Marie Buffière

Highly Ordered Hollow Oxide Nanostructures: The Kirkendall Effect at the Nanoscale

Highly ordered ultra-long oxide nanotubes are fabricated by a simple two-step strategy involving the growth of copper nanowires on nanopatterned template substrates by magnetron sputtering, followed by thermal annealing in air. The formation of such tubular nanostructures is explained according to the nanoscale Kirkendall effect. The concept of this new fabrication route is also extendable to create periodic zero-dimensional hollow nanostructures.

Electron Beam Nanosculpting of Kirkendall Oxide Nanochannels

The nanomanipulation of metal nanoparticles inside oxide nanotubes, synthesized by means of the Kirkendall effect, is demonstrated. In this strategy, a focused electron beam, extracted from a transmission electron microscope source, is used to site-selectively heat the oxide material in order to generate and steer a metal ion diffusion flux inside the nanochannels. The metal ion flux generated inside the tube is a consequence of the reduction of the oxide phase occurring upon exposure to the e-beam. We further show that the directional migration of the metal ions inside the nanotubes can be achieved by locally tuning the chemistry and the morphology of the channel at the nanoscale. This allows sculpting organized metal nanoparticles inside the nanotubes with various sizes, shapes, and periodicities. This nanomanipulation technique is very promising since it enables creating unique nanostructures that, at present, cannot be produced by an alternative classical synthesis route.

Spectral current-voltage analysis of kesterite solar cells

Current–voltage analysis using different optical band pass filters has been performed on Cu2ZnSnSe4 and Cu2ZnSn(S,Se)4 thin-film solar cells. When using red or orange light (i.e. wavelengths above 600 nm), a distortion appears in the I–V curve of the Cu2ZnSnSe4 solar cell, indicating an additional potential barrier to the current flow in the device for these conditions of illumination. This barrier is reduced when using a Cu2ZnSn(S,Se)4 absorber. Numerical simulations demonstrate that the barrier visible under red light could be explained by a positive conduction band offset at the front interface coupled with compensating defects in the buffer layer.

Study of alternative back contacts for thin film Cu2ZnSnSe4-based solar cells

Cu2ZnSnSe4 thin film solar cells are usually fabricated on a soda lime glass substrate with a molybdenum (Mo) back contact. It is suspected that degradation in electrical performance occurs due to the formation of a barrier between the absorber and Mo back contact. To overcome such degradation, Titanium Nitride (TiN), Titanium Tungsten (TiW), Chromium (Cr), Titanium (Ti) and Aluminum (Al) deposited on Mo-coated glass substrates are investigated as alternative back contact materials. Physical and electrical characterization as well as photoluminescence measurements are performed. Compositional analysis of the absorber layer on the metallized substrates identifies Mo, TiN and TiW as being the most inert during the formation of Cu2ZnSnSe4. On the other hand, Ti and Cr reacted with Se during selenization, thereby affecting the growth of the absorber, leading to low conversion efficiency. For Al, the absorber layer was etched after the standard potassium cyanide etch, hence, cannot be used as a back contact. The best device efficiencies obtained are 8.8% on TiN, 7.5% on Mo and 5.9% on TiW, respectively. The TiN back contact provides the lowest barrier value of about 15 meV which could be considered as a good ohmic contact.

KCN Chemical Etch for Interface Engineering in Cu2ZnSnSe4 Solar Cells

The removal of secondary phases from the surface of the kesterite crystals is one of the major challenges to improve the performances of Cu2ZnSn(S,Se)4 (CZTSSe) thin film solar cells. In this contribution, the KCN/KOH chemical etching approach, originally developed for the removal of CuxSe phases in Cu(In,Ga)(S,Se)2 thin films, is applied to CZTSe absorbers exhibiting various chemical compositions. Two distinct electrical behaviors were observed on CZTSe/CdS solar cells after treatment: (i) the improvement of the fill factor (FF) after 30 s of etching for the CZTSe absorbers showing initially a distortion of the electrical characteristic; (ii) the progressive degradation of the FF after long treatment time for all Cu-poor CZTSe solar cell samples. The first effect can be attributed to the action of KCN on the absorber, that is found to clean the absorber free surface from most of the secondary phases surrounding the kesterite grains (e.g., Se0, CuxSe, SnSex, SnO2, Cu2SnSe3 phases, excepting the ZnSe-based phases). The second observation was identified as a consequence of the preferential etching of Se, Sn, and Zn from the CZTSe surface by the KOH solution, combined with the modification of the alkali content of the absorber. The formation of a Cu-rich shell at the absorber/buffer layer interface, leading to the increase of the recombination rate at the interface, and the increase in the doping of the absorber layer after etching are found to be at the origin of the deterioration of the FF of the solar cells.

