Amorphous solar cells, the micromorph concept and the role of VHF-GD deposition technique

During the last two decades, the Institute of Microtechnology (IMT) has contributed in two important fields to future thin-film silicon solar cell processing and design:

(1) In 1987, IMT introduced the so-called “very high frequency glow discharge (VHF-GD)” technique, a method that leads to a considerable enhancement in the deposition rate of amorphous and microcrystalline silicon layers. As a direct consequence of reduced plasma impedances at higher plasma excitation frequencies, silane dissociation is enhanced and the maximum energy of ions bombarding the growing surface is reduced. Due to softer ion bombardment on the growing surface, the VHF process also favours the formation of microcrystalline silicon. Based on these beneficial properties of VHF plasmas, for the growth of thin silicon films, plasma excitation frequencies f_exc in the range 30–300 MHz, i.e. clearly higher than the standard 13.56 MHz, are indeed scheduled to play an important role in future production equipment.

(2) In 1994, IMT pioneered a novel thin-film solar cell, the microcrystalline silicon solar cell. This new type of thin-film absorber material––a form of crystalline silicon––opens up the way for a new concept, the so-called “micromorph” tandem solar cell concept. This term stands for the combination of a microcrystalline silicon bottom cell and an amorphous silicon top cell. Thanks to the lower band gap and to the stability of microcrystalline silicon solar cells, a better use of the full solar spectrum is possible, leading, thereby, to higher efficiencies than those obtained with solar cells based solely on amorphous silicon.

Both the VHF-GD deposition technique and the “micromorph” tandem solar cell concept are considered to be essential for future thin-film PV modules, as they bear the potential for combining high-efficiency devices with low-cost manufacturing processes.     

Corrosion protection of secondary lithium electrodes in organic electrolytes

Hydrocarbons show considerable surface activity in organic electrolytes; they, at least partially, displace the polar organic solvent molecules from any solid/electrolyte interface. Saturated hydrocarbons are chemically stable even versus lithium or lithium-rich alloys, and thus they are able to delay the irreversible reduction of organic electrolytes by these highly active negatives, i.e., they delay corrosion and surface filming of the negatives.

As surface filming of lithium strongly controls the growth of lithium dendrites during electroplating, a delay in the filming process significantly decreases dendrite growth. Prevention of dendrite growth, however, requires speedy protection of freshly created “dynamic’ surfaces and, hence, a high concentration (and solubility) of the hydrocarbon surfactant. On the other hand, for the protection of “static‘ electrodes under open cell conditions, even relatively insoluble surfactants may suffice.     

The calculation of wall and fluid temperatures for the incompressible turbulent boundary layer, with arbitrary distribution of wall heat flux

Numerical solution of the partial differential equation for heat transfer in the incompressible turbulent boundary layer has been obtained for uniform (q_w/ρC_pu_i)/√(c_f/2) and for Prandtl numbers 0–7, 1 and 7. The Spalding boundary-layer velocity law was assumed, and the Schmidt method of integration used. Boundary-layer temperature distributions up to x⁺ = 10⁶ are presented, together with the “Spalding function” St/√(c_f/2). A method is given for the application of the solutions to the case of arbitrary distribution of heat flux at the wall.     

Enhancing the elevated temperature performance of Li/LiMn2O4 cells by reducing LiMn2O4 surface area

Lithium-rich spinels were obtained with the same structure but different surface area by two different synthesis routes, namely the “once-annealed” and the “twice-annealed” methods. The elevated temperature performance of Li/Li_1+xMn₂O₄ cell is significantly improved using a spinel cathode with a small surface area: the cell at 50°C lost 5% of the initial capacity over the first 100 cycles based on a spinel cathode with the small surface area of 1.2 m²/g compared to 8% based on a large one of 6.2 m²/g. Also the mechanism responsible for the reaction of LiMn₂O₄ with LiOH to form lithium-rich spinel has been investigated.     

Rebuttal to “The Marginal Cost of CO2 Emissions”: C. Azar, Energy19, p. 1255 (1994)

In “The Marginal Cost of CO₂ Emissions”, Azar criticizes my early works on the shadow price of CO₂ emissions. In this note, I refute those criticisms.     

