Al2O3 Surface Passivation Characterized on Hydrophobic and Hydrophilic c-Si by a Combination of QSSPC, CV, XPS and FTIR

Abstract In this work, the influence of the c-Si surface finishing (hydrophobic/hydrophilic) prior to the deposition of the Al2O3 passivation layer on the passivation quality is investigated. The samples are characterized by a combination of Quasi-Steady-State-PhotoConductance (QSSPC) Capacity-Conductance (CV), X-ray Photoelectron Spectroscopy (XPS) and Fourier Transformed InfraRed (FTIR) measurements. Furthermore, FTIR measurements are used to determine the thickness of interfacial SiOx layer

Physical routes for the synthesis of kesterite

This paper provides an overview of the physical vapor technologies used to synthesize Cu2ZnSn(S,Se)4 thin films as absorber layers for photovoltaic applications. Through the years, CZT(S,Se) thin films have been fabricated using sequential stacking or co-sputtering of precursors as well as using sequential or co-evaporation of elemental sources, leading to high-efficient solar cells. In addition, pulsed laser deposition of composite targets and monograin growth by the molten salt method were developed as alternative methods for kesterite layers deposition. This review presents the growing increase of the kesterite-based solar cell efficiencies achieved over the recent years. A historical description of the main issues limiting this efficiency and of the experimental pathways designed to prevent or limit these issues is provided and discussed as well. Afinal section is dedicated to the description of promising process steps aiming at further improvements of solar cell efficiency, such as alkali doping and bandgap grading1. R Caballero and M León acknowledge financial support via the Spanish Ministry of Science, Innovation and Universities project (WINCOST, ENE2016-80788-C5-2-R) and thank H2020 EU Programme under the project INFINITE-CELL (H2020-MSCA-RISE-2017-777968). 2. S Canulescu and J Schou acknowledge the support from Innovation Fund Denmark. 3. D-H Kim acknowledges financial support via the DGIST R&D Program of the Ministry of Science and ICT, KOREA (18-BD-05). 4.C. Malerba acknowledges the support from the Italian Ministry of Economic development in the framework of the Operating Agreement with ENEA for the Research on the Electric System. 5.A Redinger acknowledges financial support via the FNR Attract program, Project : SUNSPOT, Nr.11244141. 6. E Saucedo thanks H2020 EU Programme under the projects STARCELL (H2020-NMBP-03-2016-720907) and INFINITE-CELL (H2020-MSCA-RISE-2017-777968), the Spanish Ministry of Science, Innovation and Universities for the IGNITE project (ENE2017-87671-C3-1-R), and the European Regional Development Funds (ERDF, FEDER Programa Competitivitat de Catalunya 2007–2013). IREC belong to the SEMS (Solar Energy Materials and Systems) Consolidated Research Group of the ‘Generalitat de Catalunya’ (Ref. 2017 SGR 862). 7. Taltech acknowledges financial support via the Estonian Ministry of Education and Research funding project IUT19-28 and the European Union Regional Development Fund, Project TK141. 8. B Vermang has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 Research and Innovation Programme (Grant Agreement No 715027

On the identification of Sb2Se3 using Raman scattering

Robust evidences are presented that show that the Raman mode close to 250 cm-1 in Sb2Se3 thin films does not belong to this binary compound. A study of the Raman spectrum power dependency revealed the formation of Sb2O3 for high values of power excitation when these measurements are done in normal atmospheric conditions. In order to complement this study, Sb2Se3 thin films were annealed to mimic the thermal conditions of Raman measurements and characterized by X-ray diffraction technique. These measurements showed that the compound Sb2Se3 can be replaced by Sb2O3 under those conditions and a heat-assisted chemical process explains these findings. Furthermore, it is shown what the Raman conditions that are needed for correct measurements to be performed.publishe

Voids in kesterites and the influence of lamellae preparation by focused ion beam for transmission electron microscopy analyses

