On the origin of open-circuit voltage losses in flexible n-i-p perovskite solar cells.

The possibility to manufacture perovskite solar cells (PSCs) at low temperatures paves the way to flexible and lightweight photovoltaic (PV) devices manufactured via high-throughput roll-to-roll processes. In order to achieve higher power conversion efficiencies, it is necessary to approach the radiative limit via suppression of non-radiative recombination losses. Herein, we performed a systematic voltage loss analysis for a typical low-temperature processed, flexible PSC in n-i-p configuration using vacuum deposited C60 as electron transport layer (ETL) and two-step hybrid vacuum-solution deposition for CH3NH3PbI3 perovskite absorber. We identified the ETL/absorber interface as a bottleneck in relation to non-radiative recombination losses, the quasi-Fermi level splitting (QFLS) decreases from ~1.23 eV for the bare absorber, just ~90 meV below the radiative limit, to ~1.10 eV when C60 is used as ETL. To effectively mitigate these voltage losses, we investigated different interfacial modifications via vacuum deposited interlayers (BCP, B4PyMPM, 3TPYMB, and LiF). An improvement in QFLS of ~30-40 meV is observed after interlayer deposition and confirmed by comparable improvements in the open-circuit voltage after implementation of these interfacial modifications in flexible PSCs. Further investigations on absorber/hole transport layer (HTL) interface point out the detrimental role of dopants in Spiro-OMeTAD film (widely employed HTL in the community) as recombination centers upon oxidation and light exposure.

Planar perovskite solar cells with long-term stability using ionic liquid additives.

Solar cells based on metal halide perovskites are one of the most promising photovoltaic technologies1-4. Over the past few years, the long-term operational stability of such devices has been greatly improved by tuning the composition of the perovskites5-9, optimizing the interfaces within the device structures10-13, and using new encapsulation techniques14,15. However, further improvements are required in order to deliver a longer-lasting technology. Ion migration in the perovskite active layer-especially under illumination and heat-is arguably the most difficult aspect to mitigate16-18. Here we incorporate ionic liquids into the perovskite film and thence into positive-intrinsic-negative photovoltaic devices, increasing the device efficiency and markedly improving the long-term device stability. Specifically, we observe a degradation in performance of only around five per cent for the most stable encapsulated device under continuous simulated full-spectrum sunlight for more than 1,800 hours at 70 to 75 degrees Celsius, and estimate that the time required for the device to drop to eighty per cent of its peak performance is about 5,200 hours. Our demonstration of long-term operational, stable solar cells under intense conditions is a key step towards a reliable perovskite photovoltaic technology.

Time-resolved photoluminescence on double graded Cu(In,Ga)Se2 - Impact of front surface recombination and its temperature dependence.

Time-resolved photoluminescence (TRPL) is applied to determine an effective lifetime of minority charge carriers in semiconductors. Such effective lifetimes include recombination channels in the bulk as well as at the surfaces and interfaces of the device. In the case of Cu(In,Ga)Se2 absorbers used for solar cell applications, trapping of minority carriers has also been reported to impact the effective minority carrier lifetime. Trapping can be indicated by an increased temperature dependence of the experimentally determined photoluminescence decay time when compared to the temperature dependence of Shockley-Read-Hall (SRH) recombination alone and can lead to an overestimation of the minority carrier lifetime. Here, it is shown by technology computer-aided design (TCAD) simulations and by experiment that the intentional double-graded bandgap profile of high efficiency Cu(In,Ga)Se2 absorbers causes a temperature dependence of the PL decay time similar to trapping in case of a recombinative front surface. It is demonstrated that a passivated front surface results in a temperature dependence of the decay time that can be explained without minority carrier trapping and thus enables the assessment of the absorber quality by means of the minority carrier lifetime. Comparison with the absolute PL yield and the quasi-Fermi-level splitting (QFLS) corroborate the conclusion that the measured decay time corresponds to the bulk minority carrier lifetime of 250 ns for the double-graded CIGS absorber under investigation.

Bulk and surface recombination properties in thin film semiconductors with different surface treatments from time-resolved photoluminescence measurements.

