High efficiency, low cost, and long stability are three key factors for the wide application of photovoltaics (PV) which are currently intensively studied in order to meet the increasing global renewable energy demand. Currently, the PV market is mainly based on silicon. However, solar cells based on silicon may not be capable to meet the long-term global energy demand due to their relatively high costs and high energy required for the synthesis of silicon wafers, opening the door to conventional thin films (such as Cu(In1-xGax)Se2 (CIGS)) and innovative thin films (e.g. semiconductor quantum dots (QDs), based on PbS, PbSe, CdSe QDs). The advantages of QDs as solar cell materials are the low-temperature synthesis process, the tunable band gap via control of the composition and size, and the promise of physical mechanisms that may increase efficiency above the Shockley-Queisser limit, such as multiple exciton generation (MEG), in which more than one exciton is created from a single photon. However, the low efficiency, with a current laboratory record just above 10%, and the durability are still limitations on their widespread application in the PV market. It is very important to understand the surface structure and surface-ligand interactions in order to improve the efficiency and stability of QD solar cells. For CIGS solar cells, research-cell efficiencies have reached 22.6%, which is just below the efficiencies of Si-based solar cells. Besides, various deposition approaches have been developed that can supply high-efficiency, low-cost and large-area solar cell devices. However, it is still a challenge to guarantee long-term stability of CIGS modules. CIGS solar cells can be well protected by sealing into glass plates, but this in turn increases the manufacturing cost. Therefore, understanding of the degradation mechanism is necessary.
Positron techniques are powerful tools to study the surface composition of QDs and to determine the types of open space deficiencies in thin film materials. For QDs, previous studies provided indications that positrons can trap and annihilate at the surfaces of semiconductor QDs and can effectively probe the surface composition and electronic structure of colloidal semiconductor QDs. For CIGS, previous depth-sensitive positron experiments indicated the sensitivity of positrons to probe the types of vacancy-related defects in CIGS. ... Read more

Positron annihilation lifetime spectroscopy (PALS) and Doppler broadening positron annihilation spectroscopy (DB-PAS) depth profiling demonstrate pronounced growth of vacancy clusters at the grain boundaries of as-deposited Al-doped ZnO films deposited as transparent conductive oxide (TCO) on Cu(In,Ga)Se2 (CIGS) solar cells upon accelerated degradation at 85∘C/85% relative humidity. Quantitative fractions of positrons trapped either in the vacancy clusters at the grain boundaries or in Zn monovacancies inside the grains of ZnO:Al were obtained by detailed analysis of the PALS data using a positron trapping model. The time and depth dependence of the positron Doppler depth profiles can be accurately described using a planar diffusion model, with an extracted diffusion coefficient of 35nm2/hour characteristic for in-diffusion of molecules such as H2O and CO2 into ZnO:Al TCO films via the grain boundaries, where they react with the ZnO:Al. This leads to increased open volume at the grain boundaries that imposes additional transport barriers and may lead to charge carrier trapping and nonradiative recombination. Simultaneously, a pronounced increase in series resistance and a strong reduction in efficiency of the ZnO:Al capped CIGS solar cells is observed on a remarkably similar timescale. This strongly indicates that these atomic-scale processes of molecular in-diffusion and creation of open volume at the grain boundaries play a key role in the degradation of the solar cells. ... Read more

Previous studies have shown that positron-annihilation spectroscopy is a highly sensitive probe of the electronic structure and surface composition of ligand-capped semiconductor quantum dots (QDs) embedded in thin films. The nature of the associated positron state, however, whether the positron is confined inside the QDs or localized at their surfaces, has so far remained unresolved. Our positron-annihilation lifetime spectroscopy studies of CdSe QDs reveal the presence of a strong lifetime component in the narrow range of 358-371 ps, indicating abundant trapping and annihilation of positrons at the surfaces of the QDs. Furthermore, our ab initio calculations of the positron wave function and lifetime employing a recent formulation of the weighted density approximation demonstrate the presence of a positron surface state and predict positron lifetimes close to experimental values. Our study thus resolves the long-standing question regarding the nature of the positron state in semiconductor QDs and opens the way to extract quantitative information on surface composition and ligand-surface interactions of colloidal semiconductor QDs through highly sensitive positron-annihilation techniques. ... Read more