Kesterite solar cells based in Cu2ZnSnS4 and Cu2ZnSnSe4 are potential future candidates to be used in thin film solar cells. The technology still has to be developed to a great extent and for this to happen, high levels of confidence in the characterization methods are required so that improvements can be made on solid interpretations. In this study we show that the interpretations of one of the most used characterization techniques in kesterites, scanning transmission electron microscopy (STEM), might be affected by its specimen preparation when using focused ion beam (FIB). Using complementary measurements based on scanning electron microscopy and Raman scattering spectroscopy, compelling evidences show that secondary phases of ZnSe mixed in the bulk of Cu2ZnSnSe4 are the likely cause of the appearance of voids in the STEM lamellae. Sputtering simulations support this interpretation by showing that Zn in a ZnSe matrix is preferentially sputtered compared with any metal atom in a Cu2ZnSnSe4 matrix.publishe

Growth of Sb2Se3 thin films by selenization of RF sputtered binary precursors

In this work we present a method to grow Sb2Se3 thin films with a potential use as absorber layers in solar cell structures. The films were grown on several substrates: soda-lime glass, Mo coated soda-lime glass and Si . The Sb-Se precursor’s films were deposited by RF magnetron sputtering and then selenized under a H2Se gas flow. Different selenization temperatures were tested and analysed. Compositional and morphological analyses were performed by Energy Dispersive Spectroscopy and Scanning Electron Microscopy, respectively. Phase identification and structural characterization were done by X-ray Diffraction and Raman scattering spectroscopy showing that Sb2Se3 is the dominant phase with an orthorhombic crystalline structure. Traces of rhombohedral and amorphous Se secondary phases were also observed supported by their Se-rich compositions. Visible-NIR reflectance measurements allowed to extract a direct bandgap with a value close to 1.06 eV. Photoluminescence spectroscopy shows an emission with a broad band at 0.85 eV for samples selenized at lower temperatures and an intense peak at 0.75 eV for the sample selenized at higher temperatures. Electrical characterization shows low free hole concentrations and mobilities. At low temperatures, the nearest neighbour hopping is the dominant mechanism for the electronic transport for the analysed samples. Both electrical and optical properties are influenced by the type of defects present on samples. A discussion is made on the properties that need to be improved in order that these films can be integrated into thin film solar cells.publishe

Insulator materials for interface passivation of Cu(In,Ga)Se2 thin films

In this work, Metal-Insulator-Semiconductor (MIS) structures were fabricated in order to study different types of insulators, namely, aluminum oxide (Al2O3), silicon nitride (Si3Nx) and silicon oxide (SiOx) to be used as passivation layers in Cu(In,Ga)Se2 (CIGS) thin film solar cells. The investigated stacks consisted of SLG/Mo/CIGS/insulator/Al. Raman scattering and Photoluminescence measurements were done to verify the insulator deposition influence on the CIGS surface. In order to study the electrical properties of the CIGS-insulator interface, capacitance vs. conductance and voltage (C-G-V) measurements were done to estimate the number and polarity of fixed insulator charges (Qf). The density of interface defects (Dit) was estimated from capacitance vs. conductance and frequency (C-G-f) measurements. This study evidences that the deposition of the insulators at high temperatures (300 ºC) and the use of sputtering technique cause surface modification on the CIGS surface. We found that, by varying the SiOx deposition parameters, it is possible to have opposite charges inside the insulator, which would allow its use in different device architectures. The material with lower Dit values was Al2O3 when deposited by sputtering.publishe

Evolutionary process development towards next generation crystalline silicon solar cells : a semiconductor process toolbox application

Bulk crystalline Silicon solar cells are covering more than 85% of the world’s roof top module installation in 2010. With a growth rate of over 30% in the last 10 years this technology remains the working horse of solar cell industry. The full Aluminum back-side field (Al BSF) technology has been developed in the 90’s and provides a production learning curve on module price of constant 20% in average. The main reason for the decrease of module prices with increasing production capacity is due to the effect of up scaling industrial production. For further decreasing of the price per wattpeak silicon consumption has to be reduced and efficiency has to be improved. In this paper we describe a successive efficiency improving process development starting from the existing full Al BSF cell concept. We propose an evolutionary development includes all parts of the solar cell process: optical enhancement (texturing, polishing, anti-reflection coating), junction formation and contacting. Novel processes are benchmarked on industrial like baseline flows using high-efficiency cell concepts like i-PERC (Passivated Emitter and Rear Cell). While the full Al BSF crystalline silicon solar cell technology provides efficiencies of up to 18% (on cz-Si) in production, we are achieving up to 19.4% conversion efficiency for industrial fabricated, large area solar cells with copper based front side metallization and local Al BSF applying the semiconductor toolbox

