Coevaporation Stabilizes Tin-Based Perovskites in a Single Sn-Oxidation State

in Nano Letters (2022)

Chemically processed methylammonium tin-triiodide (CH3NH3SnI3) films include Sn in different oxidation states, leading to poor stability and low power conversion efficiency of the resulting solar cells ... [more ▼]

Chemically processed methylammonium tin-triiodide (CH3NH3SnI3) films include Sn in different oxidation states, leading to poor stability and low power conversion efficiency of the resulting solar cells (PSCs). The development of absorbers with Sn [2+] only has been identified as one of the critical steps to develop all Sn-based devices. Here, we report on coevaporation of CH3NH3I and SnI2 to obtain absorbers with Sn being only in the preferred oxidation state [+2] as confirmed by X-ray photoelectron spectroscopy. The Sn [4+]-free absorbers exhibit smooth highly crystalline surfaces and photoluminescence measurements corroborating their excellent optoelectronic properties. The films show very good stability under heat and light. Photoluminescence quantum yields up to 4 × 10^-3 translate in a quasi Fermi-level splittings exceeding 850 meV under one sun equivalent conditions showing high promise in developing lead-free, high efficiency, and stable PSCs. [less ▲]

Inhomogeneities in lead halide perovskite absorbers revealed by quantitative Photoluminescence Imaging

in Phirke, Himanshu; Singh, Ajay; Hieulle, Jeremy (Eds.) et al Inhomogeneities in lead halide perovskite absorbers revealed by quantitative Photoluminescence Imaging (2022, April 20)

The impact of strain on growth mode in chemical vapor deposited mono- and few-layer MoS2

in AIP Adv. (2022), 12(6), 065010

The development of high-quality chemical vapor-deposited mono- and few-layer MoS2 is of high relevance for future applications in functional devices. Consequently, a detailed understanding of the growth ... [more ▼]

The development of high-quality chemical vapor-deposited mono- and few-layer MoS2 is of high relevance for future applications in functional devices. Consequently, a detailed understanding of the growth mode and the parameters affecting it is important. Here, we show for the case of mono- and few-layer MoS2 grown on Muscovite mica, how strain and temperature impact the growth mode. We show how misleading the determination of the number of MoS2 layers is, solely based on Raman spectroscopy due to the occurrence of strain and changes in the growth mode. A combination of atomic force microscopy, Raman spectroscopy, and ab initio calculations reveal that that the growth at 500 dgree C synthesis temperature exhibits a strained layer-by-layer growth of up to three mono-layers, whereas at 700 degree C, a strain release occurs and layer-by-layer growth is confined to the first mono-layer only. We relate the occurrence of strain to the formation of gas bubbles below the MoS2 film, escaping the mica sheets during high temperature synthesis. Our analysis shows that mica substrates can be used to study strain in 2D materials without the need to apply external stress and that a detailed knowledge of the MoS2 morphology is necessary to correctly interpret the Raman results. [less ▲]

Impact of metallic potassium post-deposition treatment on epitaxial Cu(In, Ga)Se2

in Thin Solid Films (2021)

Alkali post-deposition treatments (PDTs) of Cu(In, Ga)Se2 (CIGSe) absorbers are known to improve the power conversion efficiency of the thin-film solar cell devices. The PDTs are usually carried out via ... [more ▼]

Alkali post-deposition treatments (PDTs) of Cu(In, Ga)Se2 (CIGSe) absorbers are known to improve the power conversion efficiency of the thin-film solar cell devices. The PDTs are usually carried out via evaporation of alkali fluorides in a selenium atmosphere onto a hot substrate. In this work, an alkali metal dispenser was used to evaporate pure metallic potassium onto epitaxial CIGSe absorbers. Subsequently, the absorber layers were heated in-situ to monitor chemical reactions and diffusion into the bulk. Due to the absence of grain boundaries, fluorine, and selenium, the effect of K on CIGSe absorber properties can be directly monitored. We find that potassium effectively diffuses into the bulk of epitaxial CIGSe absorber layers. The diffusion depends on the Cucontent of the CIGSe absorbers, in which Cu-depleted films present higher diffusion rates of K. Photoluminescence (PL) imaging corroborates that K in the bulk of the CIGSe absorber increases the PL yield, suggesting a passivation of defects or an increase in doping. This work highlights that alkali PDTs are not limited by interface and grain boundary modifications but also changes the absorber bulk properties, which needs to be taken into account. [less ▲]

