Effect of rapid thermal oxidation on structure and photoelectronic properties of silicon oxide in monocrystalline silicon solar cells

This paper concerns the topic of surface passivation properties of rapid thermal oxidation on p-type monocrystalline silicon wafer for use in screen-printed silicon solar cells. It shows that inline thermal oxidation is a very promising alternative to the use of conventional batch type quartz tube furnaces for the surface passivation of industrial phosphorus-diffused emitters. Five minutes was the most favorable holding time for the rapid thermal oxidation growth of the solar cell sample, in which the average carrier lifetime was increased 19.4 μs. The Fourier transform infrared spectrum of the rapid thermal oxidation sample, whose structure was Al/Al-BSF/p-type Si/n-type SiP/SiO₂/SiN_x/Ag solar cell with an active area of 15.6 cm², contained an absorption peak at 1085 cm⁻¹, which was associated with the Si–O bonds in silicon oxide. The lowest average reflectance of this sample is 0.87%. Furthermore, for this sample, its average of internal quantum efficiency and conversion efficiency are respectively increased by 8% and 0.23%, compared with the sample without rapid thermal oxidation processing.     

Antireflective properties of disordered Si SWSs with hydrophobic surface by thermally dewetted Pt nanomask patterns for Si-based solar cells

We have theoretically and experimentally investigated the antireflective properties of the disordered subwavelength structures (SWSs) with a hydrophobic surface on silicon (Si) substrates by an inductively coupled plasma (ICP) etching in SiCl₄/Ar plasma using thermally dewetted platinum (Pt) nanopatterns as etch masks for Si-based solar cells. The Pt thin films on the SiO₂/Si surface were properly changed into the optimized dot-like nanopatterns via the thermal dewetting by rapid thermal annealing process. The antireflection properties were definitely affected by the etched profile of SWSs which can be controlled by the conditions of etching process. For the tapered Si SWS with a high average height of 724 ± 78 nm, the reflectance was significantly reduced below 5% over a wide wavelength range of 350-1030 nm, leading to a relatively low solar weighted reflectance of 2.6%. The structure exhibited reflectances less than 14.8% at wide incident angles of 8-70°. The hydrophobic surface with a water contact angle of 113.2° was obtained. For Si SWSs, the antireflective properties were also analyzed by the rigorous coupled-wave analysis simulation. These calculated results showed similar behavior to the experimental results.     

Effect of etching parameters on antireflection properties of Si subwavelength grating structures for solar cell applications

We fabricate the aluminum-doped zinc oxide (AZO) subwavelength gratings (SWG) on Si and glass substrates by holographic lithography and sequent CH₄/H₂/Ar reactive ion etching process. The etch selectivity of AZO over photoresist mask as well as the nano-scale shape is optimized for better antireflection performance. To analyze the antireflective properties of AZO SWG surface, the optical reflectivity is measured and then calculated together with a rigorous coupled-wave analysis. The reflectance spectrum can be considerably changed by incorporating the SWG into AZO film. As the SWG height of AZO on Si substrate increases, the magnitude of interference oscillations in the reflectance spectrum tends to be reduced with the larger difference between its maxima. The use of optimized SWG can significantly reduce the surface reflection of AZO film at the desired wavelengths. The measured reflectance data of AZO SWG are reasonably consistent with the simulation results. No considerable change in transmission characteristics is observed for AZO SWG structures.     

Antireflective properties of AZO subwavelength gratings patterned by holographic lithography

We fabricate the aluminum-doped zinc oxide (AZO) subwavelength gratings (SWG) on Si and glass substrates by holographic lithography and sequent CH₄/H₂/Ar reactive ion etching process. The etch selectivity of AZO over photoresist mask as well as the nano-scale shape is optimized for better antireflection performance. To analyze the antireflective properties of AZO SWG surface, the optical reflectivity is measured and then calculated together with a rigorous coupled-wave analysis. The reflectance spectrum can be considerably changed by incorporating the SWG into AZO film. As the SWG height of AZO on Si substrate increases, the magnitude of interference oscillations in the reflectance spectrum tends to be reduced with the larger difference between its maxima. The use of optimized SWG can significantly reduce the surface reflection of AZO film at the desired wavelengths. The measured reflectance data of AZO SWG are reasonably consistent with the simulation results. No considerable change in transmission characteristics is observed for AZO SWG structures.     

