The performance‐boosting effect of alkali treatments is well known for chalcogenide thin‐film solar cells based on Cu(In,Ga)Se2 (CIGS) and Cu2ZnSn(S,Se)4 (CZTSSe–kesterite) absorbers. In contrast to heavier alkali elements, lithium is expected to alloy with the kesterite phase leading to the solid solution (LixCu1−x)2ZnSn(S,Se)4 (LCZTSSe), which offers a way of tuning the semiconductor bandgap by changing the ratio Li/(Li+Cu). Here is presented an experimental series of solution‐processed LCZTSSe with lithium fraction Li/(Li+Cu) ranging from x = 0 to 0.12 in the selenized absorber as measured by means of inductively coupled plasma mass spectrometry. The proportional increase in lattice parameter a and bandgap from 1.05 to 1.18 eV confirms the lithium alloying in the kesterite phase. Increase in grain size is observed for x up to 0.07, whereas a higher lithium fraction leads to a porous absorber morphology due to an inhomogeneous distribution of Li‐containing compounds in the kesterite layer. An increase of the photoluminescence quantum yield is observed as the Li fraction increases in the absorber layer. A champion device exhibits a remarkable efficiency of 11.6% (12.2% active area) for x = 0.06, close to the world record value of 12.6% demonstrating the effectiveness of lithium alloying.
The performance of kesterite (Cu2ZnSn(S,Se)4, CZTSSe) solar cells is hindered by low open circuit voltage (Voc). The commonly used metric for Voc-deficit, namely, the difference between the absorber band gap and qVoc, is not well-defined for compositionally complex absorbers like kesterite where the bandgap is hard to determine. Here, nonradiative voltage losses are analyzed by measuring the radiative limit of Voc, using external quantum efficiency (EQE) and electroluminescence (EL) spectra, without relying on precise knowledge of the bandgap. The method is applied to a series of Cu2ZnSn(S,Se)4 devices with Sn content variation from 27.6 to 32.9 at. % and a corresponding Voc range from 423 to 465 mV. Surprisingly, the lowest nonradiative loss, and hence the highest external luminescence efficiency (QELED), were obtained for the device with the lowest Voc. The trend is assigned to better interface quality between absorber and CdS buffer layer at lower Sn content.
Indium tin oxide (ITO) is a transparent conducting material that is widely used in devices where high transparency of the electrodes is required, such as flat panel and liquid crystal displays, touch panels, smart windows, and many others. ITO layers are deposited on a large scale by magnetron sputtering and then structured by lithography to define desired patterns of transparent electrodes. Here, a method for direct printing of transparent conductive patterns from ITO nanoparticle ink is communicated. The method combines inkjet printing with fast flash lamp annealing whereby the main novelty is to use an additional layer of a colored organic dye onto printed ITO to increase light absorption. The dye coating is instantly heated together with the underlying ITO layer by a light pulse, leading to an instant rise of the surface temperature, which is translated into improved optoelectronic properties of the ITO layers. Inkjet‐printed ITO patterns processed with the dye‐assisted flash lamp annealing exhibit a transmittance of up to 88% at 550 nm and resistivity of 3.1 × 10−3 Ω cm. Transparent touch‐sensing trackpad and capacitive touch sensors are demonstrated based on the printed ITO patterns, which can be utilized in transparent security systems and other transparent Internet‐of‐Things devices.
Bandgap grading is often employed in thin film solar cell absorbers for creating the back surface field that can reduce interface recombination at the back contact. Here, we investigate different pathways to obtain back graded Cu 2 Zn(Sn 1-x ,Ge x)Se 4 thin film solar cells based on a co-sputtered metal precursor and rapid thermal annealing route. The absorber bandgap can be precisely tuned for the whole compositional range of x=0…1. While Ge does not accumulate towards the back in absorbers fabricated from uniform precursor, Ge-back graded absorbers can be obtained from stacked metal precursors. A linear back grading with a bandgap energy difference of up to 40 meV has been achieved. However, no significant improvement in open-circuit voltage and near-infrared response could be observed for the kesterite devices. This indicates that even steeper gradients are required to obtain an effective back surface field.
The rear interface of kesterite absorbers with Mo back contact represents one of the possible sources of nonradiative voltage losses (ΔV oc,nrad) because of the reported decomposition reactions, an uncontrolled growth of MoSe2, or a nonoptimal electrical contact with high recombination. Several intermediate layers (IL), such as MoO3, TiN, and ZnO, have been tested to mitigate these issues, and efficiency improvements have been reported. However, the introduction of IL also triggers other effects such as changes in alkali diffusion, altered morphology, and modifications in the absorber composition, all factors that can also influence ΔV oc,nrad. In this study, the different effects are decoupled by designing a special sample that directly compares four rear structures (SLG, SLG/Mo, SLG/Al2O3, and SLG/Mo/Al2O3) with a Na-doped kesterite absorber optimized for a device efficiency >10%. The IL of choice is Al2O3 because of its reported beneficial effect to reduce the surface recombination velocity at the rear interface of solar cell absorbers. Identical annealing conditions and alkali distribution in the kesterite absorber are preserved, as measured by time-of-flight secondary ion mass spectrometry and energy-dispersive X-ray spectroscopy. The lowest ΔV oc,nrad of 290 mV is measured for kesterite grown on Mo, whereas the kesterite absorber on Al2O3 exhibits higher nonradiative losses up to 350 mV. The anticipated field-effect passivation from Al2O3 at the rear interface could not be observed for the kesterite absorbers prepared by the two-step process, further confirmed by an additional experiment with air annealing. Our results suggest that Mo with an in situ formed MoSe2 remains a suitable back contact for high-efficiency kesterite devices.
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