Publications

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We present the results of a one year LDRD program that has focused on evaluating the use of newly developed deep ultraviolet LEDs in water purification. We describe our development efforts that have produced an LED-based water exposure set-up and enumerate the advances that have been made in deep UV LED performance throughout the project. The results of E. coli inactivation with 270-295 nm LEDs are presented along with an assessment of the potential for applying deep ultraviolet LED-based water purification to mobile point-of-use applications as well as to rural and international environments where the benefits of photovoltaic-powered systems can be realized.

Time domain reflectometry (TDR) operates by propagating a radar frequency electromagnetic pulse down a transmission line while monitoring the reflected signal. As the electromagnetic pulse propagates along the transmission line, it is subject to impedance by the dielectric properties of the media along the transmission line (e.g., air, water, sediment), reflection at dielectric discontinuities (e.g., air-water or water-sediment interface), and attenuation by electrically conductive materials (e.g., salts, clays). Taken together, these characteristics provide a basis for integrated stream monitoring; specifically, concurrent measurement of stream stage, channel profile and aqueous conductivity. Here, we make novel application of TDR within the context of stream monitoring. Efforts toward this goal followed three critical phases. First, a means of extracting the desired stream parameters from measured TDR traces was required. Analysis was complicated by the fact that interface location and aqueous conductivity vary concurrently and multiple interfaces may be present at any time. For this reason a physically based multisection model employing the S11 scatter function and Cole-Cole parameters for dielectric dispersion and loss was developed to analyze acquired TDR traces. Second, we explored the capability of this multisection modeling approach for interpreting TDR data acquired from complex environments, such as encountered in stream monitoring. A series of laboratory tank experiments were performed in which the depth of water, depth of sediment, and conductivity were varied systematically. Comparisons between modeled and independently measured data indicate that TDR measurements can be made with an accuracy of {+-}3.4x10{sup -3} m for sensing the location of an air/water or water/sediment interface and {+-}7.4% of actual for the aqueous conductivity. Third, monitoring stations were sited on the Rio Grande and Paria rivers to evaluate performance of the TDR system under normal field conditions. At the Rio Grande site (near Central Bridge in Albuquerque, New Mexico) continuous monitoring of stream stage and aqueous conductivity was performed for 6 months. Additionally, channel profile measurements were acquired at 7 locations across the river. At the Paria site (near Lee's Ferry, Arizona) stream stage and aqueous conductivity data were collected over a 4-month period. Comparisons drawn between our TDR measurements and USGS gage data indicate that the stream stage is accurate within {+-}0.88 cm, conductivity is accurate within {+-}11% of actual, and channel profile measurements agree within {+-}1.2 cm.

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The quality of low-cost multicrystalline silicon (mc-Si) has improved to the point that it forms approximately 50% of the worldwide photovoltaic (PV) power production. The performance of commercial mc-Si solar cells still lags behind c-Si due in part to the inability to texture it effectively and inexpensively. Surface texturing of mc-Si has been an active field of research. Several techniques including anodic etching [1], wet acidic etching [2], lithographic patterning [3], and mechanical texturing [4] have been investigated with varying degrees of success. To date, a cost-effective technique has not emerged.

The Sandia Photovoltaic Program conducted research in crystalline-silicon solar cells between 1986 and 2000 for the U.S. Department of Energy. This period saw rapid improvements in the fundamental understanding of c-Si materials and devices, improvements in c-Si PV manufacturing and control, and a rapid expansion of c-Si PV manufacturing capacity. Crystalline-silicon technology has provided the basis for PV to emerge as a serious option for global energy needs. The c-Si cell research at Sandia examined c-Si materials, devices, processing, and process integration. This report summarizes research conducted in this program over the past 15 years.

