Wet-chemical passivation of atomically flat and structured silicon substrates for solar cell application

Special sequences of wet-chemical oxidation and etching steps were optimised with respect to the etching behaviour of differently oriented silicon to prepare very smooth silicon interfaces with excellent electronic properties on mono- and poly-crystalline substrates. Surface photovoltage (SPV) and photoluminescence (PL) measurements, atomic force microscopy (AFM) and scanning electron microscopy (SEM) investigations were utilised to develop wet-chemical smoothing procedures for atomically flat and structured surfaces, respectively. Hydrogen-termination as well as passivation by wet-chemical oxides were used to inhibit surface contamination and native oxidation during the technological processing. Compared to conventional pre-treatments, significantly lower micro-roughness and densities of surface states were achieved on mono-crystalline Si(100), on evenly distributed atomic steps, such as on vicinal Si(111), on silicon wafers with randomly distributed upside pyramids, and on poly-crystalline EFG (Edge-defined Film-fed-Growth) silicon substrates.The recombination loss at a-Si:H/c-Si interfaces prepared on c-Si substrates with randomly distributed upside pyramids was markedly reduced by an optimised wet-chemical smoothing procedure, as determined by PL measurements. For amorphous-crystalline hetero-junction solar cells (ZnO/a-Si:H(n)/c-Si(p)/Al) with textured c-Si substrates the smoothening procedure results in a significant increase of short circuit current I_sc, fill factor and efficiency η. The scatter in the cell parameters for measurements on different cells is much narrower, as compared to conventional pre-treatments, indicating more well-defined and reproducible surface conditions prior to a-Si:H emitter deposition and/or a higher stability of the c-Si surface against variations in the a-Si:H deposition conditions.     

Formation of biaxial texture in metal films by selective ion beam etching

The formation of in-plane texture via ion bombardment of uniaxially textured metal films was investigated. In particular, selective grain Ar ion beam etching of uniaxially textured (0 0 1) Ni was used to achieve in-plane aligned Ni grains. Unlike conventional ion beam assisted deposition, the ion beam irradiates the uniaxially textured film surface with no impinging deposition flux. The initial uniaxial texture is established via surface energy minimization with no ion irradiation. Within this sequential texturing method, in-plane grain alignment is driven by selective etching and grain overgrowth. Biaxial texture was achieved for ion beam irradiation at elevated temperature.     

Effect of temperature and silicon resistivity on the elaboration of silicon nanowires by electroless etching

The morphology of silicon nanowire (SiNW) layers formed by Ag-assisted electroless etching in HF/H₂O₂ solution was studied. Prior to the etching, the Ag nanoparticles were deposited on p-type Si(1 0 0) wafers by electroless metal deposition (EMD) in HF/AgNO₃ solution at room temperature. The effect of etching temperature and silicon resistivity on the formation process of nanowires was studied. The secondary ion mass spectra (SIMS) technique is used to study the penetration of silver in the etched layers. The morphology of etched layers was investigated by scanning electron microscope (SEM).     

Peptide-induced patterning of gold nanoparticle thin films

In this work, the use of patterned proteins and peptides for the deposition of gold nanoparticles on several substrates with different surface chemistries is presented. The patterned biomolecule on the surface acts as a catalyst to precipitate gold nanoparticles from a precursor solution of HAuCl₄ onto the substrate. The peptide patterning on the surfaces was accomplished by physical adsorption or covalent attachment. It was shown that by using covalent attachment with a linker molecule, the influence of the surface properties from the different substrates on the biomolecule adsorption and subsequent nanoparticle deposition could be avoided. By adjusting the reaction conditions such as pH or HAuCl₄ concentration, the sizes and morphologies of deposited gold nanoparticle agglomerates could be controlled. Two biomolecules were used for this experiment, 3XFLAG peptide and bovine serum albumin (BSA). A micro-transfer molding technique was used to pattern the peptides on the substrates, in which a pre-patterned poly(dimethylsiloxane) (PDMS) mold was used to deposit a lift-off pattern of polypropylmethacrylate (PPMA) on the various substrates. The proteins were either physically adsorbed or covalently attached to the substrates, and an aqueous HAuCl₄ solution was applied on the substrates with the protein micropatterns, causing the precipitation of gold nanoparticles onto the patterns. SEM, AFM, and Electron Beam Induced Current (EBIC) were used for characterization.     