The knowledge of minority carrier lifetime of a semiconductor is important for the assessment of its quality and design of electronic devices. Time-resolved photoluminescence (TRPL) measurements offer the possibility to extract effective lifetimes in the nanosecond range. However, it is difficult to discriminate between surface and bulk recombination and consequently the bulk properties of the semiconductor cannot be estimated reliably. Here we present an approach to constrain systematically the bulk and surface recombination parameters in semiconducting layers and reduces to finding the roots of a mathematical function. This method disentangles the bulk and surface recombination based on TRPL decay times of samples with different surface preparations. The technique is exemplarily applied to a CuInSe2 and a back-graded Cu(In,Ga)Se2 compound semiconductor, and upper and lower bounds for the recombination parameters and the mobility are obtained. Sets of calculated parameters are extracted and used as input for simulations of photoluminescence transients, yielding a good match to experimental data and validating the effectiveness of the methodology. A script for the simulation of TRPL transients is provided.

Voids and compositional inhomogeneities in Cu(In,Ga)Se2 thin films: evolution during growth and impact on solar cell performance.

Structural defects such as voids and compositional inhomogeneities may affect the performance of Cu(In,Ga)Se2 (CIGS) solar cells. We analyzed the morphology and elemental distributions in co-evaporated CIGS thin films at the different stages of the CIGS growth by energy-dispersive x-ray spectroscopy in a transmission electron microscope. Accumulation of Cu-Se phases was found at crevices and at grain boundaries after the Cu-rich intermediate stage of the CIGS deposition sequence. It was found, that voids are caused by Cu out-diffusion from crevices and GBs during the final deposition stage. The Cu inhomogeneities lead to non-uniform diffusivities of In and Ga, resulting in lateral inhomogeneities of the In and Ga distribution. Two and three-dimensional simulations were used to investigate the impact of the inhomogeneities and voids on the solar cell performance. A significant impact of voids was found, indicating that the unpassivated voids reduce the open-circuit voltage and fill factor due to the introduction of free surfaces with high recombination velocities close to the CIGS/CdS junction. We thus suggest that voids, and possibly inhomogeneities, limit the efficiency of solar cells based on three-stage co-evaporated CIGS thin films. Passivation of the voids' internal surface may reduce their detrimental effects.

ALD-Zn xTi yO as Window Layer in Cu(In,Ga)Se2 Solar Cells.

We report on the application of Zn xTi yO deposited by atomic layer deposition (ALD) as buffer layer in thin film Cu(In,Ga)Se2 (CIGS) solar cells to improve the photovoltaic device performance. State-of-the-art CIGS devices employ a CdS/ZnO layer stack sandwiched between the absorber layer and the front contact. Replacing the sputter deposited ZnO with ALD-Zn xTi yO allowed a reduction of the CdS layer thickness without adversely affecting open-circuit voltage ( VOC). This leads to an increased photocurrent density with a device efficiency of up to 20.8% by minimizing the parasitic absorption losses commonly observed for CdS. ALD was chosen as method to deposit homogeneous layers of Zn xTi yO with varying Ti content with a [Ti]/([Ti] + [Zn]) atomic fraction up to ∼0.35 at a relatively low temperature of 373 K. The Ti content influenced the absorption behavior of the Zn xTi yO layer by increasing the optical bandgap >3.5 eV in the investigated range. Temperature-dependent current-voltage ( I- V) measurements of solar cells were performed to investigate the photocurrent blocking behavior observed for high Ti content. Possible conduction band discontinuities introduced by Zn xTi yO are discussed based on X-ray photoelectron spectroscopy (XPS) measurements.

Structural and electronic properties of CdTe1-xSex films and their application in solar cells.

The performance improvement of conventional CdTe solar cells is mainly limited by doping concentration and minority carrier life time. Alloying CdTe with an isovalent element changes its properties, for example its band gap and behaviour of dopants, which has a significant impact on its performance as a solar cell absorber. In this work, the structural, optical, and electronic properties of CdTe1-xSex films are examined for different Se concentrations. The band gap of this compound changes with composition with a minimum of 1.40 eV for x = 0.3. We show that with increasing x, the lattice constant of CdTe1-xSex decreases, which can influence the solubility of dopants. We find that alloying CdTe with Se changes the effect of Cu doping on the p-type conductivity in CdTe1-xSex, reducing the achievable charge carrier concentration with increasing x. Using a front surface CdTe1-xSex layer, compositional, structural and electronic grading is introduced to solar cells. The efficiency is increased, mostly due to an increase in the short-circuit current density caused by a combination of lower band gap and a better interface between the absorber and window layer, despite a loss in the open-circuit voltage caused by the lower band gap and reduced charge carrier concentration.

Single-graded CIGS with narrow bandgap for tandem solar cells.

