A feasibility study towards ultra-thin PV solar cell devices by MOCDV based on a p-i-n structure incorporating pyrite

FeSx layers were deposited onto aluminosilicate glass substrates over a temperature range of 180°C to 500°C using a horizontal AP-MOCVD reactor. Fe(CO)5 was used as the Fe source in combination with t-Bu2S2 or t-BuSH as S precursor to control the rate of reaction and film stoichiometry. The Fe and S partial pressures were kept at 7.5 x 103 and 3.0 mbar, giving a gas phase S/Fe ratio of 400. Reactions followed a non-Arrhenius relationship at higher temperatures. XRD revealed mixed FeSx phases in the layers, which consisted mainly of FeS and Fe1-xS. Post growth annealing of the FeSx films using S powder in a static argon atmosphere and temperatures ranging from 250°C to 400°C was carried out using a 30 minute soak time. Characterisation by XRD confirmed a transitional phase change to FeS2 for the S anneal at 400°C. These films were highly absorbing in the visible region of the solar spectrum, which extended into the NIR. Devices with a p-i-n structure were produced using either a sulphurised or non-sulphurised FeSx i-layer, and compared to p-n devices without an i-layer. A non-sulphurised p-i-n device had the best I-V results, which was attributed to reduced lateral inhomogeneity across the device relative to the thinner p-n device structures. Devices with sulphurised FeSx i-layers performed least efficiently which is suspected to be due to a less defined FeSx/CdS junction caused by severe conditions during the S annealing process

Nanowire and core-shell-structures on flexible Mo Foil for CdTe solar cell applications

CdTe films, nanowires, film-nanowire combinations and CdS-CdTe core-shell structures have been fabricated in a preliminary survey of growth methods that will generate structures for PV applications. Selectivity between film, nanowire and film plus nanowire growth was achieved by varying the pressure of N2 gas present during Au-catalysed VLS growth of CdTe, on either Mo or Si substrates. Metamorphic growth of CdTe nanowires on sputtered CdTe films, deposited on glass substrates, was demonstrated. Coating of CdTe nanowires with CBD CdS gave conformal coverage whereas coating with MOCVD (Cd,Zn)S yielded highly crystallographic dendritic growth on the wires

Reducing series resistance in Cu2ZnSn(S,Se)4 nanoparticle ink solar cells on flexible molybdenum foil substrates

Earth abundant Cu2ZnSnS4 nanoparticle inks were depostied on molybdenum foil substrates and subsequently converted to high quality thin film Cu2ZnSn(S,Se)4 photovoltaic absorbers. Integration of these absorbers within a thin film solar cell device structure yields a solar energy conversion efficiency which is comparable to identical devices processed on rigid glass substrates. Importantly, this is only achieved when a thin layer of molybdenum is first applied directly to the foil. The layer limits the formation of a thick Mo(S,Se)x layer resulting in a substantially reduced series resistance

Cadmium Telluride Solar Cells on Ultrathin Glass for Space Applications

This paper details the preliminary findings of a study to achieve a durable thin film CdTe photovoltaic device structure onto ultra-thin space qualified cover glass. An aluminium doped zinc oxide (AZO) transparent conducting oxide (TCO) was deposited directly onto cover glass using metal organic chemical vapour deposition (MOCVD). The AZO demonstrated a low sheet resistance of 10 Ω/□ and high optical transparency of 85% as well as an excellent adherence and environmental stability. Preliminary deposition of the photovoltaic layers onto the AZO on cover glass, by MOCVD, showed the possibility of such a structure yielding a device conversion efficiency of 7.2 %. High series resistance (10 Ω.cm2) and low Voc (586 mV) were identified as the limiting factors when compared to the authors platform process on indium tin oxide (ITO) coated aluminosilicate. The coverage of the Cd1-xZnxS window layer along with the front contacting of the device was shown to be the major cause of the low efficiency. Further deposition of the AZO/CdTe employing an oxygen plasma cleaning step to the cover glass and evaporated gold front contacts significantly improved the device performance. A best conversion efficiency of 10.2 % with series resistance improved to 4.4 Ω.cm2 and open circuit voltage (Voc) up to 667 mV and good adhesion has demonstrated for the first time direct deposition of CdTe solar cells onto 100 μm thick space qualified cover glass

Thin CdTe layers deposited by a chamberless inline process using MOCVD, simulation and experiment

The deposition of thin Cadmium Telluride (CdTe) layers was performed by a chamberless metalorganic chemical vapour deposition process, and trends in growth rates were compared with computational fluid dynamics numerical modelling. Dimethylcadmium and diisopropyltelluride were used as the reactants, released from a recently developed coating head orientated above the glass substrate (of area 15 × 15 cm2). Depositions were performed in static mode and dynamic mode (i.e., over a moving substrate). The deposited CdTe film weights were compared against the calculated theoretical value of the molar supply of the precursors, in order to estimate material utilisation. The numerical simulation gave insight into the effect that the exhaust’s restricted flow orifice configuration had on the deposition uniformity observed in the static experiments. It was shown that > 59% of material utilisation could be achieved under favourable deposition conditions. The activation energy determined from the Arrhenius plot of growth rate was ~ 60 kJ/mol and was in good agreement with previously reported CdTe growth using metalorganic chemical vapour deposition (MOCVD). Process requirements for using a chamberless environment for the inline deposition of compound semiconductor layers were presented

