E. García-Hemme

Development of a Selective Chemical Etch To Improve the Conversion Efficiency of Zn-Rich Cu2ZnSnS4 Solar Cells

Improvement of the efficiency of Cu(2)ZnSnS(4) (CZTS)-based solar cells requires the development of specific procedures to remove or avoid the formation of detrimental secondary phases. The presence of these phases is favored by the Zn-rich and Cu-poor conditions that are required to obtain device-grade layers. We have developed a selective chemical etching process based on the use of hydrochloric acid solutions to remove Zn-rich secondary phases from the CZTS film surface, which are partly responsible for the deterioration of the series resistance of the cells and, as a consequence, the conversion efficiency. Using this approach, we have obtained CZTS-based devices with 5.2% efficiency, which is nearly twice that of the devices we have prepared without this etching process.

Sub-bandgap spectral photo-response analysis of Ti supersaturated Si

We have analyzed the increase of the sheet conductance (ΔG□) under spectral illumination in high dose Ti implanted Si samples subsequently processed by pulsed-laser melting. Samples with Ti concentration clearly above the insulator-metal transition limit show a remarkably high ΔG□, even higher than that measured in a silicon reference sample. This increase in the ΔG□ magnitude is contrary to the classic understanding of recombination centers action and supports the lifetime recovery predicted for concentrations of deep levels above the insulator-metal transition.

Experimental verification of intermediate band formation on titanium-implanted silicon

Intermediate band formation on silicon layers for solar cell applications was achieved by titanium implantation and laser annealing. A two-layer heterogeneous system, formed by the implanted layer and by the un-implanted substrate, was formed. In this work, we present for the first time electrical characterization results which show that recombination is suppressed when the Ti concentration is high enough to overcome the Mott limit, in agreement with the intermediate band theory. Clear differences have been observed between samples implanted with doses under or over the Mott limit. Samples implanted under the Mott limit have capacitance values much lower than the un-implanted ones as corresponds to a highly doped semiconductor Schottky junction. However, when the Mott limit is surpassed, the samples have much higher capacitance, revealing that the intermediate band is formed. The capacitance increasing is due to the big amount of charge trapped at the intermediate band, even at low temperatures. Ti deep levels have been measured by admittance spectroscopy. These deep levels are located at energies which vary from 0.20 to 0.28 eV below the conduction band for implantation doses in the range 10(13)-10(14) at./cm(2). For doses over the Mott limit, the implanted atoms become nonrecombinant. Capacitance voltage transient technique measurements prove that the fabricated devices consist of two-layers, in which the implanted layer and the substrate behave as an n(+)/n junction.

Far infrared photoconductivity in a silicon based material: Vanadium supersaturated silicon

We have analyzed the spectral sub-bandgap photoresponse of silicon (Si) samples implanted with vanadium (V) at different doses and subsequently processed by pulsed-laser melting. Samples with V concentration clearly above the insulator-metal transition limit show an important increase of the photoresponse with respect to a Si reference sample. Their photoresponse extends into the far infrared region and presents a sharp photoconductivity edge that moves towards lower photon energies as the temperature decreases. The increase of the value of the photoresponse is contrary to the classic understanding of recombination centers action and supports the predictions of the insulator-metal transition theory.

Room-temperature operation of a titanium supersaturated silicon-based infrared photodetector

We report room-temperature operation of 1 × 1 cm2 infrared photoconductive photodetectors based on silicon supersaturated with titanium. We have fabricated these Si-based infrared photodetectors devices by means of ion implantation followed by a pulsed laser melting process. A high sub-band gap responsivity of 34 mV W−1 has been obtained operating at the useful telecommunication applications wavelength of 1.55 μm (0.8 eV). The sub-band gap responsivity shows a cut-off frequency as high as 1.9 kHz. These Si-based devices exhibit a non-previous reported specific detectivity of 1.7 × 104 cm Hz1/2 W−1 at 660 Hz, under a 1.55 μm wavelength light. This work shows the potential of Ti supersaturated Si as a fully CMOS-compatible material for the infrared photodetection technology.

