Area-selective electrodeposition of micro islands for CuInSe2-based photovoltaics

in Results in Physics (2019), 12

Locally-confined electrodeposition of Cu(In,Ga)Se2micro islands for micro-concentrator solar cells.

in IEEE (2018)

Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2

in Scientific Reports (2017), 7

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of ... [more ▼]

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source. [less ▲]

Photoelectrochemical Screening of Solar Cell Absorber Layers: Electron Transfer Kinetics and Surface Stabilization

in Journal of Physical Chemistry. C, Nanomaterials and interfaces (2016)

edox electrolyte contacts offer a simple way of testing the photocurrent generation/collection efficiency in partially completed thin-film solar cells without the need to complete the entire fabrication ... [more ▼]

edox electrolyte contacts offer a simple way of testing the photocurrent generation/collection efficiency in partially completed thin-film solar cells without the need to complete the entire fabrication process. However, the development of a reliable quantitative method can be complicated by the instability of the semiconductor/electrolyte interface. In the case of Cu(In,Ga)Se2 (CIGSe) solar cells, these problems can be overcome by using samples that have undergone the next processing step in solar cell fabrication, which involves chemical bath deposition of a thin (ca. 50 nm) CdS buffer layer. The choice of redox system is also critical. The frequently used Eu3+/2+ redox couple is not suitable for reliable performance predictions since it suffers from very slow electron transfer kinetics. This leads to the buildup of photogenerated electrons near the interface, resulting in electron–hole recombination. This effect, which can be seen in the transient photocurrent response, has been quantified using intensity-modulated photocurrent spectroscopy (IMPS). The study has demonstrated that the more oxidizing Fe(CN)63–/4– redox system can be used when a CdS buffer layer is deposited on the CIGSe absorber. The wide bandgap CdS acts as a barrier to hole injection, preventing decomposition of the CIGSe and formation of surface recombination centers. The IMPS response of this system shows that there is no recombination; i.e., electron scavenging is very rapid. It is shown that measurements of the external quantum efficiency made using the Fe(CN)63–/4– redox couple with CdS-coated CIGSe layers can provide reliable predictions of the short-circuit currents of the complete solar cells. Similar results have been obtained using CdS-coated GaAs layers, suggesting that the new approach may be widely applicable. [less ▲]

Doping mechanism in pure CuInSe2

in JOURNAL OF APPLIED PHYSICS (2016), 119

Optical methodology for process monitoring of chalcopyrite photovoltaic technologies: Application to low cost Cu(In,Ga)(S,Se)2 electrodeposition based processes

in Solar Energy Materials and Solar Cells (2016)

Non-destructive characterization of both single layers and completed devices are important issues for the development of efficient and low cost Cu(In,Ga)(S,Se)2 (CIGS) modules at high yields. This implies ... [more ▼]

Non-destructive characterization of both single layers and completed devices are important issues for the development of efficient and low cost Cu(In,Ga)(S,Se)2 (CIGS) modules at high yields. This implies for the need of methodologies suitable for the assessment of optical, electrical, and physico-chemical parameters that are relevant for the final device efficiency and that can be used for quality control and process monitoring at different process steps. In these applications, detection of in-homogeneities in the different layers from large area modules is especially relevant, being the presence of these inhomogeneities responsible for the existing gap between the efficiencies achieved in these technologies at cell and module levels. In this context, this work reviews the different optical methodologies that have been developed in the framework of the SCALENANO European project for the advanced assessment of the different layers in high efficiency electrodeposited – based CIGS devices. This has includes different strategies as those based on Raman scattering, Photoluminescence/Electroluminescence (PL/EL) based techniques and new photoelectrochemical based tools and firstly Raman spectroscopy is very sensitive to both composition and crystal quality parameters that are determining for device efficiency. Use of resonant Raman excitation strategies allows achieving a high sensitivity of the Raman spectra to the analysed features in the different regions of the device. This involves selection of the suitable excitation wavelength (in the broad spectral region from UV to IR) for the resonant Raman excitation of the required layer in the device. The strong increase in the intensity of the Raman peaks related to the use of resonant excitation conditions allows also decreasing the measuring time to times compatible with the implementation of these techniques at online process monitoring level. Analysed parameters include the electrical conductivity of the Al-doped ZnO window layer, the thickness of the CdS buffer layer and the chemical composition (S/(S+Se) relative content) and presence of relevant secondary phases as Cu-poor ordered vacancy compounds in the surface region of the absorbers. In addition PL/EL imaging are powerful techniques that provide direct access to the optoelectronic properties of the materials and devices. Whereas EL is performed using complete devices by injecting current in analogy to the operation of a light emitting diode, PL allows the characterization of bare absorber materials without the need for any functional or contacting layers. Moreover, semiconductor photo-electrochemistry (PEC) is a versatile technique that enables many opto-electronic properties of semiconductors to be determined. Essentially, a semiconductor on a conducting substrate placed in a solution containing redox species forms a Schottky barrier junction. The formation of such a diode enables basic semiconductor properties to be measured such as doping type, doping density, band gap and the flat band position versus the vacuum energy scale. In all these cases, quality control indicators suitable for the advanced assessment of these processes have been identified and validated for the electrodeposition-based processes developed at Nexcis Company. [less ▲]

