Felix Lang

Monolithic perovskite/silicon-heterojunction tandem solar cells processed at low temperature

Tandem solar cells combining silicon and perovskite absorbers have the potential to outperform state-of-the-art high efficiency silicon single junction devices. However, the practical fabrication of monolithic silicon/perovskite tandem solar cells is challenging as material properties and processing requirements such as temperature restrict the device design. Here, we fabricate an 18% efficient monolithic tandem cell formed by a silicon heterojunction bottom- and a perovskite top-cell enabling a very high open circuit voltage of 1.78 V. The monolithic integration was realized via low temperature processing of the semitransparent perovskite sub-cell where an energetically aligned electron selective contact was fabricated by atomic layer deposition of tin oxide. The hole selective, transparent top contact was formed by a stack of the organic hole transport material spiro-OMeTAD, molybdenum oxide and sputtered indium tin oxide. The tandem cell design is currently limited by the photocurrent generated in the silicon bottom cell that is reduced due to reflectance losses. Based on optical modelling and first experiments, we show that these losses can be significantly reduced by combining optical optimization of the device architecture including light trapping approaches.

Perovskite Solar Cells with Large-Area CVD-Graphene for Tandem Solar Cells

Perovskite solar cells with transparent contacts may be used to compensate for thermalization losses of silicon solar cells in tandem devices. This offers a way to outreach stagnating efficiencies. However, perovskite top cells in tandem structures require contact layers with high electrical conductivity and optimal transparency. We address this challenge by implementing large-area graphene grown by chemical vapor deposition as a highly transparent electrode in perovskite solar cells, leading to identical charge collection efficiencies. Electrical performance of solar cells with a graphene-based contact reached those of solar cells with standard gold contacts. The optical transmission by far exceeds that of reference devices and amounts to 64.3% below the perovskite band gap. Finally, we demonstrate a four-terminal tandem device combining a high band gap graphene-contacted perovskite top solar cell (Eg = 1.6 eV) with an amorphous/crystalline silicon bottom solar cell (Eg = 1.12 eV).

It Takes Two to Tango—Double-Layer Selective Contacts in Perovskite Solar Cells for Improved Device Performance and Reduced Hysteresis

Solar cells made from inorganic-organic perovskites have gradually approached market requirements as their efficiency and stability have improved tremendously in recent years. Planar low-temperature processed perovskite solar cells are advantageous for possible large-scale production but are more prone to exhibiting photocurrent hysteresis, especially in the regular n-i-p structure. Here, a systematic characterization of different electron selective contacts with a variety of chemical and electrical properties in planar n-i-p devices processed below 180 °C is presented. The inorganic metal oxides TiO2 and SnO2, the organic fullerene derivatives C60, PCBM, and ICMA, as well as double-layers with a metal oxide/PCBM structure are used as electron transport materials (ETMs). Perovskite layers deposited atop the different ETMs with the herein applied fabrication method show a similar morphology according to scanning electron microscopy. Further, surface photovoltage spectroscopy measurements indicate comparable perovskite absorber qualities on all ETMs, except TiO2, which shows a more prominent influence of defect states. Transient photoluminescence studies together with current-voltage scans over a broad range of scan speeds reveal faster charge extraction, less pronounced hysteresis effects, and higher efficiencies for devices with fullerene compared to those with metal oxide ETMs. Beyond this, only double-layer ETM structures substantially diminish hysteresis effects for all performed scan speeds and strongly enhance the power conversion efficiency up to a champion stabilized value of 18.0%. The results indicate reduced recombination losses for a double-layer TiO2/PCBM contact design: First, a reduction of shunt paths through the fullerene to the ITO layer. Second, an improved hole blocking by the wide band gap metal oxide. Third, decreased transport losses due to an energetically more favorable contact, as implied by photoelectron spectroscopy measurements. The herein demonstrated improvements of multilayer selective contacts may serve as a general design guideline for perovskite solar cells.

Radiation Hardness and Self‐Healing of Perovskite Solar Cells

The radiation hardness of CH3 NH3 PbI3 -based solar cells is evaluated from in situ measurements during high-energy proton irradiation. These organic-inorganic perovskites exhibit radiation hardness and withstand proton doses that exceed the damage threshold of crystalline silicon by almost 3 orders of magnitude. Moreover, after termination of the proton irradiation, a self-healing process of the solar cells commences.

Correlation between Electronic Defect States Distribution and Device Performance of Perovskite Solar Cells

Abstract In the present study, random current fluctuations measured at different temperatures and for different illumination levels are used to understand the charge carrier kinetics in methylammonium lead iodide CH3NH3PbI3‐based perovskite solar cells. A model, combining trapping/detrapping, recombination mechanisms, and electron–phonon scattering, is formulated evidencing how the presence of shallow and deeper band tail states influences the solar cell recombination losses. At low temperatures, the observed cascade capture process indicates that the trapping of the charge carriers by shallow defects is phonon assisted directly followed by their recombination. By increasing the temperature, a phase modification of the CH3NH3PbI3 absorber layer occurs and for temperatures above the phase transition at about 160 K the capture of the charge carrier takes place in two steps. The electron is first captured by a shallow defect and then it can be either emitted or thermalize down to a deeper band tail state and recombines subsequently. This result reveals that in perovskite solar cells the recombination kinetics is strongly influenced by the electron–phonon interactions. A clear correlation between the morphological structure of the perovskite grains, the energy disorder of the defect states, and the device performance is demonstrated.

