Real Time Spectroscopic Ellipsometry Analysis of First Stage CuIn1-xGaxSe2 Growth: Indium-Gallium Selenide Co-Evaporation

Real time spectroscopic ellipsometry (RTSE) has been applied for in-situ monitoring of the first stage of copper indium-gallium diselenide (CIGS) thin film deposition by the three-stage co-evaporation process used for fabrication of high efficiency thin film photovoltaic (PV) devices. The first stage entails the growth of indium-gallium selenide (In1-xGax)₂Se₃ (IGS) on a substrate of Mo-coated soda lime glass maintained at a temperature of 400 °C. This is a critical stage of CIGS deposition because a large fraction of the final film thickness is deposited, and as a result precise compositional control is desired in order to achieve the optimum performance of the resulting CIGS solar cell. RTSE is sensitive to monolayer level film growth processes and can provide accurate measurements of bulk and surface roughness layer thicknesses. These in turn enable accurate measurements of the bulk layer optical response in the form of the complex dielectric function ε = ε₁ - iε₂, spectra. Here, RTSE has been used to obtain the (ε₁, ε₂) spectra at the measurement temperature of 400 °C for IGS thin films of different Ga contents (x) deduced from different ranges of accumulated bulk layer thickness during the deposition process. Applying an analytical expression in common for each of the (ε₁, ε₂) spectra of these IGS films, oscillator parameters have been obtained in the best fits and these parameters in turn have been fitted with polynomials in x. From the resulting database of polynomial coefficients, the (ε₁, ε₂) spectra can be generated for any composition of IGS from the single parameter, x. The results have served as an RTSE fingerprint for IGS composition and have provided further structural information beyond simply thicknesses, for example information related to film density and grain size. The deduced IGS structural evolution and the (ε₁, ε₂) spectra have been interpreted as well in relation to observations from scanning electron microscopy, X-ray diffractometry and energy-dispersive X-ray spectroscopy profiling analyses. Overall the structural, optical and compositional analysis possible by RTSE has assisted in understanding the growth and properties of three stage CIGS absorbers for solar cells and shows future promise for enhancing cell performance through monitoring and control

Role of band alignment at the transparent front contact/emitter interface in the performance of wide bandgap thin film solar cells

Recent numerical modeling and experimental work have shown that appropriate conduction band alignment at the emitter/absorber interface is critically important for high efficiency CdTe solar cells. To date, however, the properties of the transparent conducting oxide (TCO)/emitter interface have not been thoroughly investigated. Here, we use numerical modeling to determine the role of the conduction band alignment at the TCO/emitter interface. Our findings are increasingly important to device performance as efforts are made to widen the bandgap of the absorber. We also investigate the relative importance of the barrier caused by poor front contact versus the barrier at the back contact. It is well known that a barrier at the back contact can reduce the open circuit voltage of the device and produce rollover in the current density-voltage but is not well appreciated that a barrier at the front of the device can play a completely analogous role. We also show that for optimum device performance at any absorber bandgap, the conduction band of the TCO must be no more than 0.3 eV below the conduction band of the emitter

Perovskite Solar Cell Stability in Humid Air: Partially Reversible Phase Transitions in the PbI2-CH3NH3I-H2O System

After rapid progress over the past five years, organic-inorganic perovskite solar cells (PSCs) currently exhibit photoconversion efficiencies comparable to the best commercially available photovoltaic technologies. However, instabilities in the materials and devices, primarily due to reactions with water, have kept PSCs from entering the marketplace. Here, laser beam induced current imaging is used to investigate the spatial and temporal evolution of the quantum efficiency of perovskite solar cells under controlled humidity conditions. Several interesting mechanistic aspects are revealed as the degradation proceeds along a four-stage process. Three of the four stages can be reversed, while the fourth stage leads to irreversible decomposition of the photoactive perovskite material. A series of reactions in the PbI2-CH3NH3I-H2O system explains the interplay between the interactions with water and the overall stability. Understanding of the degradation mechanisms of PSCs on a microscopic level gives insight into improving the long-term stability

In-situ observation of moisture-induced degradation of perovskite solar cells using laser-beam induced current

Song Z, Abate A, Watthage SC, et al. In-situ observation of moisture-induced degradation of perovskite solar cells using laser-beam induced current. In: 2016 IEEE 43rd Photovoltaic Specialists Conference (PVSC). Piscataway, NJ: IEEE; 2016: 1202-1206.Solar cells based on organic-inorganic metal halide perovskites have been the focus of photovoltaic research over the past few years due to high power conversion efficiencies up to 22.1% and inexpensive manufacturing costs. However, commercialization of perovskite PV technology is hindered by lack of long-term stability. To elucidate the degradation mechanisms in the state of the art perovskite solar cells, we used laser beam induced current (LBIC) mapping to spatially resolve the device degradation during aging under high humidity conditions. We confirm that perovskites are prone to decomposition in the presence of water. By varying the absorber and hole-transport materials of the devices, we are able to compare performance and identify the water ingress and degradation mechanisms. These results provide insight into the design of materials and device architectures that may improve operational stability of perovskite solar cells