Positron annihilation depth-profiling is used as an innovative tool to monitor the evolution of vacancy defects in two series of ZnO:Al transparent conductive oxide (TCO) layers for Cu(In,Ga)Se2 (CIGS) solar cells under accelerated degradation at 85??C/85% relative humidity. The first series of ZnO:Al layers are deposited directly on flat glass substrates, leading to low densities of (extended) grain boundaries in the ZnO:Al. These ZnO:Al layers only show an increase in open volume upon degradation in the near-surface range. The second series of ZnO:Al layers are deposited on the more corrugated surface of CdS/CIGS/Mo solar cells, and show, on the other hand, a pronounced formation of open volume throughout the layer. Its depth-dependence is consistent with in-diffusion of molecules such as H2O and CO2 into the ZnO:Al layer via the grain boundaries, as primary driver for the degradation. The detected time-dependence of the growth of open volume at the grain boundaries in the ZnO:Al TCO layer matches the time scale of the observed reduction in solar cell efficiency and series resistance, suggesting that the generated open volume induces a significant barrier against charge carrier transport. ... Read more

Positron annihilation lifetime spectroscopy (PALS) and Doppler broadening positron annihilation spectroscopy DB-PAS) depth profiling demonstrate pronounced growth of vacancy clusters at the grain boundaries of as-deposited Al-doped ZnO films deposited as transparent conductive oxide (TCO) on Cu(In, Ga)Se2 (CIGS) solar cells upon accelerated degradation at 85 ◦C/85% relative humidity. Quantitative fractions of positrons trapped either in the vacancy clusters at the grain boundaries or in Zn monovacancies inside the grains of ZnO:Al were obtained by detailed analysis of the PALS data using a positron trapping model. The time and depth dependence of the positron Doppler depth profiles can be accurately described using a planar diffusion model, with an extracted diffusion coefficient of 35 nm2/hour characteristic for in-diffusion of molecules such as H2O andCO2 into ZnO:Al TCO films via the grain boundaries, where they react with the ZnO:Al. This leads to increased open volume at the grain boundaries that imposes additional transport barriers and may lead to charge carrier trapping and nonradiative recombination. Simultaneously, a pronounced increase in series resistance and a strong reduction in efficiency of the ZnO:Al capped CIGS solar cells is observed on a remarkably similar timescale. This strongly indicates that these atomic-scale processes of molecular in-diffusion and creation of open volume at the grain boundaries play a key role in the degradation of the solar cells. PhySH: Solar Cells, Positron Annihilation Spectroscopy, Grain Boundaries, Vacancies, Thin Films, Diffusion, Electrical Properties, Solid State Chemistry, Optoelectronics ... Read more

Recent studies showed that positron annihilation methods can provide key insights into the nanostructure and electronic structure of thin film solar cells. In this study, positron annihilation lifetime spectroscopy (PALS) is applied to investigate CdSe quantum dot (QD) light absorbing layers, providing evidence of positron trapping at the surfaces of the QDs. This enables one to monitor their surface composition and electronic structure. Further, 2D-Angular Correlation of Annihilation Radiation (2D-ACAR) is used to investigate the nanostructure of divacancies in photovoltaic-high-quality a-Si:H films. The collected momentum distributions were converted by Fourier transformation to the direct space representation of the electron-positron autocorrelation function. The evolution of the size of the divacancies as a function of hydrogen dilution during deposition of a-Si:H thin films was examined. Finally, we present a first positron Doppler Broadening of Annihilation Radiation (DBAR) study of the emerging class of highly efficient thin film solar cells based on perovskites. ... Read more

Positron Two Dimensional Angular Correlation of Annihilation Radiation (2D-ACAR) measurements reveal modifications of the electronic structure and composition at the surfaces of PbSe quantum dots (QDs), deposited as thin films, produced by various ligands containing either oxygen or nitrogen atoms. In particular, the 2D-ACAR measurements on thin films of colloidal PbSe QDs capped with oleic acid ligands yield an increased intensity in the electron momentum density (EMD) at high momenta compared to PbSe quantum dots capped with oleylamine. Moreover, the EMD of PbSe QDs is strongly affected by the small ethylenediamine ligands, since these molecules lead to small distances between QDs and favor neck formation between near neighbor QDs, inducing electronic coupling between neighboring QDs. The high sensitivity to the presence of oxygen atoms at the surface can be also exploited to monitor the surface oxidation of PbSe QDs upon exposure to air. Our study clearly demonstrates that positron annihilation spectroscopy applied to thin films can probe surface transformations of colloidal semiconductor QDs embedded in functional layers. ... Read more