Atom-Scale Chemistry in Chalcopyrite-Based Photovoltaic Materials Visualized by Atom Probe Tomography.

Chalcopyrite-based materials for photovoltaic devices tend to exhibit complex structural imperfections originating from their polycrystalline nature; nevertheless, properly controlled devices are surprisingly irrelevant to them in terms of resulting device performances. The present work uses atom probe tomography to characterize co-evaporated high-quality Cu(In,Ga)Se2 (CIGS) films on flexible polyimide substrates either with or without doping with Na or doping with Na followed by K via a post-deposition treatment. The intent is to elucidate the unique characteristics of the grain boundaries (GBs) in CIGS, in particular the correlations/anti-correlations between matrix elements and the alkali dopants. Various compositional fluctuations are identified at GBs irrespective of the presence of alkali elements. However, [Cu-poor and Se/In,Ga-rich] GBs are significantly more common than [Cu-rich and Se/In,Ga-poor] ones. In addition, the anti-correlations between Cu and the other matrix elements are found to show not only regular trends among themselves but also the association with the degree of alkali segregation at GBs. The Na and K concentrations exhibited a correlation at the GBs but not in the intragrain regions. Density functional theory calculations are used to explain the compositional fluctuations and alkali segregation at the GBs. Our experimental and theoretical findings not only reveal the benign or beneficial characteristics of the GBs of CIGS but also provide a fundamental understanding of the GB chemistry in CIGS-based materials.

Optimal CdS Buffer Thickness to Form High-Quality CdS/Cu(In,Ga)Se2 Junctions in Solar Cells without Plasma Damage and Shunt Paths.

CdS has been known to be one of the best junction partners for Cu(In,Ga)Se2 (CIGS) in CIGS solar cells. However, the use of thick CdS buffer decreases the short-circuit current density of CIGS solar cells. There are two obstacles that limit the use of ultrathin CdS. The first is plasma damage to CIGS during the preparation of transparent conducting windows and the second is a low shunt resistance due to the direct contact between the window and CIGS via pinholes in the thin CdS buffer. In other words, to avoid plasma damage and shunt paths, we may have to use a CdS buffer that is thicker than necessary to form a high-quality CdS/CIGS junction. This work aims to determine how thin the CdS buffer can be employed without sacrificing device performance while also eliminating the above two obstacles. We investigate the effect of CdS thickness on the performance of CIGS solar cells with silver nanowire-based window layers, which can eliminate both obstacles. An approximately 13 nm thick CdS buffer allows us to achieve high short-circuit current density and fill factor values. To attain an even high open-circuit voltage, an additional CdS buffer with a thickness of 13 nm is needed. The data from this study imply that an approximately 26 nm thick CdS buffer is sufficient to form a high-quality CdS/CIGS junction.

Fabrication of Robust Nanoscale Contact between a Silver Nanowire Electrode and CdS Buffer Layer in Cu(In,Ga)Se2 Thin-film Solar Cells.

Silver nanowire transparent electrodes have been employed as window layers for Cu(In,Ga)Se2 thin-film solar cells. Bare silver nanowire electrodes normally result in very poor cell performance. Embedding or sandwiching silver nanowires using moderately conductive transparent materials, such as indium tin oxide or zinc oxide, can improve cell performance. However, the solution-processed matrix layers can cause a significant number of interfacial defects between transparent electrodes and the CdS buffer, which can eventually result in low cell performance. This manuscript describes how to fabricate robust electrical contact between a silver nanowire electrode and the underlying CdS buffer layer in a Cu(In,Ga)Se2 solar cell, enabling high cell performance using matrix-free silver nanowire transparent electrodes. The matrix-free silver nanowire electrode fabricated by our method proves that the charge-carrier collection capability of silver nanowire electrode-based cells is as good as that of standard cells with sputtered ZnO:Al/i-ZnO as long as the silver nanowires and CdS have high-quality electrical contact. The high-quality electrical contact was achieved by depositing an additional CdS layer as thin as 10 nm onto the silver nanowire surface.