The authors have developed novel metal-assisted texturing processes that have led to optically favorable surfaces for solar cells. Large area ({approximately} 200 cm{sup 2}) uniform texturing has been achieved. The physical dimensions of the chamber limited texturing of even larger wafers. Surface contamination and residual RIE-induced damage were removed by incorporation of a complete RCA clean process followed by wet-chemical etching treatments. RIE-textured solar cells with optimized profiles providing performance comparable to the random, wet-chemically etched cells have been demonstrated. A majority of the texture profiles exhibit an enhanced IQE response in the near IR region.using scanning electron microscope measurements, they carried out a detailed analysis of the microstructure of random RIE-textured surfaces. The random microstructure represents a superposition of sub-{micro}m grating structures with a wide distribution of periods, depths, and profiles as determined by the SEM measurements. These structures were modeled using GSOLVER{trademark} software for periodic patterns. The enhanced IR response from random, RIE-textured surfaces is attributed to enhanced coupling of light into the transmitted diffraction orders. These obliquely propagating diffraction orders generate electron-hole pairs closer to the surface, thus, reducing bulk recombination losses relative to a non-scattering, planar surface with identical hemispherical reflection. The optimized texture and damage removal processes have been applied to large area (100--132 cm{sup 2}) multi-crystalline wafers. initial results have demonstrated improved performance relative to planar, control wafers. However, the texture and solar cell fabrication processes require further optimization in the RCA clean, DRE treatments, and emitter formation in order to fully realize the benefits of the low-reflection ({approximately}1-2%) textured surfaces.

The overall objectives of this program are to (1) develop rapid and low-cost processes for manufacturing that can improve yield, throughput, and performance of silicon photovoltaic devices, (2) design and fabricate high-efficiency solar cells on promising low-cost materials, and (3) improve the fundamental understanding of advanced photovoltaic devices. Several rapid and potentially low-cost technologies are described in this report that were developed and applied toward the fabrication of high-efficiency silicon solar cells.

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The overall objectives of this program are (1) to develop rapid and low-cost processes for manufacturing that can improve yield, throughput, and performance of silicon photovoltaic devices, (2) to design and fabricate high-efficiency solar cells on promising low-cost materials, and (3) to improve the fundamental understanding of advanced photovoltaic devices. Several rapid and potentially low-cost technologies are described in this report that were developed and applied toward the fabrication of high-efficiency silicon solar cells.

In this paper, the authors examined the areas in c-Si growth, materials, and processing that require improvement through research to overcome barriers to the implementation of the photovoltaic road maps's Si goals. To obtain PV module throughput to the roadmap target of 200 MW/factory/year, the typical Si PV factory must produce >4,000 m{sup 2}/day of silicon.

Hemispherical reflectance and internal quantum efficiency measurements have been employed to evaluate the response of Si nanostructured surfaces formed by using random and periodic reactive ion etching techniques. Random RIE-textured surfaces have demonstrated solar weighted reflectance of {approx} 3% over 300--1,200-nm spectral range even without the benefit of anti-reflection films. Random RIE-texturing has been found to be applicable over large areas ({approximately} 180 cm{sup 2}) of both single and multicrystalline Si surfaces. Due to the surface contamination and plasma-induced damage, RIE-textured surfaces did not initially provide increased short circuit current as expected from the enhanced absorption. Improved processing combined with wet-chemical damage removal etches resulted in significant improvement in the short circuit current with IQEs comparable to the random, wet-chemically textured surfaces. An interesting feature of the RIE-textured surfaces was their superior performance in the near IR spectral range. The response of RIE-textured periodic surfaces can be broadly classified into three distinct regimes. One-dimensional grating structures with triangular profiles are characterized by exceptionally low, polarization-independent reflective behavior. The reflectance response of such surfaces is similar to a graded-index anti-reflection film. The IQE response from these surfaces is severely degraded in the UV-Visible spectral region due to plasma-induced surface damage. One-dimensional grating structures with rectangular profiles exhibit spectrally selective absorptive behavior with somewhat similar IQE response. The third type of grating structure combines broadband anti-reflection behavior with significant IQE enhancement in 800--1,200-nm spectral region. The hemispherical reflectance of these 2D grating structures is comparable to random RIE-textured surfaces. The IQE enhancement in the long wavelength spectral region can be attributed to increased coupling into obliquely propagating transmitted diffracted orders inside the Si substrate. Random RIE texturing techniques are expected to find widespread commercial applicability in low-cost, large-area multicrystalline Si solar cells. Grating-texturing techniques are expected to find applications in thin-film and space solar cells.

A maskless plasma texturing technique using Reactive Ion Etching for silicon solar cells results in a very low reflectance of 5.4 % before, and 3.9 % after SiN deposition. A detailed study of surface recombination and emitter properties was made, then solar cells were fabricated using the DOSS solar cell process. Different plasma-damage removal treatments are tested to optimize low lifetime solar cell efficiencies. Highest efficiencies are observed for little or no plasma-damage removal etching on mc-Si. Increased Jsc due to the RIE texture proved superior to a single layer anti-reflection coating. This indicates that RIE texturing is a promising texturing technique, especially applicable on lower lifetime (multicrystalline) silicon. The use of non-toxic, non-corrosive SF6 makes this process attractive for mass production.