Multi-junction solar cells show the highest photovoltaic energy conversion efficiencies, but the current technologies based on wafers and epitaxial growth of multiple layers are very costly. Therefore, there is a high interest in realizing multi-junction tandem devices based on cost-effective thin film technologies. While the efficiency of such devices has been limited so far because of the rather low efficiency of semitransparent wide bandgap top cells, the recent rise of wide bandgap perovskite solar cells has inspired the development of new thin film tandem solar devices. In order to realize monolithic, and therefore current-matched thin film tandem solar cells, a bottom cell with narrow bandgap (~1 eV) and high efficiency is necessary. In this work, we present Cu(In,Ga)Se2 with a bandgap of 1.00 eV and a maximum power conversion efficiency of 16.1%. This is achieved by implementing a gallium grading towards the back contact into a CuInSe2 base material. We show that this modification significantly improves the open circuit voltage but does not reduce the spectral response range of these devices. Therefore, efficient cells with narrow bandgap absorbers are obtained, yielding the high current density necessary for thin film multi-junction solar cells.

Aluminum Chloride-Graphite Batteries with Flexible Current Collectors Prepared from Earth-Abundant Elements.

In the search for low-cost and large-scale stationary storage of electricity, nonaqueous aluminum chloride-graphite batteries (AlCl3-GBs) have received much attention due to the high natural abundances of their primary constituents, facile manufacturing, and high energy densities. Much research has focused on the judicious selection of graphite cathode materials, leading to the most notable recent advances in the performance of AlCl3-GBs. However, the major obstacle to commercializing this technology is the lack of oxidatively stable, inexpensive current collectors that can operate in chloroaluminate ionic liquids and are composed of earth-abundant elements. This study presents the use of titanium nitride (TiN) as a compelling material for this purpose. Flexible current collectors can be fabricated by coating TiN on stainless steel or flexible polyimide substrates by low-cost, rapid, scalable methods such as magnetron sputtering. When these current collectors are used in AlCl3-GB coin or pouch cells, stable cathodic operation is observed at voltages of up to 2.5 V versus Al3+/Al. Furthermore, these batteries have a high coulombic efficiency of 99.5%, power density of 4500 W kg-1, and cyclability of at least 500 cycles.

Refractive indices of layers and optical simulations of Cu(In,Ga)Se2 solar cells.

Cu(In,Ga)Se2 based solar cells have reached efficiencies close to 23%. Further knowledge-driven improvements require accurate determination of the material properties. Here, we present refractive indices for all layers in Cu(In,Ga)Se2 solar cells with high efficiency. The optical bandgap of Cu(In,Ga)Se2 does not depend on the Cu content in the explored composition range, while the absorption coefficient value is primarily determined by the Cu content. An expression for the absorption spectrum is proposed, with Ga and Cu compositions as parameters. This set of parameters allows accurate device simulations to understand remaining absorption and carrier collection losses and develop strategies to improve performances.

Compositionally Graded Absorber for Efficient and Stable Near-Infrared-Transparent Perovskite Solar Cells.

Compositional grading has been widely exploited in highly efficient Cu(In,Ga)Se2, CdTe, GaAs, quantum dot solar cells, and this strategy has the potential to improve the performance of emerging perovskite solar cells. However, realizing and maintaining compositionally graded perovskite absorber from solution processing is challenging. Moreover, the operational stability of graded perovskite solar cells under long-term heat/light soaking has not been demonstrated. In this study, a facile partial ion-exchange approach is reported to achieve compositionally graded perovskite absorber layers. Incorporating compositional grading improves charge collection and suppresses interface recombination, enabling to fabricate near-infrared-transparent perovskite solar cells with power conversion efficiency of 16.8% in substrate configuration, and demonstrate 22.7% tandem efficiency with 3.3% absolute gain when mechanically stacked on a Cu(In,Ga)Se2 bottom cell. Non-encapsulated graded perovskite device retains over 93% of its initial efficiency after 1000 h operation at maximum power point at 60 °C under equivalent 1 sun illumination. The results open an avenue in exploring partial ion-exchange to design graded perovskite solar cells with improved efficiency and stability.

Ni-Al-Cr superalloy as high temperature cathode current collector for advanced thin film Li batteries.

To obtain full advantage of state-of-the-art solid-state lithium-based batteries, produced by sequential deposition of high voltage cathodes and promising oxide-based electrolytes, the current collector must withstand high temperatures (>600 °C) in oxygen atmosphere. This imposes severe restrictions on the choice of materials for the first layer, usually the cathode current collector. It not only must be electrochemically stable at high voltage, but also remain conductive upon deposition and annealing of the subsequent layers without presenting a strong diffusion of its constituent elements into the cathode. A novel cathode current collector based on a Ni-Al-Cr superalloy with target composition Ni0.72Al0.18Cr0.10 is presented here. The suitability of this superalloy as a high voltage current collector was verified by determining its electrochemical stability at high voltage by crystallizing and cycling of LiCoO2 directly onto it.