Influence of the flow,etching time and reactor cleaning method on the etching rate and selectivity of reactive ion etching of SiO2 — Photoresist system

Reactive ion etching (RIE) in a cold plasma of fluoro- and chlorocarbons is one of the most widespread etching methods used in semiconductor industry. The repeatability of etching is influt enced by many factors like the deposition on the electrodes and reactor walls, adsorption of watevapour from air in the case of reactor bleeding, deposition during etching etc. In the presenr work we study the influence of the flow of the etching gas and of the method of reactor cleaning before etching on the etching rate and selectivity in the system SiO₂ —photoresist; the etching gas was trifluorochloromethane (Freon 23, CHF₃) and the etching method was RIE.     

Metal nanorod production in silicon matrix by electroless process

Metal filled Si nanopores, that is, metal nanorods in an Si matrix, are produced by an electroless process that consists of three steps: (1) electroless displacement deposition of metal nanoparticles from a metal salt solution containing HF; (2) Si nanopore formation by metal-particle-enhanced HF etching; and (3) metal filling in nanopores by autocatalytic electroless deposition. Ag nanoparticles produce Si nanopores whose sizes are a few tens of nm in diameter and ca. 50 nm deep. Au nanoparticles produce finer and straighter nanopores on Si than the Ag case. These nanopores are filled with a Co or a Co-Ni alloy by autocatalytic deposition using dimethylamine-borane as a reducing agent. Phosphinate can be used as a reducing agent for the Au-deposited-and-pore-formed Si. The important feature of this process is that the metal nanoparticles, that is, the initiation points of the autocatalytic metal deposition, are present on the bottoms of the Si nanopores.     

Electron‐transfer transparency of graphene: Fast reduction of metal ions on graphene‐covered donor surfaces

The mechanism of charge transfer through nanomaterials such as graphene remains unclear, and the amount of charge that can be transferred from/to graphene without damaging its structural integrity is unknown. In this communication, we show that metallic nanoparticles can be decorated onto graphene surfaces as a result of charge transfer from the supporting substrate to an adjoining solution containing metal ions. Au or Pt nanoparticles were formed with relatively high yield on graphene‐coated substrates that can reduce these metal ions, such as Ge, Si, GaAs, Al, and Cu. However, metal ions were not reduced on graphene surfaces coated onto non‐reducing substrates such as SiO₂ or ZnO. These results confirm that graphene can be doped by exploiting charge transfer from the underlying substrate; thus graphene is not only transparent with respect to visible light, but also with respect to the charge transfer. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Fabrication of nanostructured silicon surface using selective chemical etching

A two-stage process based on selective chemical etching induced by metal nanoclusters is used to fabricate nanostructured surfaces of silicon plates with a relatively low reflectance. At silicon surfaces covered with silver nanoclusters, the SERS effect is observed for rhodamine concentrations of about 10^–12 M. At certain technological parameters, the depth of the nanostructured layer weakly depends on the conditions for the two-stage etching, in particular, etching time. Under otherwise equal conditions for etching, the rate of the formation of textured layer in the p-type silicon is two times greater than the formation rate in the n-type silicon.     

Semiconductor nanostructures enabled by aerosol technology

Aerosol technology provides efficient methods for producing nanoparticles with well-controlled composition and size distribution. This review provides an overview of methods and results obtained by using aerosol technology for producing nanostruetures for a variety of applications in semiconductor physics and device technology. Examples are given from： production of metal and metal alloy particles： semiconductor nanoparticles; semiconductor nanowires, grown both in the aerosol phase and on substrates; physics studies based on individual aerosol-generated devices; and large area deviees based on aerosol particles.     

