop in the base layer. The fill factor starts falling at high-illumination.     

SHORT COMMUNICATION: ACCELERATED PUBLICATION: Diode characteristics in state‐of‐the‐art ZnO/CdS/Cu(In1−xGax)Se2 solar cells

We report a new state of the art in thin‐film polycrystalline Cu(In,Ga)Se₂‐based solar cells with the attainment of energy conversion efficiencies of 19·5%. An analysis of the performance of Cu(In,Ga)Se₂ solar cells in terms of some absorber properties and other derived diode parameters is presented. The analysis reveals that the highest‐performance cells can be associated with absorber bandgap values of ∼1·14 eV, resulting in devices with the lowest values of diode saturation current density (∼3×10⁻⁸ mA/cm²) and diode quality factors in the range 1·30 < A < 1·35. The data presented also support arguments of a reduced space charge region recombination as the reason for the improvement in the performance of such devices. In addition, a discussion is presented regarding the dependence of performance on energy bandgap, with an emphasis on wide‐bandgap Cu(In,Ga)Se₂ materials and views toward improving efficiency to > 1;20% in thin‐film polycrystalline Cu(In,Ga)Se₂ solar cells. Published in 2005 John Wiley & Sons, Ltd.     

Measurements of bandgap narrowing in Si bipolar transistors

Theory predicts appreciable bandgap narrowing in silicon for impurity concentrations greater than about 10¹⁷ cm^?3. This effect influences strongly the electrical behaviour of silicon devices, particularly the minority carrier charge storage and the minority carrier current flow in heavily doped regions. The few experimental data known are from optical absorption measurements on uniformly doped silicon samples. New experiments in order to determine the bandgap in silicon are described here. The bipolar transistor itself is used as the vehicle for measuring the bandgap in the base. Results giving the bandgap narrowing (ΔV_g0) as a function of the impurity concentration (N) in the base (in the range of 4.10¹⁵–2.5 10¹⁹ cm^?3) are discussed. The experimental values of ΔV_g0 as a function of N can be fitted by:

$\text{δV}{}_{\mathrm{g0}}\text{= V}{}_1\text{ln}\text{N}\text{N}{}_0\text{+}\text{ln}{}^2\text{N}\text{N}{}_0\text{+C}$

where V₁, N₀ and C are constants.It is also shown how the effective intrinsic carrier concentration (n_ie) is related with the bandgap narrowing (ΔV_g0).     

Two-dimensional analysis of the interdigited back-contact solar cell

Using two-dimensional computer analysis, the interdigited back contact silicon solar cell (IBC) was analyzed at high illumination levels and the results were compared with the conventional Front Junction cell. The change of effectiveness of Chockley-Read-Hall bulk and surface recombination centers at high currents as well as the induced internal electric field are argued to explain the improved efficiency predicted for IBC cells at high illumination levels. For a 100 μm cell thickness and lifetime τ_p0 = 10 μsec the efficiency is indicated to increase from 7.5% at 1 sun to 14.0% at 100 suns AMO, when a surface recombination velocity (s₀) equal to 1000 cm/sec is assumed. The substrate thickness to provide maximum efficiency was found to be approximately 50 μm. It is confirmed that the surface lifetime is a significant factor in determining the device conversion efficiency. Since surface recombination dominates the efficiency, a new IBC cell design with a front doping gradient has been introduced to suppress the surface recombination. The IBC cell with 10¹⁸/cm³ front surface n⁺-doping concentration is optimum for an impurity diffusion depth of 10 μm, s₀ = 1000 cm/sec, τ_p0 = 10 μsec, for which an efficiency of 12% is computed at 1 sum AMO. A useful efficiency of about 8% at 1 sun AMO, even with s₀ = 10⁵ cm/sec, is predicted with front doping.     

Auger recombination in heavily doped shallow-emitter silicon p-n-junction solar cells, diodes, and transistors

A rigorous analytic evaluation of an emitter model that includes Auger recombination but excludes bandgap narrowing is presented. It is shown that such a model cannot explain the experimentally observed values of the open-circuit voltage VOCin p-n-junction silicon solar cells. Thus physical mechanisms in addition to Auger recombination are responsible for the experimentally observed values of VOCin silicon solar cells and the common-emitter current gain in bipolar transistors.     