CdCl2 treatment related diffusion phenomena in Cd1xZnxS/CdTe solar cells

Utilisation of wide bandgap Cd1_xZnxS alloys as an alternative to the CdS window layer is an attractive route to enhance the performance of CdTe thin film solar cells. For successful implementation, however, it is vital to control the composition and properties of Cd1_xZnxS through device fabrication processes involving the relatively high-temperature CdTe deposition and CdCl2 activation steps. In this study, cross-sectional scanning transmission electron microscopy and depth profiling methods were employed to investigate chemical and structural changes in CdTe/Cd1_xZnxS/CdS superstrate device structures deposited on an ITO/boro-aluminosilicate substrate. Comparison of three devices in different states of completion—fully processed (CdCl2 activated), annealed only (without CdCl2 activation), and a control (without CdCl2 activation or anneal)—revealed cation diffusion phenomena within the window layer, their effects closely coupled to the CdCl2 treatment. As a result, the initial Cd1_xZnxS/CdS bilayer structure was observed to unify into a single Cd1_xZnxS layer with an increased Cd/Zn atomic ratio; these changes defining the properties and performance of the Cd1_xZnxS/CdTe device

Enhanced Carrier Collection in Cd/In-Based Dual Buffers in Kesterite Thin-Film Solar Cells from Nanoparticle Inks

Increasing the power conversion efficiency (PCE) of kesterite Cu2ZnSn­(S,Se)4 (CZTSSe) solar cells has remained challenging over the past decade, in part due to open-circuit voltage (V OC)-limiting defect states at the absorber/buffer interface. Previously, we found that substituting the conventional CdS buffer layer with In2S3 in CZTSSe devices fabricated from nanoparticle inks produced an increase in the apparent doping density of the CZTSSe film and a higher built-in voltage arising from a more favorable energy-band alignment at the absorber/buffer interface. However, any associated gain in V OC was negated by the introduction of photoactive defects at the interface. This present study incorporates a hybrid Cd/In dual buffer in CZTSSe devices that demonstrate an average relative increase of 11.5% in PCE compared to CZTSSe devices with a standard CdS buffer. Current density–voltage analysis using a double-diode model revealed the presence of (i) a large recombination current in the quasi-neutral region (QNR) of the CZTSSe absorber in the standard CdS-based device, (ii) a large recombination current in the space-charge region (SCR) of the hybrid buffer CZTSSe–In2S3–CdS device, and (iii) reduced recombination currents in both the QNR and SCR of the CZTSSe–CdS–In2S3 device. This accounts for a notable 9.0% average increase in the short-circuit current density (J SC) observed in CZTSSe–CdS–In2S3 in comparison to the CdS-only CZTSSe solar cells. Energy-dispersive X-ray, secondary-ion mass spectroscopy, and grazing-incidence X-ray diffraction compositional analysis of the CZTSSe layer in the three types of kesterite solar cells suggest that there is diffusion of elemental In and Cd into the absorbers with a hybrid buffer. Enhanced Cd diffusion concomitant with a double postdeposition heat treatment of the hybrid buffer layers in the CZTSSe–CdS–In2S3 device increases carrier collection and extraction and boosts J SC. This is evidenced by electron-beam-induced current measurements, where higher current generation and collection near to the p–n junction is observed, accounting for the increase in J SC in this device. It is expected that optimization of the heat treatment of the hybrid buffer layers will lead to further improvements in the device performance

MOCVD of Cd(1-x)Zn(x)S/CdTe PV cells using an ultra-thin absorber layer

Ultra-thin Cd(₁ ₋ ₓ)Zn(ₓ)S/CdTe devices were produced by atmospheric pressure metal organic chemical vapour deposition (AP-MOCVD) with varying CdTe absorber thicknesses ranging from 1.0 to 0.2 mm and compared to baseline cells with total CdTe thickness of 2.25μ. The ultra-thin CdTe layers (≤1 μm) were intentionally doped with As to induce p-type conductivity in the absorber. Cell performance reduced with CdTe thickness, with the magnitude of photo-current generation loss becoming more significant for the very thin CdTe layers. The decline in cell performance was lower than the optically limited performance relating to a decrease in shunt resistance, Rsh, especially for the thinnest cells due to areas of incomplete CdTe coverage and large presence of pin-holes leading to micro-shorts. Incorporation of Zn into the CdS window layer improved cell performance for all devices except when 0.2 μm thick CdTe was used. This improvement was markedly in the blue region owing to enhanced optical transparency of the window layer. External quantum efficiency (EQE) measurements showed a red-shift of the window layer absorption edge due to leaching out of Zn during the CdCl₂ treatment. Reduction of the CdCl₂ deposition time was demonstrated to recover the blue response of the ultra-thin cells

Chemical analysis of Cd12xZnxS/CdTe solar cells by plasma profiling TOFMS

Thin film CdTe photovoltaic (PV) devices and reference layers obtained by the atmospheric pressure metalorganic vapour deposition (AP-MOCVD) method have been studied for their chemical structure using plasma profiling time-of-flight-mass spectroscopy (PP-TOFMS, also called glow discharge TOFMS). Different levels of arsenic (As) dopant in CdTe films were measured by PP-TOFMS and compared to results obtained from a more conventional depth profiling method (secondary ion mass spectrometry or SIMS). This comparison showed that PPTOFMS has the sufficient sensitivity towards detection of the As dopant in CdTe and hence is suited as a rapid, low vacuum tool in controlling the large scale production of CdTe PV materials

Real-time electron nanoscopy of photovoltaic absorber formation from kesterite nanoparticles

Cu2ZnSnS4 nanocrystals are annealed in a Se-rich atmosphere inside a transmission electron microscope. During the heating phase, a complete S-Se exchange reaction occurs while the cation sublattice and morphology of the nanocrystals are preserved. At the annealing temperature, growth of large Cu2ZnSnSe4 grains with increased cation ordering is observed in real-time. Thisyields an annealing protocol which is transferred to an industrially-similar solar cell fabrication process resulting in a 33% increase in the device open circuit voltage. The approach can be applied to improve the performance of any photovoltaic technology that requires annealing because of the criticality of the process step