The impact of Kelvin probe force microscopy operation modes and environment on grain boundary band bending in perovskite and Cu(In,Ga)Se2 solar cells

in Nano Energy (2021), 88

An in-depth understanding of the electronic properties of grain boundaries (GBs) in polycrystalline semiconductor absorbers is of high importance since their charge carrier recombination rates may be very ... [more ▼]

An in-depth understanding of the electronic properties of grain boundaries (GBs) in polycrystalline semiconductor absorbers is of high importance since their charge carrier recombination rates may be very high and hence limit the solar cell device performance. Kelvin Probe Force Microscopy (KPFM) is the method of choice to investigate GB band bending on the nanometer scale and thereby helps to develop passivation strategies. Here, it is shown that the workfunction, measured with amplitude modulation (AM)-KPFM, which is by far the most common KPFM measurement mode, is prone to exhibit measurement artifacts at grain boundaries on typical solar cell absorbers such as Cu(In,Ga)Se2 and CH3NH3PbI3. This is a direct consequence of a change in the cantilever–sample distance that varies on rough samples. Furthermore, we critically discuss the impact of different environments (air versus vacuum) and show that air exposure alters the GB and facet contrast, which leads to erroneous interpretations of the GB physics. Frequency modulation (FM)-KPFM measurements on non-air-exposed CIGSe and perovskite absorbers show that the amount of band bending measured at the GB is negligible and that the electronic landscape of the semiconductor surface is dominated by facet-related contrast due to the polycrystalline nature of the absorbers. [less ▲]

Nanoscale interfacial engineering enables highly stable and efficient perovskite photovoltaics

in Energy and Environmental Science (2021)

Passivation of the CuInSe2 surface via cadmium pre-electrolyte treatment

in Physical Review Materials (2020)

Surface characterization of epitaxial Cu-rich CuInSe2 absorbers

in IEEE (2020)

Surface characterization of epitaxial Cu-rich CuInSe2 absorbers

in IEEE Photovoltaic Specialists Conference. Conference Record (2019, July)

We investigated the electrical properties of epitaxial Cu-rich CuInSe 2 by Kelvin probe force microscopy (KPFM) under ambient and ultra-high vacuum conditions. We first measured the sample under ambient ... [more ▼]

We investigated the electrical properties of epitaxial Cu-rich CuInSe 2 by Kelvin probe force microscopy (KPFM) under ambient and ultra-high vacuum conditions. We first measured the sample under ambient conditions before and after potassium cyanide (KCN) etching. In both cases, we do not see any substantial contrast in the surface potential data; furthermore, after the KCN etching we observed outgrowths with a height around 2nm over the sample surface. On the other hand, the KPFM measurements under ultra-high vacuum conditions show a work function dependence according to the surface orientation of the Cu-rich CuInSe 2 crystal. Our results show the possibility to increase the efficiency of epitaxial Cu-rich CuInSe 2 by growing the materials in the appropriated surface orientation where the variations in work function are reduced. [less ▲]

Fermi-level pinning in methylammonium lead iodide perovskites

in Nanoscale (2019)

Hybrid organic inorganic perovskites are ideal candidates for absorber layers in next generation thin film photovoltaics. The polycrystalline nature of these layers imposes substantial complications for ... [more ▼]

Hybrid organic inorganic perovskites are ideal candidates for absorber layers in next generation thin film photovoltaics. The polycrystalline nature of these layers imposes substantial complications for the design of high efficiency devices since the optoelectronic properties can vary on the nanometre scale. Here we show via scanning tunnelling microscopy and spectroscopy that different grains and grain facets exhibit variations in the local density of states. Modeling of the tunneling spectroscopy curves allows us to quantify the density and fluctuations of surface states and estimate the variations in workfunction on the nanometre scale. The simulations corroborate that the high number of surface states leads to Fermi-level pinning of the methylammonium lead iodide surfaces. We do not observe a variation of the local density of states at the grain boundaries compared to the grain interior. These results are in contrast to other reported SPM measurements in literature. Our results show that most of the fluctuations of the electrical properties in these polycrystalline materials arise due to grain to grain variations and not due to distinct electronic properties of the grain boundaries. The measured workfunction changes at the different grains result in local variations of the band alignment with the carrier selective top contact and the varying number of surface states influence the recombination activity in the devices. [less ▲]