Influence of Si substrate preparation on surface chemistry and morphology of L-CVD SnO2 thin films studied by XPS and AFM

Results of experimental studies of the influence of substrate preparation on the surface chemistry and surface morphology of the laser-assisted chemical vapour deposition (L-CVD) SnO₂ thin films are presented in this paper. The native Si(1 0 0) substrate cleaned by UHV thermal annealing (TA) as well as thermally oxidized Si(1 0 0) substrate cleaned by ion bombardment (IBA) have been used as the substrates. X-ray photoemission spectroscopy (XPS) has been used for the control of surface chemistry of the substrates as well as of deposited films. Atomic force microscopy (AFM) has been used to control the surface morphology of the L-CVD SnO₂ thin films deposited on differently prepared substrates. Our XPS shows that the L-CVD SnO₂ thin films deposited on thermally oxidized Si(1 0 0) substrate after cleaning with ion bombardment exhibit the same stoichiometry, i.e. ratio [O]/[Sn] = 1.30 as that of the layers deposited on Si(1 0 0) substrate previously cleaned by UHV prolonged heating. AFM shows that L-CVD SnO₂ thin films deposited on thermally oxidized Si(1 0 0) substrate after cleaning with ion bombardment exhibit evidently increasing rough surface topography with respect to roughness, grain size range and maximum grain height as the L-CVD SnO₂ thin films deposited on atomically clean Si substrate at the same surface chemistry (nonstoichiometry) reflect the higher substrate roughness after cleaning with ion bombardment.     

Characterization of silicon nanowires grown on silicon, stainless steel and indium tin oxide substrates

Silicon nanowires (SiNWs) have been grown on crystalline silicon (Si), indium tin oxide (ITO) and stainless steel (SS) substrates using a gold catalyst coating with a thickness of 200 nm via pulsed plasma-enhanced chemical vapor deposition (PPECVD). Their morphological, mineralogical and surface characteristics have been investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman analysis. SiNWs growth is accompanied by oxidation, thus yielding partially (SiO _x ) and fully oxidized (SiO₂) Si sheaths. The mean diameters of these SiNWs range from 140 to 185 nm. Si with (111) and (220) planes exists in SiNWs grown on all three substrates while Si with a (311) plane is detected only for Si and ITO substrates. Computational simulation using density functional theory (DFT) has also been conducted to supplement the experimental Raman analyses for crystalline Si and SiO₂. XPS results reveal that ca. 30 % of the SiNWs have been oxidized for all substrates. The results presented in this paper can be used to aid selection of appropriate substrates for SiNW growth, depending on specific applications.     

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.     

Stability of La2O3 and GeO2 passivated Ge surfaces during ALD of ZrO2 high-k dielectric

La₂O₃ grown by atomic layer deposition (ALD) and thermally grown GeO₂ are used to establish effective electrical surface passivations on n-type (1 0 0)-Ge substrates for high-k ZrO₂ dielectrics, grown by ALD at 250 °C substrate temperature. The electrical characterization of MOS capacitors indicates an impact of the Ge-surface passivation on the interfacial trap density and the frequency dependent capacitance in the inversion regime. Lower interface trap densities can be obtained for GeO₂ based passivation even though a chemical decomposition of the oxidation states occur during the ALD of ZrO₂. As a consequence the formation of a ZrGeO_x compound inside the ZrO₂ matrix and a decline of the interfacial GeO₂ are observed. The La₂O₃ passivation provides a stable amorphous lanthanum germanate phase at the Ge interface but also traces of Zr germanate are indicated by X-ray-Photoelectron-Spectroscopy and Transmission-Electron-Microscopy.     

On the topographic and optical properties of SiC/SiO2 surfaces

The roughness of the semiconductor surface substantially influences properties of the whole structure, especially when thin films are created. In our work 3C SiC, 4H SiC and Si/a-SiC:H/SiO₂ structures treated by various oxidation a passivation procedures are studied by atomic force microscopy (AFM) and scanning tunnelling microscopy (STM). Surface roughness properties are studied by fractal geometry methods. The complexity of the analysed surface is sensitive to the oxidation and passivation steps and the proposed fractal complexity measure values enable quantification of the fine surface changes. We also determined the optical properties of oxidized and passivated samples by using visual modelling and stochastic optimization.      

Mechanism for crystalline Si surface passivation by the combination of SiO2 tunnel oxide and µc‐SiC:H thin film