Voltage dependent admittance spectroscopy for the detection of near interface defect states for thin film solar cells.

Recently recorded efficiencies of Cu(In,Ga)Se2 based solar cells were mainly achieved by surface treatment of the absorber that modifies the buffer-absorber interface region. However, only little is known about the electronic properties within this region. In this manuscript voltage dependent admittance spectroscopy is applied to low temperature grown Cu(In,Ga)Se2 based solar cells to detect near interface defect states in the absorber. Under non-equilibrium conditions even defect states close to the interface may cross the Fermi level and hence are detectable using capacitance based measurement methods, in contrast to the case of zero bias conditions. Such defects are of potential importance for understanding device limitations and hence, adequate characterization is necessary. A SCAPS model is developed including a near interface deep acceptor state, which explains the frequency and voltage dependence of the capacitance. Using the same model, also the experimental apparent doping density is explained.

Formation of a K-In-Se Surface Species by NaF/KF Postdeposition Treatment of Cu(In,Ga)Se2 Thin-Film Solar Cell Absorbers.

A NaF/KF postdeposition treatment (PDT) has recently been employed to achieve new record efficiencies of Cu(In,Ga)Se2 (CIGSe) thin film solar cells. We have used a combination of depth-dependent soft and hard X-ray photoelectron spectroscopy as well as soft X-ray absorption and emission spectroscopy to gain detailed insight into the chemical structure of the CIGSe surface and how it is changed by different PDTs. Alkali-free CIGSe, NaF-PDT CIGSe, and NaF/KF-PDT CIGSe absorbers grown by low-temperature coevaporation have been interrogated. We find that the alkali-free and NaF-PDT CIGSe surfaces both display the well-known Cu-poor CIGSe chemical surface structure. The NaF/KF-PDT, however, leads to the formation of bilayer structure in which a K-In-Se species covers the CIGSe compound that in composition is identical to the chalcopyrite structure of the alkali-free and NaF-PDT absorber.

CIGS thin-film solar module processing: case of high-speed laser scribing.

In this paper, we investigate the laser processing of the CIGS thin-film solar cells in the case of the high-speed regime. The modern ultra-short pulsed laser was used exhibiting the pulse repetition rate of 1 MHz. Two main P3 scribing approaches were investigated - ablation of the full layer stack to expose the molybdenum back-contact, and removal of the front-contact only. The scribe quality was evaluated by SEM together with EDS spectrometer followed by electrical measurements. We also modelled the electrical behavior of a device at the mini-module scale taking into account the laser-induced damage. We demonstrated, that high-speed process at high laser pulse repetition rate induced thermal damage to the cell. However, the top-contact layer lift-off processing enabled us to reach 1.7 m/s scribing speed with a minimal device degradation. Also, we demonstrated the P3 processing in the ultra-high speed regime, where the scribing speed of 50 m/s was obtained. Finally, selected laser processes were tested in the case of mini-module scribing. Overall, we conclude, that the top-contact layer lift-off processing is the only reliable solution for high-speed P3 laser scribing, which can be implemented in the future terawatt-scale photovoltaic production facilities.

Surface Passivation for Reliable Measurement of Bulk Electronic Properties of Heterojunction Devices.

Quantum efficiency measurements of state of the art Cu(In,Ga)Se2 (CIGS) thin film solar cells reveal current losses in the near infrared spectral region. These losses can be ascribed to inadequate optical absorption or poor collection of photogenerated charge carriers. Insight on the limiting mechanism is crucial for the development of more efficient devices. The electron beam induced current measurement technique applied on device cross-sections promises an experimental access to depth resolved information about the charge carrier collection probability. Here, this technique is used to show that charge carrier collection in CIGS deposited by multistage co-evaporation at low temperature is efficient over the optically active region and collection losses are minor as compared to the optical ones. Implications on the favorable absorber design are discussed. Furthermore, it is observed that the measurement is strongly affected by cross-section surface recombination and an accurate determination of the collection efficiency is not possible. Therefore it is proposed and shown that the use of an Al2 O3 layer deposited onto the cleaved cross-section significantly improves the accuracy of the measurement by reducing the surface recombination. A model for the passivation mechanism is presented and the passivation concept is extended to other solar cell technologies such as CdTe and Cu2 (Zn,Sn)(S,Se)4 .