Interface Engineering Enhances the Photovoltaic Performance of Wide Bandgap FAPbBr3 Perovskite for Application in Low-Light Environments

Underwater solar cells (UWSCs) provide an ideal alternative to the energy supply for long-endurance autonomous underwater vehicles. However, different from conventional solar cells situated on land or above water, UWSCs give preference to use wide bandgap semiconductors (≥1.8 eV) as light absorber to match underwater solar spectra. Among wide bandgap semiconductors, FAPbBr₃ perovskite is under prime consideration owing to its matching optical bandgap (≈2.3 eV), outstanding photoelectric properties, easier processability, etc. Unfortunately, for FAPbBr₃ solar cells, substantial interface defects greatly limit the charge carrier extraction efficiency, thus limiting the device performance, especially in underwater low-light environments. This study employs a molecular self-assembly strategy to effectively eliminate the interfacial defects. As a result, a great improvement in power conversion efficiency (PCE) from 6.44% to 7.49% is obtained, which is among the best efficiency reported for inverted FAPbBr₃ solar cells up to date. Besides, a champion PCE of 30% is obtained under 520 nm monochromatic light irradiation (4.8 mW cm⁻²). These results demonstrate that FAPbBr₃ solar cells present a tremendously promising application in UWSCs.     

Influence of absorber doping in a-SiC：H/a-Si：H/a-SiGe：H solar cells

This work deals with the design evaluation and influence of absorber doping for a-Si:H/a-SiC:H/a-SiGe:H based thin-film solar cells using a two-dimensional computer aided design (TCAD) tool. Various physical parameters of the layered structure, such as doping and thickness of the absorber layer, have been studied. For reliable device simulation with realistic predictability, the device performance is evaluated by implementing necessary models (e.g., surface recombinations, thermionic field emission tunneling model for carrier transport at the heterojunction, Schokley-Read Hall recombination model, Auger recombination model, bandgap narrowing effects, doping and temperature dependent mobility model and using Fermi-Dirac statistics). A single absorber with a graded design gives an efficiency of 10.1% for 800 nm thick multiband absorption. Similarly, a tandem design shows an efficiency of 10.4% with a total absorber of thickness of 800 nm at a bandgap of 1.75 eV and 1.0 eV for the top a-Si and bottom a-SiGe component cells. A moderate n-doping in the absorber helps to improve the efficiency while p doping in the absorber degrades efficiency due to a decrease in the V_OC (and fill factor) of the device.     

Experimental investigation of the excess charge

The open-circuit voltage of about 600 mV developed by 0.1 ohm-cm silicon solar cells under air mass zero illumination is about 100 mV less than voltages predicted from simple diffusion theory. The lower measured voltages appear to be controlled by junction current transport processes associated with the thin top diffused layer. Mechanisms such as low n⁺ layer minority carrier lifetime and bandgap narrowing due to heavy doping effects (HDE) have been suggested to explain these results. Experimental determinations of the properties of the diffused layer are required to assess which of these mechanisms predominate. While direct measurement is difficult, an indirect measurement methodology exists by which the lifetime or transit time in the diffused layer can be obtained. Nine p-type, 1×2 cm, 〈111〉 orientation silicon wafers were phosphorus diffused at 880°C for 45 minutes using P0Cl₃. Open-circuit voltages of 595-612 mV, typical of all 0.1 ohm-cm cell voltages, were obtained. From the open-circuit voltage and short-circuit current, the diffusion controlled I₀ was obtained. In addition to illuminated I-V characteristics, the time constants from the Open-Circuit Voltage Decay method, and the minority carrier diffusion lengths in the base region were measured. The base region charge was determined using the base region diffusion length measured by an X-ray method. The data from these experiments combined with simple theory can imply the minority carrier time constant and the excess charge in the diffused layer. From this, certain conclusions are drawn about the relative roles of bandgap shrinkage and recombination rates in the diffused layer.     

Control of Solid‐State Dye‐Sensitized Solar Cell Performance by Block‐Copolymer‐Directed TiO2 Synthesis

Hybrid dye‐sensitized solar cells are typically composed of mesoporous titania (TiO₂), light‐harvesting dyes, and organic molecular hole‐transporters. Correctly matching the electronic properties of the materials is critical to ensure efficient device operation. In this study, TiO₂ is synthesized in a well‐defined morphological confinement that arises from the self‐assembly of a diblock copolymer—poly(isoprene‐b‐ethylene oxide) (PI‐b‐PEO). The crystallization environment, tuned by the inorganic (TiO₂ mass) to organic (polymer) ratio, is shown to be a decisive factor in determining the distribution of sub‐bandgap electronic states and the associated electronic function in solid‐state dye‐sensitized solar cells. Interestingly, the tuning of the sub‐bandgap states does not appear to strongly influence the charge transport and recombination in the devices. However, increasing the depth and breadth of the density of sub‐bandgap states correlates well with an increase in photocurrent generation, suggesting that a high density of these sub‐bandgap states is critical for efficient photo‐induced electron transfer and charge separation.     