This work demonstrates that the combination of a wet‐chemically grown SiO₂ tunnel oxide with a highly‐doped microcrystalline silicon carbide layer grown by hot‐wire chemical vapor deposition yields an excellent surface passivation for phosphorous‐doped crystalline silicon (c‐Si) wafers. We find effective minority carrier lifetimes of well above 6 ms by introducing this stack. We investigated its c‐Si surface passivation mechanism in a systematic study combined with the comparison to a phosphorous‐doped polycrystalline‐Si (pc‐Si)/SiO₂ stack. In both cases, field effect passivation by the n‐doping of either the µc‐SiC:H or the pc‐Si is effective. Hydrogen passivation during µc‐SiC:H growth plays an important role for the µc‐SiC:H/SiO₂ combination, whereas phosphorous in‐diffusion into the SiO₂ and the c‐Si is operative for the surface passivation via the Pc‐Si/SiO₂ stack. The high transparency and conductivity of the µc‐SiC:H layer, a low thermal budget and number of processes needed to form the stack, and the excellent c‐Si surface passivation quality are advantageous features of µc‐SiC:H/SiO₂ that can be beneficial for c‐Si solar cells. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Improvement of plasmonic field-matter interaction by subwavelength dielectric gratings

We experimentally and theoretically investigate that detection sensitivity in surface plasmon resonance (SPR) biosensors can be significantly enhanced by employing subwavelength dielectric gratings deposited on a gold film. The enhancement originates from an improvement of field-matter interaction: enhanced evanescent field intensity at the binding region and increased surface reaction area. Using a large-area SiO₂ grating array fabricated by nanoimprint lithography, experimental sensor performance measured by parylene film coating shows that the SPR substrates combined with a dielectric grating provide a notable sensitivity improvement compared to a conventional bare gold film. We also demonstrate that plasmon field can be more confined and enhanced at the dielectric gratings with a larger width. The proposed SPR structure could potentially be useful in a variety of plasmonic applications including high-sensitivity biosensors.     

Passivation of structured p-type silicon interfaces: Effect of surface morphology and wet-chemical pre-treatment

The effect of both surface morphology and wet-chemical pre-treatment on electronic surface and interface properties was investigated for mono- and polycrystalline silicon substrates with special surface structures. Surface charge, energetic distribution, and density of rechargeable states on these surfaces were determined by surface photovoltage (SPV) measurements. These results were correlated to previously reported findings on atomically flat Si(111) and Si(100) surfaces of monocrystalline wafers. In this paper, a specially optimised sequence of cleaning, wet-chemical oxidation, and oxide removal procedures is described in detail for the first time. This method was successfully applied in order to remove contaminations and damaged surface layers and to obtain atomically flat areas on substrates with evenly distributed atomic steps, polycrystalline and monocrystalline substrates with randomly distributed pyramids. A significant reduction in surface micro-roughness, interface state density, and recombination loss was achieved. Using passivation by wet-chemical oxidation or H-termination, respectively, the optimised surface state can be preserved by the time of following preparation steps and during subsequent a-Si:H plasma enhanced chemical vapour deposition (PECVD).     

Silicon surface passivation by aluminium oxide studied with electron energy loss spectroscopy

The origin behind crystalline silicon surface passivation by Al₂O₃ films is studied in detail by means of spatially‐resolved electron energy loss spectroscopy. The bonding configurations of Al and O are studied in as‐deposited and annealed Al₂O₃ films grown on c‐Si substrates by plasma‐assisted and thermal atomic layer deposition. The results confirm the presence of an interfacial SiO₂‐like film and demonstrate changes in the ratio between tetrahedrally and octahedrally coordinated Al in the films after annealing. These observations reveal the underlying origin of c‐Si surface passivation by Al₂O₃. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Passivation of black silicon boron emitters with atomic layer deposited aluminum oxide

The nanostructured surface – also called black silicon (b‐Si) – is a promising texture for solar cells because of its extremely low reflectance combined with low surface recombination obtained with atomic layer deposited (ALD) thin films. However, the challenges in keeping the excellent optical properties and passivation in further processing have not been addressed before. Here we study especially the applicability of the ALD passivation on highly boron doped emitters that is present in crystalline silicon solar cells. The results show that the nanostructured boron emitters can be passivated efficiently using ALD Al₂O₃ reaching emitter saturation current densities as low as 51 fA/cm². Furthermore, reflectance values less than 0.5% after processing show that the different process steps are not detrimental for the low reflectance of b‐Si. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Broadband long-wavelength infrared Si/SiO2 subwavelength grating reflector

A long-wavelength IR broadband reflector is demonstrated using a high-index-contrast subwavelength grating based on a Si/SiO2 system. The field response has been computationally and experimentally verified to exhibit broadband reflectance in the spectral range of 13-16 μm with Δλ/λ=18.5% for reflectance >70%. The gratings exhibit incident field polarization dependence with an average extinction ratio of 1:1.6.     

