Silicon nitride/silicon oxide interlayers for solar cell passivating contacts based on PECVD amorphous silicon

This Letter demonstrates improved passivating contacts for silicon solar cells consisting of doped silicon films together with tunnelling dielectric layers. An improvement is demonstrated by replacing the commonly used silicon oxide interfacial layer with a silicon nitride/silicon oxide double interfacial layer. The paper describes the optimization of such contacts, including doping of a PECVD intrinsic a‐Si:H film by means of a thermal POCl₃ diffusion process and an exploration of the effect of the refractive index of the SiN_x. The n⁺ silicon passivating contact with SiN_x /SiO_x double layer achieves a better result than a single SiN_x or SiO_x layer, giving a recombination current parameter of ～7 fA/cm² and a contact resistivity of ～0.005 Ω cm², respectively. These self‐passivating electron‐selective contacts open the way to high efficiency silicon solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Improvement of photoluminescence and electrical properties of porous silicon layer treated with lanthanum

The influence of surface treatment of porous silicon (PS) in lanthanum (La) containing solution during different times on its photoluminescence and electrical properties has been investigated. For this purpose, chemical composition, structural, vibrational, photoluminescence and electrical characteristics of the porous silicon layer with and without lanthanum were examined using X-ray diffractometry (XRD), energy dispersive X-ray (EDX) spectroscopy, Fourier transmission infrared (FTIR) spectroscopy, photoluminescence (PL) spectroscopy and current–voltage (I–V) measurements. The results indicate that porous silicon layers treated with lanthanum exhibit an enhancement of photoluminescence intensity and show an improvement current intensity compared to untreated porous silicon layer.     

Activation of Al2O3 passivation layers on silicon by microwave annealing

Thin aluminum oxide layers deposited on silicon by thermal atomic layer deposition can be used to reduce the electronic recombination losses by passivating the silicon surfaces. To activate the full passivation ability of such layers, a post-deposition annealing step at moderate temperatures (≈400 ^°C, duration≈30 min) is required. Such an annealing step is commonly done in an oven in air, nitrogen, or forming gas atmosphere. In this work, we investigate the ability to reduce the duration of the annealing step by heating the silicon wafer with a microwave source. The annealing time is significantly reduced to durations below 1 min while achieving effective minority carrier lifetimes similar or higher to that of conventionally oven-annealed samples.     

The origin for tubular growth of TiO2 nanotubes: A fluoride rich layer between tube-walls

High resolution Scanning Auger Electron Spectroscopy (AES) is used to demonstrate the compositional variation across self-organized TiO₂ nanotube layers grown in fluoride containing ethylene glycol electrolytes. The analysis results show a distinct fluoride rich layer in between the TiO₂ nanotubes and particularly in the triple points of the hexagonally ordered nanotubular arrays. AES analysis further revealed that extended e-beam exposure leads to a decrease in the fluoride signal (electron beam induced decomposition of fluoride species). The proof of the existence of a fluoride rich layer located between the tube walls strongly supports fluoride dissolution as the reason for a transition from a porous to a tubular morphology.     

Heteroepitaxial GaN films on silicon substrates with porous buffer layers

New complex buffer layers based on a porous material have been developed for epitaxial growth of GaN films on Si substrates. The characteristics of gallium nitride heteroepitaxial layers grown on silicon substrates with new buffer layers by metal-organic vapor phase epitaxy are investigated. It is shown that the porous buffer layers improve the electric homogeneity and increase the photoluminescence intensity of epitaxial GaN films on Si substrates to the values comparable with those for reference GaN films on Al₂O₃ substrates. It is found that a fianite layer in a complex buffer is a barrier for silicon diffusion from the substrate into a GaN film.     

Surface characterization of porous silicon after pore opening processes inducing chemical modifications

In this paper, we present a study on the porous silicon surface with the aim of filling porous silicon layers with organics. We discuss on two processes used to remove the outer parasitic layer created during the porous silicon formation. We demonstrate that these etching processes influences the surface properties, in particular wetting ability. By XPS and infrared absorption spectroscopy studies, we show that a SF₆ plasma treatment does not modify irreversibly the chemistry of porous silicon surface, nor the surface morphology. We also point out that NaOH etching does bring significant morphological modifications and influences the hydrophilicity of the porous silicon surface. This last treatment increases the polar groups (SiO) concentration on the pore surface and therefore allows a better filling of a porous silicon layer with organics, like dibromo-EDOT which can be thermally converted into PEDOT.     

Characterization of thermal, optical and carrier transport properties of porous silicon using the photoacoustic technique

In this work, the porous silicon layer was prepared by the electrochemical anodization etching process on n-type and p-type silicon wafers. The formation of the porous layer has been identified by photoluminescence and SEM measurements. The optical absorption, energy gap, carrier transport and thermal properties of n-type and p-type porous silicon layers were investigated by analyzing the experimental data from photoacoustic measurements. The values of thermal diffusivity, energy gap and carrier transport properties have been found to be porosity-dependent. The energy band gap of n-type and p-type porous silicon layers was higher than the energy band gap obtained for silicon substrate (1.11 eV). In the range of porosity (50-76%) of the studies, our results found that the optical band-gap energy of p-type porous silicon (1.80-2.00 eV) was higher than that of the n-type porous silicon layer (1.70-1.86 eV). The thermal diffusivity value of the n-type porous layer was found to be higher than that of the p-type and both were observed to increase linearly with increasing layer porosity.     