Vapour phase alkali species for Cu(In,Ga)Se2 solar cells

Scientific Conference (2015, September)

Alkalis are essential in Cu(In,Ga)Se2 absorber layers for efficient solar cells. Current doping methods rely on solid state diffusion of an alkali through to the absorber layer, e.g. a thin NaF layer on ... [more ▼]

Alkalis are essential in Cu(In,Ga)Se2 absorber layers for efficient solar cells. Current doping methods rely on solid state diffusion of an alkali through to the absorber layer, e.g. a thin NaF layer on Mo or NaCl dissolved in a metal precursor ink[1]. The apparent concentration of alkali in the final absorber is determined by the initial alkali dosing and the use of an interfacial barrier to stop alkali diffusion from the substrate. Until now the vapor–absorber interface as a source or sink of alkali doping has been largely ignored. We show that device efficiency improves from 2 to 8% by gas phase Na adsorption alone. Conversely initial results show that Na can also be desorbed to the gas phase. Although these efficiencies are lower than those obtained by including Na directly in the precursor (device efficiency 13.3% [1]), the findings are relevant to all chalcogenide growers as they show that exact doping, and thus control of device efficiency, is only possible when gas phase adsorption/desorption processes are controlled. [less ▲]

Electrodeposition of Kesterite thin films for photovoltaic applications: Quo vadis?

in Physica Status Solidi A. Applications and Materials Science (2015), 212(1), 88-102

This paper aims at providing an updated overview of the main achievements in the development of solar cells based on Cu2ZnSn(S,Se)4 (CZTS(Se)) kesterite absorbers obtained by electrodeposition. Although ... [more ▼]

This paper aims at providing an updated overview of the main achievements in the development of solar cells based on Cu2ZnSn(S,Se)4 (CZTS(Se)) kesterite absorbers obtained by electrodeposition. Although undoubtedly challenging, the ultimate goal is to learn from the past works and build a solid framework for future advances in this field. What is the reason for the lower efficiency of electrodeposited CZTS(Se)-based devices (8%) compared to the world record efficiency achieved with a hydrazine-based solution approach (12.6%)? Can this gap be filled, or there are intrinsic limitations for this achievement? The review is divided into the three main electrodeposition approaches: sequential elemental layer, alloy co-deposition, and chalcogenide co-deposition. It is argued that considerable technical challenges must be overcome for the latter approach to be successfully applied. [less ▲]

Cu2ZnSnSe4 device obtained by formate chemistry for metallic precursor layer fabrication

in Solar Energy (2015), 116

Quantification of surface ZnSe in Cu2ZnSnSe4-based solar cells by analysis of the spectral response

in Solar Energy Materials and Solar Cells (2014), 123

Absorber layers consisting of Cu2ZnSnSe4 (CZTSe) and surface ZnSe in variable ratios were prepared by selenization of electroplated Cu/Sn/Zn precursors and completed into full devices with up to 5.6 ... [more ▼]

Absorber layers consisting of Cu2ZnSnSe4 (CZTSe) and surface ZnSe in variable ratios were prepared by selenization of electroplated Cu/Sn/Zn precursors and completed into full devices with up to 5.6 % power conversion efficiency. The loss of short circuit current density for samples with increasing ZnSe content is consistent with an overall reduction of spectral response, pointing to a ZnSe current blocking behavior. A feature in the spectral response centered around 3 eV was identified and attributed to light absorption by ZnSe. A model is proposed to account for additional collection of the carriers generated underneath ZnSe capable of diffusing across to the space charge region. The model satisfactorily reproduces the shape of the spectral response and the estimated ZnSe surface coverage is in good qualitative agreement with analysis of the Raman spectral mapping. The model emphasizes the importance of the ZnSe morphology on the spectral response, and its consequences on the solar cell device performance. [less ▲]