New method to measure whole-wavelength transmittance of TCO substrates for thin-film silicon solar cells

High transmittance of transparent conductive oxide (TCO) substrates is one of the most important factors for achieving high efficiency in thin-film silicon solar cells. Immersion (IM) method with CH₂I₂ liquid is widely used for the evaluation of optical properties (transmittance, reflectance and absorption) for TCO substrates with textured surface in order to reduce the scattering at the TCO surface. However, in order to measure transmittance accurately, three problems have been found. (1) CH₂I₂ liquid itself absorbs the light in short wavelength region. (2) The transmittance around the absorption edge of CH₂I₂ liquids is very sensitive to its amount. (3) Scattering cannot be suppressed when the scattering surfaces are more than 2 surfaces (for example, TCO on reactive ion etching (RIE) processed glass). To overcome these problems, we proposed a new setup to measure optical properties of TCO substrates by holding the samples inside the integral sphere. As the results, we have confirmed that their absorption in all wavelength could be measured accurately and the transmittance measured by the new method was well consistent with the external quantum efficiency (EQE) of the fabricated cell while the transmittance measured with conventional IM method showed differently. Therefore, this new method could be a useful tool to evaluate TCO substrates for thin-film silicon solar cells.     

Growth and structure of Bi0.5(Na0.7K0.2Li0.1)0.5TiO3 thin films prepared by pulsed laser deposition technique

Bi_0.5(Na_0.7K_0.2Li_0.1)_0.5TiO₃ (BNKLT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition (PLD) technique. The films prepared were examined by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The effects of the processing parameters, such as oxygen pressure, substrate temperature and laser power, on the crystal structure, surface morphology, roughness and deposition rates of the thin films were investigated. It was found that the substrate temperature of 600 °C and oxygen pressure of 30 Pa are the optimized technical parameters for the growth of textured film, and all the thin films prepared have granular structure, homogeneous grain size and smooth surfaces.     

Effect of two-step functionalization of Ti by chemical processes on protein adsorption

Titanium and its alloys are widely used for orthopedic and dental implants because of their superior mechanical properties, low modulus, excellent corrosion resistance and good biocompatibility. However, it takes several months for titanium implants and bone tissue to reach integration. Hence, there is growing interest in shortening the process of osseointegration and thereby reducing surgical restrictions. Various surface modifications have been applied to form a bioactive titanium oxide layer on the metal surface, which is known to accelerate osseointegration.The present work shows that titanium dioxide (TiO₂) layers formed on titanium substrates by etching in a solution of sodium hydroxide (NaOH) or hydrogen peroxide/phosphoric acid (H₃PO₄/H₂O₂, with a volume ratio of 1:1) are highly suitable pre-treatments for apatite-like coating deposition. Using a two-step procedure (etching in an alkaline or acidic solution followed by soaking in Hanks’ medium), biomimetic calcium phosphate coatings were deposited on porous TiO₂ layers. The combined effects of surface topography and chemistry on the formation of the calcium phosphate layer are presented. The topography of the TiO₂ layers was characterized using HR-SEM and AFM techniques. The nucleation and growth of calcium phosphate (Ca-P) coatings deposited on TiO₂ porous layers from Hanks’ solution was investigated using HR-SEM microscopy. AES, XPS and FTIR surface analytical techniques were used to characterize the titanium dioxide layers before and after deposition of the calcium phosphate coatings, as well as after the process of protein adsorption. To evaluate the potential use of such materials for biomedical applications, the adsorption of serum albumin, the most abundant protein in the blood, was studied on such surfaces.     

Wet-chemical treatment and electronic interface properties of silicon solar cell substrates

On textured n-type silicon substrates for solar cell manufacturing, the relation between light trapping behavior, structural imperfections, energetic distribution of interface state densities and interface recombination losses were investigated by applying surface sensitive techniques. The field-modulated surface photovoltage (SPV), in-situ photoluminescence (PL) measurements, total hemispherical UV-NIR-reflectance measurements and electron microscopy (SEM) were employed to yield detailed information on the influence of wet-chemical treatments on preparation induced micro-roughness and electronic properties of polished and textured silicon substrates. It was shown that isotropic as well as anisotropic etching of light trapping structures result in high surface micro-roughness and density of interface states. Removing damaged surface layers in the nm range by wet-chemical treatments, the density of these states and the related interface recombination loss can be reduced. In-situ PL measurements were applied to optimise HF-treatment times aimed at undamaged, oxide-free and hydrogen-terminated substrate surfaces as starting material for subsequent solar cell preparations.      