The p recombination layer in tunnel junctions for micromorph tandem solar cells

A new tunnel recombination junction is fabricated for n–i–p type micromorph tandem solar cells. We insert a thin heavily doped hydrogenated amorphous silicon (a-Si:H) p + recombination layer between the n a-Si:H and the p hydrogenated nanocrystalline silicon (nc-Si:H) layers to improve the performance of the n–i–p tandem solar cells. The effects of the boron doping gas ratio and the deposition time of the p-a-Si:H recombination layer on the tunnel recombination junctions have been investigated. The current-voltage characteristic of the tunnel recombination junction shows a nearly ohmic characteristic, and the resistance of the tunnel recombination junction can be as low as 1.5 ·cm 2 by using the optimized p-a-Si:H recombination layer. We obtain tandem solar cells with open circuit voltage V oc = 1.4 V, which is nearly the sum of the V oc s of the two corresponding single cells, indicating no V oc losses at the tunnel recombination junction.     

Investigation of Porous Silicon Wetting by Raman Scattering

Wetting phenomena in porous silicon layers are experimentally investigated by Raman scattering. The experimental results show a reversible blue-shift of Raman spectra of wetted porous silicon layers with respect to the unperturbed layers. We ascribe the shift to a compressive stress due to the increased lattice mismatch between the porous silicon layer and the bulk silicon substrate in wetting conditions.     

Efficient luminescence from porous silicon

Photoluminescence measurements are carried out on porous silicon layers. We show the enhancement and stabilization of the luminescence when depositing a silicon nitride layer on top of porous layers.We also demonstrate that direct- and remote-plasma nitridation are good ways to reduce the ageing effect of porous silicon layers due to a passivation of dangling bonds.     

Simulation and fabrication study of porous silicon photonic crystal

The present work reports design and fabrication of porous silicon based one-dimensional (1D) photonic crystal. Distributed Bragg reflector (DBR) is a 1D photonic crystal composed of multilayer stack of high and low refractive index layers. Design of porous silicon DBR is a complex one and requires appropriate control in optical parameters of its constituent layers. In order to design DBR, two porous silicon single layer samples were fabricated using current density of 10 and 50 mA/cm². Optical characterization of single layer samples showed series of interference fringes. Reflective interferometric Fourier transform spectroscopy (RIFTS) method was employed to determine optical constants of porous silicon single layers. DBR simulation was carried out based on transfer matrix method. DBR was then fabricated using optical parameters obtained from RIFTS method. Reflection bandwidth of prepared DBR was found to be 216 nm, which is comparable to the simulated value of 203 nm.     

Low-porosity porous silicon nanostructures on monocrystalline silicon solar cells

In this work we present a study of low-porosity porous silicon (PS) nanostructures stain etched on monocrystalline silicon solar cells. The PS layers reduce the reflectance, improve the diffusion of dopants by rapid thermal processes, and increase the homogeneity of the sheet resistance. Some samples were subjected to chemical oxidation in HNO₃ to reduce the porosity of the surface layer. After the diffusion process, deposition of a SiN_x antireflection layer, and screen printing of the samples, an efficiency of 15.5% is obtained for low-porosity PS solar cells, compared with an efficiency of 10.0% for standard PS cells and 14.9% for the reference Cz cells.     

Anodic oxidation of porous silicon bilayers

This paper focuses on the study of the effect of anodic oxidation in porous silicon bilayers composed of two porous layers of different porosities. The order of the two types of layers has been alternated, and the thicknesses and refractive indices have been optically characterized by Fourier transform infrared spectroscopy. The results show that the refractive index of anodic oxidized porous silicon is reduced significantly with respect to just formed porous silicon. It is also observed that the quality of the oxidation is related to the porosity of the inner porous layer of the silicon bilayer structure. This effect is interpreted in terms of quantum size effects.     

Size Control of Porous Silicon Nanoparticles by Electrochemical Perforation Etching

Size‐controlled porous silicon‐based nanoparticles are prepared by pulsed electrochemical etching of single crystal silicon wafers, followed by ultrasonic fracture of the freestanding porous layer. When high‐current density pulses are applied periodically during the porous layer etching process, a porous multilayer results in which porous layers are separated by thin layers of much higher porosity. Ultrasonic fracture selectively cleaves the porous film along these high‐porosity perforations, providing greater size control and improved yields (by 5x) of the resulting porous nanoparticles. The effect of pulse width and repetition rate is systematically studied: tunability of the average nanoparticle size in the range 160–350 nm is demonstrated.     