Fabrication of high band gap kesterite solar cell absorber materials for tandem applications

© 2018 Using the thermal annealing of evaporated metallic precursors in successive H2Se and H2S atmospheres, it was possible to reproducibly manufacture kesterite absorber material for solar cell applications with a sulfur content varying from 30% to 100%. Respective band gaps for these sulfur inclusions were measured at approximately 1.45 eV and 2.0 eV. A recipe was devised for which results could be reproduced within an error margin of ±5% and the influence of the H2S pressure during the post sulfurization was negligible on all measurable and observable parameters. The evolution of the S/Se ratio in the sample was observed to be linearly dependent on the annealing time. It was also observed that at very early stages of the post-sulfurization, both the original Cu2(Zn,Ge)Se4 (CZGSe) and a primary Cu2(Zn,Ge)(S,Se)4 (CZGSSe) phase with a sulfur inclusion of ~30% coexist in the sample. The (112) x-ray diffraction (XRD) reflection of the CZGSe phase progressively disappears in favor for the first mixed CZGSSe phase. Using grazing incidence-XRD, the S/Se ratio was shown to be inhomogeneous. Indeed, the XRD measurement of the top layers led to the calculation of higher sulfur inclusions than was the case when measuring the bulk material. Top-scanning electron microscopy (SEM) as well as cross-SEM measurements were taken in order to determine the impact of the sulfur inclusion on the crystal growth and the overall quality of the produced absorber layers. The obtained images revealed a reduction in crystal size and the appearance of numerous holes in the layer as the S/Se ratio is increased.status: publishe

Electrical Characterization of Al2O3 Passivation Layers for p-Type CZ-Si PERC Solar Cells

This work characterizes p-type Silicon surface passivation using a high-k material (Al2O3 or HfO2) combining capacitance voltage (CV) and lifetime measurements. For Al2O3 samples, the Silicon substrate bulk and surface quality is equivalent to CZ Silicon used in industrial solar cell processing. While Al2O3 has been proven to provide high quality surface passivation on p-type doped Silicon surfaces, the influence of the growth conditions and the post-deposition annealing is not yet completely understood. The dielectric thin film has been deposited by common techniques (ALD, PECVD) on H-/OH- terminated Silicon surfaces (hydrophobic and hydrophilic, respectively). The impact of the roughness of the surface prior to the deposition has been also considered. Then, the passivation of each layer has been investigated as a function of different Al2O3 thicknesses (5 to 20 nm) and post-deposition annealing temperatures (300 to 800 \ub0C). CV measurements have been used to characterize chemical passivation (= interface trap density, Dit) and field effect passivation (= fixed charge density, Qf). Lifetime measurements have been used to assess the effective surface passivation. The results of both types of electrical characterization fit well together. (i) Prior post-deposition anneal, only either chemical passivation (ALD) or field effect passivation (PECVD) is adequate, resulting in lower effective lifetimes. (ii) At higher annealing temperatures, a negative net charge in the Al2O3 and a low Dit at the interface are measured, ideal for p-type CZ Silicon passivation and causing maximal effective lifetimes. (iii) At too high annealing temperatures, chemical passivation is destroyed resulting in decreasing effective lifetimes even though negative field effect remains in many cases. Another candidate as passivation layer on Silicon is HfO2. Being a new material in photovoltaics, it has been studied on FZ Silicon substrates and its electrical characterization has demonstrated interesting passivation properties at low anneal temperatures (also without thermal treatment)

Progress in Cleaning and Wet Processing for Kesterite Thin Film Solar Cells

Copper indium gallium selenide/sulfide (CIGS) and copper zinc tin selenide/sulfide (CZTS) are two thin film photovoltaic materials with many similar properties. Therefore, three new processing steps – which are well-known to be beneficial for CIGS solar cell processing – are developed, optimized and implemented in CZTS solar cells. For all these novel processing steps an increase in minority carrier lifetime and cell conversion efficiency is measured, as compared to standard CZTS processing. The scientific explanation of these effects is very similar to its CIGS equivalent: the incorporation of alkali metals, ammonium sulfide surface cleaning, and Al2O3 surface passivation leads to electrical enhancement of the CZTS bulk, front surface and reduced front interface recombination, respectively