The Epilift technique for Si solar cells

We present an overview of the Epilift technique, which allows the fabrication of single-crystal silicon films, suitable for photovoltaic purposes. Epitaxial layers are grown by liquid phase epitaxy on partially masked, single-crystal silicon substrates. The layers are detached from the substrate by selective chemical or electrochemical etching, allowing the substrate to be re-used. Epilayers grown on (100) substrates display highly textured surfaces as well as narrow overgrowth widths of the epitaxial layer over the oxide, making them particularly suitable for photovoltaic devices. Received: 1 March 1999 / Accepted: 28 March 1999 / Published online: 1 July 1999     

Nanofabricated periodic arrays of silver elliptical discs as SERS substrates

Signal enhancement observed in surface‐enhanced Raman spectroscopy (SERS) is attributable to the presence of noble‐metal nanostructures on substrate surfaces. The rational development of SERS‐active substrates depends critically on the homogeneity and intensity of surface plasmon resonances, properties that are strongly dependent on both the morphology and dielectric properties of the metals and composite materials making up the SERS substrates. Enhancement can be controlled by the shape, size, and spacing of metallic nanoparticles. Previous studies in our group have shown that arrays of elliptical nanodiscs have promising geometries for this purpose. Using electron beam lithography (EBL), we fabricate close‐packed arrays of these discs with lateral dimensions ranging from 300:50 to 300:300 nm (long axis : short axis). The arrays are composed of a negative photoresist that, once the lithography process is complete, are coated with a noble metal through physical vapor deposition (PVD). In this work, optimum thickness and deposition rate of noble metal are determined for these substrates. The lithographically produced nanopatterns are studied by Raman spectroscopy to examine the effect of altering the elliptical aspect ratio on SERS activity, while scanning electron microscopy (SEM) is used to examine pattern surfaces post lithographic development and post noble‐metal deposition. Atomic force microscopy (AFM) is used to inspect the roughness of substrate surfaces. Reproducibility between different arrays of the same pattern ranges from 12 to 28%. Homogeneity of our uniform‐morphology EBL/PVD‐fabricated substrates is examined and compared to our random‐morphology polymer nanocomposite substrates. Using rhodamine 6G as an analyte, an increase in SERS signal is noted as the aspect ratio of ellipses goes from 6:1 to 6:6. Our experimental data, in terms of trends in SERS activity, correlate with trends in field enhancements calculated using a simple electrostatic model and with the magnitude of the broad red‐shifted spectral continuum observed for the substrates. Copyright © 2008 John Wiley & Sons, Ltd.     

Nanocrystalline ZnO film deposited by ultrasonic spray on textured silicon substrate as an anti-reflection coating layer

A ZnO thin film was successfully synthesized on glass, flat surface and textured silicon substrates by chemical spray deposition. The textured silicon substrate was carried out using two solutions (NaOH/IPA and Na₂CO₃). Textured with Na₂CO₃ solution, the sample surface exhibits uniform pyramids with an average height of 5 μm. The properties and morphology of ZnO films were investigated. X-ray diffraction (XRD) spectra revealed a preferred orientation of the ZnO nanocrystalline film along the c-axis where the low value of the tensile strain 0.26% was obtained. SEM images show that all films display a granular, polycrystalline morphology. The morphology of the ZnO layers depends dramatically on the substrate used and follows the contours of the pyramids on the substrate surface. The average reflectance of the textured surface was found to be around 13% and it decreases dramatically to 2.57% after deposition of a ZnO antireflection coating. FT-IR peaks arising from the bonding between Zn–O are clearly represented using a silicon textured surface. A very intense photoluminescence (PL) emission peak is observed for ZnO/textured Si, revealing the good quality of the layer. The PL peak at 380.5 nm (UV emission) and the high-intensity PL peak at 427.5 nm are observed and a high luminescence occurs when using a textured Si substrate.     