Solar cells with porous silicon: modification of surface-recombination velocity

Laser-induced transient-grating measurements were performed to monitor the influence of porous silicon on the surface recombination of a highly doped n⁺-silicon emitter of solar cells. With this technique, photocarrier diffusion and recombination with a time resolution of some tens of picoseconds can be studied. Using pulses of the second- and third-harmonic radiation from an Nd³⁺:YAG laser (quantum energy 2.34 and 3.51 eV, respectively), two different-depth regions of the emitter were excited. Using a kinetic model, which includes carrier diffusion and recombination at the surface and in the bulk of the emitter, surface-recombination velocities in a series of samples typical for each successive operation of solar-cell technology with different surface-doping level and surface preparation were evaluated. From the analysis, we conclude that porous silicon formed on the emitter passivates the surface of the silicon layer, i.e. reduces the rate of surface recombination at the porous silicon–crystalline silicon interface. Ytterbium as a co-dopant of the emitter increases the surface-recombination velocity. Received: 26 June 2000 / Accepted: 4 December 2000 / Published online: 26 April 2001     

Properties of erbium silicate doped with chromium in porous silicon

The possible formation of chromium-doped erbium silicate Er₂SiO₅: Cr in thin layers of porous silicon is demonstrated. This paper reports on studies of the photoluminescence, electron paramagnetic resonance, and transverse current transport in porous silicon layers (with different chromium and erbium contents) grown on n-and p-silicon single crystals heavily doped with shallow impurities. The Er₂SiO₅: Cr phase with the photoluminescence maxima at approximately 1.3 and 1.5 μm manifests itself after high-temperature annealing at 1000°C. The introduction of erbium and annealing at 700°C increase the intensity of the red photoluminescence of porous silicon by several factors. The decrease in the electrical conductivity of porous silicon suggests the onset of the formation of erbium silicate. The current-voltage characteristics exhibit a nonlinear behavior with an exponential dependence of the current on the voltage due to the discrete electron tunneling. An electron paramagnetic resonance spectrum of P _b centers in p-type heavily doped silicon is observed for the first time.     

Study of birefringence in porous silicon layers by IR Fourier spectroscopy

Birefringence in porous silicon layers prepared with different etching currents on a (110) substrate is studied by IR Fourier spectroscopy. The spectra exhibit beats in the intensity of transmitted and reflected radiation due to the summation of the intensities of the ordinary and extraordinary waves interfering in the porous layer. An analysis of the spectra shows the layers to exhibit properties of a negative uniaxial crystal with the optical axis lying in the layer plane. The difference between the refractive indices of the ordinary and extraordinary waves for a layer with a porosity of 80% reaches 18%. The experimental data are in agreement with the calculations based on the effective-medium approximation, which takes into account the anisotropy of silicon nanocrystal arrangement in a porous layer.     

Lanthanum,samarium, and dysprosium fluoride antireflection coatings for silicon photoelectric devices

An investigation was made of the wavelength dependences of light transmission through rare-earth fluoride films and of the effect of using these materials to produce antireflection surface coatings on silicon photoelectric converters. It was established that films of lanthanum, samarium, and dysprosium fluorides are highly transparent in the wavelength range 400–1100 nm and enable the optical reflection coefficient of a silicon surface to be reduced to 3.3–4.0%. It was shown that antireflection layers of these rare-earth fluorides increased the wavelength-resolved value of the short-circuit photoelectric current and the efficiency of a silicon photoelectric converter by more than 43%.State University, Samara. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 7–10, April, 1994.     

Electrochemical and hydrothermal deposition of ZnO on silicon: from continuous films to nanocrystals

This article presents the study of the electrochemical deposition of zinc oxide from the non-aqueous solution based on dimethyl sulfoxide and zinc chloride into the porous silicon matrix. The features of the deposition process depending on the thickness of the porous silicon layer are presented. It is shown that after deposition process the porous silicon matrix is filled with zinc oxide nanocrystals with a diameter of 10–50 nm. The electrochemically deposited zinc oxide layers on top of porous silicon are shown to have a crystalline structure. It is also shown that zinc oxide crystals formed by hydrothermal method on the surface of electrochemically deposited zinc oxide film demonstrate ultra-violet luminescence. The effect of the porous silicon layer thickness on the morphology of the zinc oxide is shown. The structures obtained demonstrated two luminescence bands peaking at the 375 and 600 nm wavelengths. Possible applications of ZnO nanostructures, porous and continuous polycrystalline ZnO films such as gas sensors, light-emitting diodes, photovoltaic devices, and nanopiezo energy generators are considered. Aspects of integration with conventional silicon technology are also discussed.     

X-ray luminescence of disperse SiO2 and porous silicon

We carry out a comparison between the luminescence spectra (photo-and x-ray luminescence) of porous silicon and disperse SiO₂, which by its physical characteristics is most similar to oxide films on porous silicon. The photoluminescence of porous silicon was also investigated using fluorescence (excitation by a nitrogen laser) and metallographic microscopes. We found that the natures of the luminescence centers of porous silicon and disperse SiO₂ are identical. A porous layer on single-crystal silicon ensures the creation of a highly branched surface of oxide film. Luminescence centers are located on its inner (as viewed from the porous silicon) surface. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 2, pp. 247–251, March–April, 1998.