UV and visible Raman scattering of ultraheavily Ti implanted Si layers for intermediate band formation

We assess the degree of crystallinity by means of UV and visible Raman scattering measurements of Ti implanted Si layers with very high doses (1015–5 × 1016 cm−2) subsequently annealed by nanosecond pulsed laser melting (PLM). We obtain ultraheavily impurified Si layers with Ti concentrations six orders of magnitude above the solid solubility limit in a layer several tens of nanometers thick. The PLM annealing processes are needed to recover the crystal quality and to keep the high Ti concentration required to form an intermediate band (IB). The UV Raman analysis permits us to evaluate the lattice crystallinity of the different implanted doses probing only the implanted region and points out Ti interstitial location in the host lattice in agreement with theoretical predictions for IB formation. By contrast, visible Raman spectra are only sensitive to the presence of a fully amorphized implanted layer as in the rest of the crystalline layers the probing depth far exceeds the implanted layer thickness and the signal is dominated by the undamaged Si.

Electrical decoupling effect on intermediate band Ti-implanted silicon layers

We investigated the electrical transport properties of ultraheavily Ti-implanted silicon layers subsequently pulsed laser melted (PLM). After PLM, the samples exhibit anomalous electrical behaviour in sheet resistance and Hall mobility measurements, which is associated with the formation of an intermediate band (IB) in the implanted layer. An analytical model that assumes IB formation and a current limitation effect between the implanted layer and the substrate was developed to analyse this anomalous behaviour. This model also describes the behaviour of the function V/Delta V and the electrical function F that can be extracted from the electrical measurements in the bilayer. After chemical etching of the implanted layer, the anomalous electrical behaviour observed in sheet resistance and Hall mobility measurements vanishes, recovering the unimplanted Si behaviour, in agreement with the analytical model. The behaviour of V/Delta V and the electrical function F can also be successfully described in terms of the analytical model in the bilayer structure with the implanted layer entirely stripped.

Ruling out the impact of defects on the below band gap photoconductivity of Ti supersaturated Si

In this study, we present a structural and optoelectronic characterization of high dose Ti implanted Si subsequently pulsed-laser melted (Ti supersaturated Si). Time-of-flight secondary ion mass spectrometry analysis reveals that the theoretical Mott limit has been surpassed after the laser process and transmission electron microscopy images show a good lattice reconstruction. Optical characterization shows strong sub-band gap absorption related to the high Ti concentration. Photoconductivity measurements show that Ti supersaturated Si presents spectral response orders of magnitude higher than unimplanted Si at energies below the band gap. We conclude that the observed below band gap photoconductivity cannot be attributed to structural defects produced by the fabrication processes and suggest that both absorption coefficient of the new material and lifetime of photoexcited carriers have been enhanced due to the presence of a high Ti concentration. This remarkable result proves that Ti supersaturated Si is a promising material for both infrared detectors and high efficiency photovoltaic devices.

Energy levels distribution in supersaturated silicon with titanium for photovoltaic applications

In the attempt to form an intermediate band in the bandgap of silicon substrates to give it the capability to absorb infrared radiation, we studied the deep levels in supersaturated silicon with titanium. The technique used to characterize the energy levels was the thermal admittance spectroscopy. Our experimental results showed that in samples with titanium concentration just under Mott limit there was a relationship among the activation energy value and the capture cross section value. This relationship obeys to the well known Meyer-Neldel rule, which typically appears in processes involving multiple excitations, like carrier capture/emission in deep levels, and it is generally observed in disordered systems. The obtained characteristic Meyer-Neldel parameters were Tmn = 176 K and kTmn = 15 meV. The energy value could be associated to the typical energy of the phonons in the substrate. The almost perfect adjust of all experimental data to the same straight line provides further evidence of the validity of the Meyer Neldel rule, and may contribute to obtain a deeper insight on the ultimate meaning of this phenomenon.

Meyer Neldel rule application to silicon supersaturated with transition metals

This paper presents the results for the transverse conductance across a bilayer formed by supersaturating with diverse transition metals a thin layer of a silicon wafer. The layer is formed by ion implantation and annealed by pulsed laser melting. The transverse conductance is exponentially activated, obtaining values ranging from 0.018 to 0.7 eV for the activation energy and pre-exponential factors of 10^-2-10^12 S depending on the annealing energy density. A semi-logarithmic plot of the pre-exponential factor versus activation energy shows an almost perfect linear behavior as stated by the Meyer Neldel rule. The Meyer Neldel energy obtained for implantation with different transition metals and also annealed in different conditions is 22meV, which is within the range of silicon phonons, thus confirming the hypothesis of the Multi Excitation Entropy theory.