Microstructural analysis of 9.7% efficient Cu2ZnSnSe4 thin film solar cells

This work presents a detailed analysis of the microstructure and the composition of our record Cu2ZnSnSe4 (CZTSe)-CdS-ZnO solar cell with a total area efficiency of 9.7%. The average composition of the CZTSe crystallites is Cu1.94Zn1.12Sn0.95Se3.99. Large crystals of ZnSe secondary phase (up to 400 nm diameter) are observed at the voids between the absorber and the back contact, while smaller ZnSe domains are segregated at the grain boundaries and close to the surface of the CZTSe grains. An underlying layer and some particles of CuxSe are observed at the Mo-MoSe2-Cu2ZnSnSe4 interface. The free surface of the voids at the back interface is covered by an amorphous layer containing Cu, S, O, and C, while the presence of Cd, Na, and K is also observed in this region.

Investigation of Properties Limiting Efficiency in Cu 2 ZnSnSe 4 -Based Solar Cells

We have investigated different nonidealities in Cu2ZnSnSe4-CdS-ZnO solar cells with 9.7% conversion efficiency, in order to determine what is limiting the efficiency of these devices. Several nonidealities could be observed. A barrier of about 300 meV is present for electron flow at the absorber-buffer heterojunction leading to a strong crossover behavior between dark and illuminated current-voltage curves. In addition, a barrier of about 130 meV is present at the Mo-absorber contact, which could be reduced to 15 meV by inclusion of a TiN interlayer. Admittance spectroscopy results on the devices with the TiN backside contact show a defect level with an activation energy of 170 meV. Using all parameters extracted by the different characterization methods for simulations of the two-diode model including injection and recombination currents, we come to the conclusion that our devices are limited by the large recombination current in the depletion region. Potential fluctuations are present in the devices as well, but they do not seem to have a special degrading effect on the devices, besides a probable reduction in minority carrier lifetime through enhanced recombination through the band tail defects.

Growth control, structure, chemical state, and photoresponse of CuO-CdS core-shell heterostructure nanowires

The growth of single-crystal CuO nanowires by thermal annealing of copper thin films in air is studied. We show that the density, length, and diameter of the nanowires can be controlled by tuning the morphology and structure of the copper thin films deposited by DC magnetron sputtering. After identifying the optimal conditions for the growth of CuO nanowires, chemical bath deposition is employed to coat the CuO nanowires with CdS in order to form p-n nanojunction arrays. As revealed by high-resolution TEM analysis, the thickness of the polycrystalline CdS shell increases when decreasing the diameter of the CuO core for a given time of CdS deposition. Near-edge x-ray absorption fine-structure spectroscopy combined with transmission x-ray microscopy allows the chemical analysis of isolated nanowires. The absence of modification in the spectra at the Cu L and O K edges after the deposition of CdS on the CuO nanowires indicates that neither Cd nor S diffuse into the CuO phase. We further demonstrate that the core-shell nanowires exhibit the I-V characteristic of a resistor instead of a diode. The electrical behavior of the device was found to be photosensitive, since increasing the incident light intensity induces an increase in the collected electrical current.

Controlling the Formation of Nanocavities in Kirkendall Nanoobjects through Sequential Thermal Ex Situ Oxidation and In Situ Reduction Reactions

Controlling the porosity, the shape, and the morphology of Kirkendall hollow nanostructures is the key factor to tune the properties of these tailor-made nanomaterials which allow in turn broadening their applications. It is shown that by applying a continuous oxidation to copper nanowires following a temperature ramp protocol, one can synthesize cuprous oxide nanotubes containing periodic copper nanoparticles. A further oxidation of such nanoobjects allows obtaining cupric oxide nanotubes with a bamboo-like structure. On the other hand, by applying a sequential oxidation and reduction reactions to copper nanowires, one can synthesize hollow nanoobjects with complex shapes and morphologies that cannot be obtained using the Kirkendall effect alone, such as necklace-like cuprous oxide nanotubes, periodic solid copper nanoparticles or hollow cuprous oxide nanospheres interconnected with single crystal cuprous oxide nanorods, and aligned and periodic hollow nanospheres embedded in a cuprous oxide nanotube. The strategy demonstrated in this study opens new avenues for the engineering of hollow nanostructures with potential applications in gas sensing, catalysis, and energy storage.

Development of co-evaporated In2S3 buffer layer for Cu2ZnSnSe4 thin film solar cells

In this work, we focus on the replacement of the commonly used but toxic Cd-based buffer layer by In₂S₃ thin films deposited by co-evaporation for application in Cu₂ZnSnSe₄ (CZTSe) solar cells. The impact of the deposition conditions of the buffer layer on the electrical behavior of CZTSe/In₂S₃ devices is first investigated. The best solar cell efficiencies were obtained for relatively thick In₂S₃ buffer layers (~100 nm) deposited at low temperature (<;100 °C). It is also observed that low [Cu]/([Zn]+[Sn]) ratio (CZT~0.75) in the kesterite absorber leads to high efficiency for In-based buffered CZTSe solar cells, while the effect of the CZT ratio on CZTSe/CdS solar cell performances is not so clear. A conversion efficiency of 5.7 % on CZTSe/In₂S₃ thin film solar cell is achieved.