Ta2Si short time thermal oxidized layers in N2O and O2 to form high-k gate dielectric on SiC

In this work, we report on two properties of the oxidation of tantalum silicide (Ta₂Si) on SiC substrates making this material of interest as insulator for many wide bandgap or compound semiconductors. The relatively high oxidation rate of tantalum silicide to form high-k insulator layers and its ability for being oxidized in diluted N₂O ambient in a manner similar to the oxidation in O₂ are investigated. Metal-insulator-semiconductor capacitors have been used to establish the actual applicability and constrain of the high-k insulator depending on the oxidation conditions. At 1050 °C, the reduction of the oxidation time from 1 h to 5 min affects primordially the SiO_x interfacial layer formed between the bulk insulator and the substrate. This interfacial layer strongly influences the metal-insulator-semiconductor performances of the oxidized Ta₂Si layer. The bulk insulator basically remains unaffected although some structural differences arise when the oxidation is performed in N₂O.     

Initial oxidation of HF-acid treated Si(1 0 0) surfaces under air exposure studied by synchrotron radiation X-ray photoelectron spectroscopy

Initial oxidation of HF-acid treated Si(1 0 0) surfaces with air exposure has been studied by using synchrotron radiation X-ray photoelectron spectroscopy. We demonstrate that the initial oxidation is explained not by a layer-by-layer process, but by a non-uniform mechanism. Just after dipping a Si substrate in HF-acid and spin-drying, the Si surface is immediately oxidized partly with a coverage of 0.2. It is considered that the non-uniform oxidation takes place at surface defects on H passivated Si surfaces. With increasing the air exposure up to 1 week, we have found that the non-oxidized part is oxidized uniformly at slower rates compared to the beginning. IR absorption spectroscopy with a multiple-internal-reflection geometry clearly indicates the backbond oxidation of surface Si takes place despite the H passivation produced by the HF-acid treatment.     

Passivation of defect states in Si-based and GaAs structures

Formation of defect states on semiconductor surfaces, at its interfaces with thin films and in semiconductor volumes is usually predetermined by such parameters as semiconductor growth process, surface treatment procedures, passivation, thin film growth kinetics, etc. This paper presents relation between processes leading to formation of defect states and their passivation in Si and GaAs related semiconductors and structures. Special focus is on oxidation kinetics of yttrium stabilized zirconium/SiO₂/Si and Sm/GaAs structures. Plasma anodic oxidation of yttrium stabilized zirconium based structures reduced size of polycrystalline silicon blocks localised at thin film/Si interface. Samarium deposited before oxidation on GaAs surface led to elimination of EL2 and/or ELO defects in MOS structures. Consequently, results of successful passivation of deep traps of interface region by CN⁻ atomic group using HCN solutions on oxynitride/Si and double oxide layer/Si structures are presented and discussed. By our knowledge, we are presenting for the first time the utilization of X-ray reflectivity method for determination of both density of SiO₂ based multilayer structure and corresponding roughnesses (interfaces and surfaces), respectively.     

On ultra-thin oxide/Si and very-thin oxide/Si structures prepared by wet chemical process

The properties of ultra-thin oxide/Si and very-thin oxide/Si structures prepared by wet chemical oxidation in nitric acid aqueous solutions (NAOS) and passivated in HCN aqueous solutions were investigated by electrical, optical and structural methods. n- and p-doped (1 0 0) crystalline Si substrates were used. There were identified more types of interface defect states in dependence on both post-oxidation treatment and passivation procedure. On samples prepared on n-type Si, continuous spectrum of defect states of 0.05-0.2 eV range and discrete defect traps, ∼E_CB − 0.26 eV and ∼E_CB − 0.39 eV, were found. All mentioned defects are related with various types of Si dangling bonds and/or with SiO_x precipitates. Post-metallization annealing of investigated MOS structures reduced the interface defect density and suppressed the leakage currents. It did not change spectral profile of interface defect states in the Si band gap. In addition, there are presented following two optical phenomena: relation between amplitude of photoluminescence signal of NAOS samples and parameters of chemical oxidation process and quantum confinement effect observed on samples containing Si grains of size less as ∼2 nm.     

Spectroscopic ellipsometry modeling of ZnO thin films with various O2 partial pressures

ZnO films were deposited on thermally oxidized SiO₂/p-type Si (100) substrates and glass substrates by DC magnetron sputtering using a metal Zn target. Three types of samples were prepared with various O₂/(Ar + O₂) ratios (O₂ partial pressure) of 20%, 50%, and 80%. The properties of these ZnO thin films were investigated using X-ray diffraction (XRD), optical transmittance, atomic force microscopy (AFM), and spectroscopic ellipsometry in the spectral region of 1.7–3.1 eV. The structural and optical properties of ZnO thin films were affected by O₂ partial pressure. Relationships between crystallinity, the ZnO surface roughness layer, and the refractive index (n) were investigated with varying O₂ partial pressure. It was shown that the spectroscopic ellipsometry extracted parameters well represented the ZnO thin film characteristics for different O₂ partial pressures.