Carbon-Impurity Affected Depth Elemental Distribution in Solution-Processed Inorganic Thin Films for Solar Cell Application.

A common feature of the inorganic thin films including Cu(In,Ga)(S,Se)2 fabricated by nonvacuum solution-based approaches is the doubled-layered structure, with a top dense inorganic film and a bottom carbon-containing residual layer. Although the latter has been considered to be the main efficiency limiting factor, (as a source of high series resistance), the exact influence of this layer is still not clear, and contradictory views are present. In this study, using a CISe as a model system, we report experimental evidence indicating that the carbon residual layer itself is electrically benign to the device performance. Conversely, carbon was found to play a significant role in determining the depth elemental distribution of final film, in which carbon selectively hinders the diffusion of Cu during selenization, resulting in significantly Cu-deficient top CISe layer while improving the film morphology. This carbon-affected compositional and morphological impact on the top CISe films is a determining factor for the device efficiency, which was supported by the finding that CISe solar cells processed from the precursor film containing intermediate amount of carbon demonstrated high efficiencies of up to 9.15% whereas the performances of the devices prepared from the precursor films with very high and very low carbon were notably poor.

Amorphous Cu-In-S nanoparticles as precursors for CuInSe2 thin-film solar cells with a high efficiency.

CuInSe2 (CISe) absorber layers for thin-film solar cells were fabricated through the selenization of amorphous Cu-In-S nanoparticles, which were prepared by using a low-temperature colloidal process within one minute without any external heating. Two strategies for obtaining highly dense CISe absorber films were used in this work; the first was the modification of nanoparticle surface through chelate complexation with ethanolamine, and the second strategy utilized the lattice expansion that occurred when S atoms in the precursor particles were replaced with Se during selenization. The synergy of these two strategies allowed formation of highly dense CISe thin films, and devices fabricated using the absorber layer demonstrated efficiencies of up to 7.94% under AM 1.5G illumination without an anti-reflection coating.

Mechanism and nanosize products of the sol-gel reaction using diphenylsilanediol and 3-methacryloxypropyltrimethoxysilane as precursors.

We use a first-principles calculation and small-angle neutron scattering (SANS) to investigate the mechanism and the nanosize products of the sol-gel reaction with diphenylsilanediol (DPD) and 3-methacryloxypropyltrimethoxysilane (MEMO) precursors in synthesizing a hybrid waveguide material. It is predicted that switching between a DPD hydroxyl and a MEMO methoxy with a reaction rate of 6.8 x 10(-6) s(-1) at 300 K is the fastest process for the first reaction step, thus generating diphenylmethoxysilanol (DPM) and 3-methacryloxypropyldimethoxysilanol (MEDO) as products. However, we determine that this reaction pathway could be modified by the presence of the H2O released from a catalyst such as Ba(OH)2.H2O. Next, switching between the DPM hydroxyl and the MEDO methoxy is followed to generate diphenyldimethoxysilane (DPDM) and 3-methacryloxypropylmethoxysilanediol (MEMDO). However, condensation between a MEMDO hydroxyl and a DPDM methoxy is found to be most favorable for the third reaction step, which generates the DPDM-MEMDO dimer and CH3OH molecule as products. In a similar fashion, a DPDM methoxy of the DPDM-MEMDO dimer can condense with a MEMDO hydroxyl of the second DPDM-MEMDO dimer to increase the chain, but its reaction rate of 2.8 x 10(-11) s(-1) is predicted to be about 5 times smaller than that between a DPDM methoxy and a MEMDO hydroxyl. This implies that the reaction rate for the larger nanostructures becomes smaller. Additionally, our SANS measurements determine that the final products from our sol-gel reaction are on the nanometer scale, at sizes from 1.76 to 2.36 nm.