Optical Properties of Magnesium-Zinc Oxide for Thin Film Photovoltaics

Motivated by their utility in CdTe-based thin film photovoltaics (PV) devices, an investigation of thin films of the magnesium-zinc oxide (MgxZn1−xO or MZO) alloy system was undertaken applying spectroscopic ellipsometry (SE). Dominant wurtzite phase MZO thin films with Mg contents in the range 0 ≤ x ≤ 0.42 were deposited on room temperature soda lime glass (SLG) substrates by magnetron co-sputtering of MgO and ZnO targets followed by annealing. The complex dielectric functions ε of these films were determined and parameterized over the photon energy range from 0.73 to 6.5 eV using an analytical model consisting of two critical point (CP) oscillators. The CP parameters in this model are expressed as polynomial functions of the best fitting lowest CP energy or bandgap E0 = Eg, which in turn is a quadratic function of x. As functions of x, both the lowest energy CP broadening and the Urbach parameter show minima for x ~ 0.3, which corresponds to a bandgap of 3.65 eV. As a result, it is concluded that for this composition and bandgap, the MZO exhibits either a minimum concentration of defects in the bulk of the crystallites or a maximum in the grain size, an observation consistent with measured X-ray diffraction line broadenings. The parametric expression for ε developed here is expected to be useful in future mapping and through-the-glass SE analyses of partial and complete PV device structures incorporating MZO.Applied Science, Faculty ofNon UBCEngineering, School of (Okanagan)ReviewedFacult

Real Time Spectroscopic Ellipsometry Analysis of First Stage CuIn1−xGaxSe2 Growth: Indium-Gallium Selenide Co-Evaporation

Real time spectroscopic ellipsometry (RTSE) has been applied for in-situ monitoring of the first stage of copper indium-gallium diselenide (CIGS) thin film deposition by the three-stage co-evaporation process used for fabrication of high efficiency thin film photovoltaic (PV) devices. The first stage entails the growth of indium-gallium selenide (In1−xGax)2Se3 (IGS) on a substrate of Mo-coated soda lime glass maintained at a temperature of 400 °C. This is a critical stage of CIGS deposition because a large fraction of the final film thickness is deposited, and as a result precise compositional control is desired in order to achieve the optimum performance of the resulting CIGS solar cell. RTSE is sensitive to monolayer level film growth processes and can provide accurate measurements of bulk and surface roughness layer thicknesses. These in turn enable accurate measurements of the bulk layer optical response in the form of the complex dielectric function ε = ε1 − iε2, spectra. Here, RTSE has been used to obtain the (ε1, ε2) spectra at the measurement temperature of 400 °C for IGS thin films of different Ga contents (x) deduced from different ranges of accumulated bulk layer thickness during the deposition process. Applying an analytical expression in common for each of the (ε1, ε2) spectra of these IGS films, oscillator parameters have been obtained in the best fits and these parameters in turn have been fitted with polynomials in x. From the resulting database of polynomial coefficients, the (ε1, ε2) spectra can be generated for any composition of IGS from the single parameter, x. The results have served as an RTSE fingerprint for IGS composition and have provided further structural information beyond simply thicknesses, for example information related to film density and grain size. The deduced IGS structural evolution and the (ε1, ε2) spectra have been interpreted as well in relation to observations from scanning electron microscopy, X-ray diffractometry and energy-dispersive X-ray spectroscopy profiling analyses. Overall the structural, optical and compositional analysis possible by RTSE has assisted in understanding the growth and properties of three stage CIGS absorbers for solar cells and shows future promise for enhancing cell performance through monitoring and control

Enhanced Grain Size, Photoluminescence, and Photoconversion Efficiency with Cadmium Addition during the Two-Step Growth of CH₃NH₃PbI₃

Control over grain size and crystallinity is important for preparation of methylammonium lead iodide (MAPbI₃) solar cells. We explore the effects of using small concentrations of Cd²⁺ and unusually high concentrations of methylammonium iodide during the growth of MAPbI₃ in the two-step solution process. In addition to improved crystallinity and an enhancement in the size of the grains, time-resolved photoluminescence measurements indicated a dramatic increase in the carrier lifetime. As a result, devices constructed with the Cd-modified perovskites showed nearly a factor of 2 improvement in the power conversion efficiency (PCE) relative to similar devices prepared without Cd addition. The grains also showed a higher degree of orientation in the ⟨110⟩ direction, indicating a change in the growth mechanism, and the films were compact and smooth. We propose a Cd-modified film growth mechanism that invokes a critical role for low-dimensional Cd perovskites to explain the experimental observations