Surface‐enhanced Raman scattering investigations on silver nanoparticles deposited on alumina and titania nanotubes: influence of the substrate material on surface‐enhanced Raman scattering activity of Ag nanoparticles

Silver nanoparticles deposited on various ‘inert’ porous materials (mainly Al₂O₃ and TiO₂) are often used as substrates for surface‐enhanced Raman scattering (SERS) measurements. In this study, we used the sputter deposition technique to cover tubular arrays of Al₂O₃ and TiO₂ with Ag nanoparticles. Raman spectra of pyridine (as a probe molecule) and of two selected dyes (5‐(4‐dimethylaminobenzylidene)rhodanine and 5‐(4‐(dimethylamino)benzylidene)‐3‐(3‐methoxypropyl)rhodanine) adsorbed on fabricated Ag/TiO₂‐n/Ti and Ag/Al₂O₃‐n/Al substrates were measured. We found that the SERS spectra of pyridine adsorbed on Ag nanoparticles deposited on an Al₂O₃‐n/Al substrate are distinctly different from those measured for an Ag/TiO₂‐n/Ti composite. Similar effects were observed for dyes adsorbed on the surface of both composites. The spectral differences between two kinds of composites (Ag/TiO₂‐n/Ti and Ag/Al₂O₃‐n/Al) are discussed in terms of (1) the modified electronic structure of the Ag nanoparticles due to their interaction with different substrate materials and (2) the different atomic topology of the metal particles thus deposited on the surfaces of the substrates. Composite samples were also studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Copyright © 2012 John Wiley & Sons, Ltd.     

Characterization of Ag nanoparticles on Si wafer prepared using Tollen's reagent and acid-etching

Ag nanoparticles on SiO₂/Si surfaces synthesized using the Tollen's reagent and a subsequent acid-etching were characterized using X-ray photoelectron spectroscopy (XPS). Combining the reduction of the Tollen's reagent and the chemical etching, one can create naked Ag nanoparticles with various sizes in the size range below ∼10 nanometers (nm). The reduced particle size by the chemical etching was identified using positive core level shifts with increasing etching time. Ag nanoparticles smaller than ∼3 nm undergo a reversible oxidation and reduction cycle by reacting with H₂O₂/H₂O and a subsequent heating under vacuum to 150 °C, which was not found for the bulk counterparts and larger particles, demonstrating unique chemical properties of nanoparticles compared to the bulk counterparts.     

Embedded Nanoparticles in Schottky and Ohmic Contacts: A Review

Schottky and Ohmic contacts are essential parts of electronic and optoelectronic devices based on semiconductor materials. Controlling the contact/semiconductor interface properties is the key to obtaining a contact with an optimum performance. Contacts incorporated by nanomaterials, i.e., nano-sized particles that are embedded at the interface of contact/semiconductor, can transform the conventional approaches of contact fabrication, resulting in more reproducible, tunable and efficient electronic, and optoelectronic devices. This article is a review of theoretical and fabrication progress on the last two decades to produce contacts with embedded nanoparticles (NPs). The review covers common routes of NPs deposition on different substrates (e.g., Si, Ge, SiC, GaN, GaAs₆₇P₃₃, and InP) for nanostructured contact fabrication and the theoretical models to investigate the NPs effects on the conduction mechanism and electrical properties of devices.     

A hybrid substrate for surface‐enhanced Raman scattering spectroscopy: coupling metal nanoparticles to strong localised fields on a micro‐structured surface

Electromagnetic coupling between localised plasmons on metal nanoparticles and the strong localised fields on a micro‐structured surface is demonstrated as a means to increase the enhancement factor in surface‐enhanced Raman scattering (SERS) spectroscopy. Au nanoparticles of diameter 20 nm were deposited on a micro‐structured Au surface consisting of a periodic array of square‐based pyramidal pits (Klarite). The spectra of 4‐aminothiophenol (4‐ATP) were compared before and after deposition of Au nanoparticles on the micro‐structured surface. The addition of Au nanoparticles is shown to provide significantly higher signal intensities, with improvements of the order of ∼10³ per molecule compared with spectra obtained from the micro‐structured substrate alone. This hybrid approach offers promise for combining nanoparticles with micro‐ and nano‐structured surfaces in order to design SERS substrates with higher sensitivities. Copyright © 2011 John Wiley & Sons, Ltd.