Modeling the efficiency of multijunction solar cells

The efficiency of multijunction solar cells (MSCs) η is calculated taking into account radiative recombination, Shockley-Read recombination, front and rear surface recombination, recombination in the space-charge regions, and recombination at heterojunctions. Calculation is performed by self-consistent solution of the photocurrent, photovoltage, and heat-balance equations. MSC cooling by increasing the numbers of cells n and improvement in the conditions of heat removal is taken into account. An effect leading to a decrease in the photocurrent with increasing n, associated with narrowing of the energy ranges of photons incident on the MSC cell, is considered. It is found that a significant increase in the MSC efficiency can be achieved by improving the heat-removal conditions, in particular, through the use of radiators and increasing the MSC grayness factor to unity. The results obtained are compared to those of other authors. It is shown that the calculated dependences η(n) are in agreement with experimental values.     

Photovoltaic measurement of bandgap narrowing in moderately doped silicon

Solar cells have been fabricated on n-type and p-type moderately doped Si. The shrinkage of the Si bandgap has been obtained by measuring the internal quantum efficiency in the near infrared spectrum (hv = 1.00?1.25 eV) around the fundamental absorption edge. The results agree with previous optical measurements of bandgap narrowing in Si. It is postulated that this optically-determined bandgap narrowing is the rigid shrinkage of the forbidden gap due to many-body effects. The “device bandgap narrowing” obtained by measuring the pn product in bipolar devices leads to discrepant values because (i) the density of states in the conduction and valence band is modified due to the potential fluctuations originated in the variations in local impurity density, and (ii) the influence of Fermi-Dirac statistics.     

Defects Passivation via Potassium Iodide Post-Treatment for Antimony Selenosulfide Solar Cells with Improved Performance

Antimony selenosulfide (Sb₂(S,Se)₃) has been emerging as a promising light absorber in the past few years owing to tunable bandgap (1.1–1.7 eV), high absorption coefficient (>10⁵ cm⁻¹) and excellent phase and environmental stability. However, the efficiency of Sb₂(S,Se)₃ solar cells lags far behind the Shockley–Queisser limit. One of the critical obstacles originates from various extrinsic and intrinsic defects. They mostly locate in the deep energy levels and are prone to form recombination centers, inhibiting the improvement of device performance. Herein, surface post-treatment via potassium iodide is introduced to fabricate high-quality Sb₂(S,Se)₃ films and solar cells. The surface post-treatment not only manipulates the crystal growth process to form compact films with larger grain size but also forms better band alignment and inhibits the formation of deep-level defects antimony antisite (Sb_Se), thus improving the quality of heterojunction. Consequently, the resultant Sb₂(S,Se)₃ solar cells achieve a champion power conversion efficiency  of 9.22%. This study provides a new strategy of passivating deep-level intrinsic defects via surface post-treatment for high-efficiency Sb₂(S,Se)₃ solar cells.     

Naphthacenodithiophene Based Polymers—New Members of the Acenodithiophene Family Exhibiting High Mobility and Power Conversion Efficiency

Wide‐bandgap conjugated polymers with a linear naphthacenodithiophene (NDT) donor unit are herein reported along with their performance in both transistor and solar cell devices. The monomer is synthesized starting from 2,6‐dihydroxynaphthalene with a double Fries rearrangement as the key step. By copolymerization with 2,1,3‐benzothiadiazole (BT) via a palladium‐catalyzed Suzuki coupling reaction, NDT‐BT co‐polymers with high molecular weights and narrow polydispersities are afforded. These novel wide‐bandgap polymers are evaluated as the semiconducting polymer in both organic field effect transistor and organic photovoltaic applications. The synthesized polymers reveal an optical bandgap in the range of 1.8 eV with an electron affinity of 3.6 eV which provides sufficient energy offset for electron transfer to PC₇₀BM acceptors. In organic field effect transistors, the synthesized polymers demonstrate high hole mobilities of around 0.4 cm² V^–1 s^–1. By using a blend of NDT‐BT with PC₇₀BM as absorber layer in organic bulk heterojunction solar cells, power conversion efficiencies of 7.5% are obtained. This value is among the highest obtained for polymers with a wider bandgap (larger than 1.7 eV), making this polymer also interesting for application in tandem or multijunction solar cells.