On the chemical stability of post-lithiated garnet Al-stabilized Li7La3Zr2O12 solid state electrolyte thin films.

Garnet-based Al-doped Li7La3Zr2O12 has the potential to be used as a solid state electrolyte for future lithium microbattery architectures, due to its relatively high Li(+) conductivity and stability against Li. Through this work, a model experiment is presented in which the effect of post-lithiation on phase formation and chemical stability is studied for pulsed laser deposited Al-doped Li7La3Zr2O12 thin films on MgO substrates. We report the implications of the newly suggested post-lithiation route for films with thicknesses between 90 and 380 nm. The phase changes from cubic, to a mix of cubic and tetragonal Li7La3Zr2O12, to a cubic Li7La3Zr2O12 and La2Zr2O7 containing film is accompanied by a reduction in the degree of de-wetting as the thickness increases. This study reveals that the thicker, dense, and continuous films remain predominantly in a mixed phase containing cubic Li7La3Zr2O12 and the lithium free La2Zr2O7 phase whereas the thinner, de-wetted films exhibit improved lithium incorporation resulting in the absence of the lithium free phase. For tuning the electrical conductivity and effective use of these structures in future batteries, understanding this material system is of great importance as the chemical stability of the cubic Li7La3Zr2O12 phase in the thin film system will control its effective use. We report a conductivity of 1.2 × 10(-3) S cm(-1) at 325 °C for a 380 nm thick solid state electrolyte film on MgO for potential operation in future all solid state battery assemblies.

Potassium Postdeposition Treatment-Induced Band Gap Widening at Cu(In,Ga)Se2 Surfaces--Reason for Performance Leap?

Direct and inverse photoemission were used to study the impact of alkali fluoride postdeposition treatments on the chemical and electronic surface structure of Cu(In,Ga)Se2 (CIGSe) thin films used for high-efficiency flexible solar cells. We find a large surface band gap (E(g)(Surf), up to 2.52 eV) for a NaF/KF-postdeposition treated (PDT) absorber significantly increases compared to the CIGSe bulk band gap and to the Eg(Surf) of 1.61 eV found for an absorber treated with NaF only. Both the valence band maximum (VBM) and the conduction band minimum shift away from the Fermi level. Depth-dependent photoemission measurements reveal that the VBM decreases with increasing surface sensitivity for both samples; this effect is more pronounced for the NaF/KF-PDT CIGSe sample. The observed electronic structure changes can be linked to the recent breakthroughs in CIGSe device efficiencies.

Low-temperature-processed efficient semi-transparent planar perovskite solar cells for bifacial and tandem applications.

Semi-transparent perovskite solar cells are highly attractive for a wide range of applications, such as bifacial and tandem solar cells; however, the power conversion efficiency of semi-transparent devices still lags behind due to missing suitable transparent rear electrode or deposition process. Here we report a low-temperature process for efficient semi-transparent planar perovskite solar cells. A hybrid thermal evaporation-spin coating technique is developed to allow the introduction of PCBM in regular device configuration, which facilitates the growth of high-quality absorber, resulting in hysteresis-free devices. We employ high-mobility hydrogenated indium oxide as transparent rear electrode by room-temperature radio-frequency magnetron sputtering, yielding a semi-transparent solar cell with steady-state efficiency of 14.2% along with 72% average transmittance in the near-infrared region. With such semi-transparent devices, we show a substantial power enhancement when operating as bifacial solar cell, and in combination with low-bandgap copper indium gallium diselenide we further demonstrate 20.5% efficiency in four-terminal tandem configuration.

High-Efficiency Polycrystalline Thin Film Tandem Solar Cells.

A promising way to enhance the efficiency of CIGS solar cells is by combining them with perovskite solar cells in tandem devices. However, so far, such tandem devices had limited efficiency due to challenges in developing NIR-transparent perovskite top cells, which allow photons with energy below the perovskite band gap to be transmitted to the bottom cell. Here, a process for the fabrication of NIR-transparent perovskite solar cells is presented, which enables power conversion efficiencies up to 12.1% combined with an average sub-band gap transmission of 71% for photons with wavelength between 800 and 1000 nm. The combination of a NIR-transparent perovskite top cell with a CIGS bottom cell enabled a tandem device with 19.5% efficiency, which is the highest reported efficiency for a polycrystalline thin film tandem solar cell. Future developments of perovskite/CIGS tandem devices are discussed and prospects for devices with efficiency toward and above 27% are given.