Unravelling the low-temperature metastable state in perovskite solar cells by noise spectroscopy

The hybrid perovskite methylammonium lead iodide CH3NH3PbI3 recently revealed its potential for the manufacturing of low-cost and efficient photovoltaic cells. However, many questions remain unanswered regarding the physics of the charge carrier conduction. In this respect, it is known that two structural phase transitions, occurring at temperatures near 160 and 310 K, could profoundly change the electronic properties of the photovoltaic material, but, up to now, a clear experimental evidence has not been reported. In order to shed light on this topic, the low-temperature phase transition of perovskite solar cells has been thoroughly investigated by using electric noise spectroscopy. Here it is shown that the dynamics of fluctuations detect the existence of a metastable state in a crossover region between the room-temperature tetragonal and the low-temperature orthorhombic phases of the perovskite compound. Besides the presence of a noise peak at this transition, a saturation of the fluctuation amplitudes is observed induced by the external DC current or, equivalently, by light exposure. This noise saturation effect is independent on temperature, and may represent an important aspect to consider for a detailed explanation of the mechanisms of operation in perovskite solar cells.

Enhancement of photocurrent in an ultra-thin perovskite solar cell by Ag nanoparticles deposited at low temperature

Ultra-thin perovskite absorber layers have attracted increasing interest since they are suitable for application in semi-transparent perovskite and tandem solar cells. In this study, size and density controlled plasmonic silver nanoparticles are successfully incorporated into ultra-thin perovskite solar cells through a low temperature spray chemical vapor deposition method. Incorporation of Ag nanoparticles leads to a significant enhancement of 22.2% for the average short-circuit current density. This resulted in a relative improvement of 22.5% for the average power conversion efficiency. Characterization by surface photovoltage and photoluminescence provides evidence that the implemented silver nanoparticles can enhance the charge separation and the trapping of electrons into the TiO2 layer at the CH3NH3PbI3/TiO2 interface. The application of these silver nanoparticles therefore has promise to enhance the ultra-thin perovskite solar cells.

Influence of Radiation on the Properties and the Stability of Hybrid Perovskites

Organic-inorganic perovskites are well suited for optoelectronic applications. In particular, perovskite single and perovskite tandem solar cells with silicon are close to their market entry. Despite their swift rise in efficiency to more than 21%, solar cell lifetimes are way below the needed 25 years. In fact, comparison of the time when the device performance has degraded to 80% of its initial value (T80 lifetime) of numerous solar cells throughout the literature reveals a strongly reduced stability under illumination. Herein, the various detrimental effects are discussed. Most notably, moisture- and heat-related degradation can be mitigated easily by now. Recently, however, several photoinduced degradation mechanisms have been observed. Under illumination, mixed perovskites tend to phase segregate, while, further, oxygen catalyzes deprotonation of the organic cations. Additionally, during illumination photogenerated charge can be trapped in the NH antibonding orbitals causing dissociation of the organic cation. On the other hand, organic-inorganic perovskites exhibit a high radiation hardness that is superior to crystalline silicon. Here, the proposed degradation mechanisms reported in the literature are thoroughly reviewed and the microscopic mechanisms and their implications for solar cells are discussed.

Influence of the Grain Size on the Properties of CH3NH3PbI3 Thin Films

Hybrid perovskites have already shown a huge success as an absorber in solar cells, resulting in the skyrocketing rise in the power conversion efficiency to more than η = 22%. Recently, it has been established that the crystal quality is one of the most important parameters to obtain devices with high efficiencies. However, the influence of the crystal quality on the material properties is not fully understood. Here, the influence of the morphology on electronic properties of CH3NH3PbI3 thin films is investigated. Postannealing was used to vary the average grain size continuously from ≈150 to ≈1000 nm. Secondary grain growth is thermally activated with an activation energy of Ea = 0.16 eV. The increase in the grain size leads to an enhancement of the photoluminescence, indicating an improvement in the material quality. According to surface photovoltage measurements, the charge-carrier transport length exhibits a linear increase with increasing grain size. The charge-carrier diffusion length is limited by grain boundaries. Moreover, an improved morphology leads to a drastic increase in power conversion efficiency of the devices.

Creation and annealing of metastable defect states in CH3NH3PbI3 at low temperatures

Methylammonium lead iodide (CH3NH3PbI3), an organic-inorganic perovskite widely used for optoelectronic applications, is known to dissociate under illumination with light at photon energies around 2.7 eV and higher. Here, we show that photo-induced dissociation is not limited to ambient temperatures but can be observed even at 5 K. The photo-induced dissociation of N–H bonds results in the formation of metastable states. Photoluminescence (PL) measurements reveal the formation of defect states that are located 100 meV within the bandgap. This is accompanied by a quenching of the band-to-band PL by one order of magnitude. Defect generation is reversible and annealing at 30 K recovers the band-to-band PL, while the light-induced defect states disappear concurrently.