Sub-wavelength periodic texturing (gratings) of crystalline-silicon (c-Si) surfaces for solar cell applications can be designed for maximizing optical absorption in thin c-Si films. We have investigated c-Si grating structures using rigorous modeling, hemispherical reflectance, and internal quantum efficiency measurements. Model calculations predict almost ∼ 100 % energy coupling into obliquely propagating diffraction orders. By fabrication and optical characterization of a wide range of ID & 2D c-Si grating structures, we have achieved broadband, low (∼ 5 %) reflectance without an anti-reflection film. By integrating grating structures into conventional solar cell designs, we have demonstrated short-circuit current density enhancements of 3.4 and 4.1 mA/cm2 for rectangular and triangular 1D grating structures compared to planar controls. The effective path length enhancements due to these gratings were 2.2 and 1.7, respectively. Optimized 2D gratings are expected to have even better performance.

In October 1996, an interdisciplinary team began a three-year LDRD project to study the plasma processes of reactive ion etching and plasma-enhanced chemical vapor deposition on large-area silicon devices. The goal was to develop numerical models that could be used in a variety of applications for surface cleaning, selective etching, and thin-film deposition. Silicon solar cells were chosen as the experimental vehicle for this project because an innovative device design was identified that would benefit from immediate performance improvement using a combination of plasma etching and deposition processes. This report presents a summary of the technical accomplishments and conclusions of the team.

Surface texture promotes enhanced light absorption in Si solar cells. The quality of lower cost multicrystalline-silicon (mc-Si) has increased to the point that its cell performance is close to that of single c-Si cells, with the major difference resulting from the inability to texture mc-Si affordably. This has reduced the cost-per-watt advantage of mc-Si. Surface texturing aimed at enhanced absorption in Si has been historically obtained by creating multimicrometer-sized pyramids using anisotropic wet etchants on single-crystalline silicon that take advantage of its single crystalline orientation. Since the surface feature sizes are several times the length of the incident solar wavelengths involved, the optical analysis of the reflected and absorbed light can be understood using geometrical optics. Geometrical textures reduce reflection and improve absorption by double-bounce and oblique light coupling into the semiconductor. However, geometrical texturing suffers from several disadvantages that limit its effectiveness. Some of these are listed below: (a) Wet-chemical anisotropic etching used to form random pyramids on <100> crystal orientation is not effective in the texturing of low-cost multicrystalline wafers, (b) Anti-reflection films deposited on random features to reduce reflection have a resonant structure limiting their effectiveness to a narrow range of angles and wavelengths. Various forms of surface texturing have been applied to mc-Si in research, including laser-structuring, mechanical grinding, porous-Si etching, and photolithographically defined etching. However, these may be too costly to ever be used in large-scale production. A Japanese firm has reported the development of an RIE process using Cl{sub 2} gas, which textures multiple wafers per batch, making it attractive for mass-production [1]. Using this process, they have produced a 17.1% efficient 225-cm{sup 2} mc-Si cell, which is the highest efficiency mc-Si cell of its size ever reported. This proves that RIE texturing does not cause performance-limiting damage to Si cells. In this paper, we will discuss an RIE texturing process that avoids the use of toxic and corrosive Cl{sub 2} gas.

Sandia National Laboratories has demonstrated significant performance gains in crystalline silicon solar cell technology through the use of plasma-processing for the deposition of silicon nitride by Plasma Enhanced Chemical Vapor Deposition (PECVD), plasma-hydrogenation of the nitride layer, and reactive-ion etching of the silicon surface prior to the deposition to decrease the reflectivity of the surface. One of the major problems of implementing plasma processing into a cell production line is the batch configuration and/or low throughput of the systems currently available. This report describes the concept of a new in-line plasma processing system that could meet the industrial requirements for a high-throughput and cost effective solution for mass production of solar cells.

The performance of a solar cell is critically dependent on absorption of incident photons and their conversion into electrical current. This report describes research efforts that have been directed toward the use of nanoscale surface texturing techniques to enhance light absorption in Si. This effort has been divided into two approaches. The first is to use plasma-etching to produce random texturization on multicrystalline Si cells for terrestrial use, since multicrystalline Si cannot be economically textured in any other way. The second approach is to use interference lithography and plasma-etching to produce gettering structures on Si cells for use in space, so that long-wavelength light can be absorbed close to the junction and make the cells more resistant to cosmic radiation damage.

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