Investigation of evacuated tube heated by solar trough concentrating system

Two types of solar evacuated tube have been used to measure their heating efficiency and temperature with fluids of water and N₂ respectively with a parabolic trough concentrator. Experiments demonstrate that both evacuated tubes present a good heat transfer with the fluid of water, the heating efficiency is about 70–80%, and the water is easy to boil when liquid rate is less than 0.0046 kg/s. However, the efficiency of solar concentrating system with evacuated tube for heating N₂ gas is less than 40% when the temperature of N₂ gas reaches 320–460 °C. A model for evacuated tube heated by solar trough concentrating system has been built in order to further analyze the characteristics of fluid which flow evacuated tube. It is found that the model agrees with the experiments to within 5.2% accuracy. The characteristics of fluid via evacuated tube heated by solar concentrated system are analyzed under the varying conditions of solar radiation and trough aperture area. This study supports research work on using a solar trough concentrating system to perform ammonia thermo-chemical energy storage for 24 h power generation. The current research work also has application to solar refrigeration.     

“Active Flux” DTFC-SVM Sensorless Control of IPMSM

This paper proposes an implementation of a motion-sensorless control system in wide speed range based on “active flux” observer, and direct torque and flux control with space vector modulation (DTFC-SVM) for the interior permanent magnet synchronous motor (IPMSM), without signal injection. The concept of “active flux” (or “torque producing flux”) turns all the rotor salient-pole ac machines into fully nonsalient-pole ones. A new function for $L_{q}$ inductance depending on torque is introduced to model the magnetic saturation. Notable simplification in the rotor position and speed estimation is obtained, because the active flux position is identical with the rotor position. Extensive experimental results are presented to verify the principles and to demonstrate the effectiveness of the proposed sensorless control system. With the active flux observer, the IPMSM drive system operates from very low speed of 2 r/min at half full-load up to 1400 r/min. Higher speed is possible, in principle, with flux weakening.      

The origin of soot in flames: is the nucleus an ion?

There are two schools of thought on how soot originates in a fuel-rich flame. On the one hand, the ionic theory postulates that small ions, such as C₃H₃⁺, act as nuclei, so that species such as C₂H₂ and C₄H₂ add on to them, and occasionally liberate H₂ in a repetitive growth process. Once these ions become large (≈2000 a.m.u.) they supposedly dissociate and produce an uncharged, but large, hydrocarbon “molecule,” which can grow, coalesce or coagulate to give soot particles. Simultaneously this dissociation produces a very small ion, which repeats the process of adding on C₂, C₃, and C₄ species, etc. The other school of thought believes that fairly similar processes occur, but the species involved are not ions, but uncharged radicals and molecules. This present study has spectroscopically monitored the level of sooting in the earliest stages of its production in a premixed, oxyacetylene flame at 1 atm. If soot originates from ions such as C₃H₃⁺, the addition of a relatively large quantity of easily ionized cesium removes C₃H₃⁺ ions from the flame. In that case there should also be less soot produced. When either distilled water or a strong aqueous solution of CsCl was nebulized into the sooting flame, the intensity of the emission fell by the same amount. This was by only 1% in the earliest part of the burned gas, but rose to a larger drop farther downstream of the reaction zone. Thus cesium itself has no effect on the sooting level early in this premixed flame, indicating that there is no evidence here for ions acting as nuclei for soot. However, the addition of water alone does inhibit the production of soot.     

Cycle characterizations of LiMxMn2−xO4 (M=Co, Ni) materials for lithium secondary battery at wide voltage region

LiM_xMn_2−xO₄ (M=Co, Ni) materials have been synthesized by a melt-impregnation method using γ-MnOOH as the manganese source. Highly crystallized LiM_xMn_2−xO₄ compounds were synthesized at a calcination temperature of 800°C for 24 h in air. All compounds show a single phase except for LiNi_0.5Mn_1.5O₄ based on the X-ray diffraction (XRD) diagram. With the increase of the doping content from 0.1 to 0.5, the capacity of doping materials decreases mainly in the 4 V region.

Although LiM_0.5Mn_1.5O₄ (M=Co, Ni) compound shows a small capacity in the (3+4) V region compared with parent LiMn₂O₄, it is a very effective material in reducing capacity loss in the 3 V region that is caused by the Jahn–Teller distortion. The doping of Co and Ni ions in the LiMn₂O₄ cathode material promotes the stability of this structure and provides an excellent cyclability.     

A further study on the theory of “falling ponds”

The theory of “falling pond” is investigated and the stability requirements of such ponds are discussed. Based on the possible maximum temperature gradients, curves determining the regions of operation of stable falling solar ponds are presented. Also the effects of the thickness of the non-convecting layer and the bottom temperature on the stability of such ponds are discussed. Comparison between a MgCl₂ and NaCl falling solar pond is made and typical profiles for concentration are presented.     

Active MgH2---Mg-systems for hydrogen storage

Novel, highly active MgH₂-Mg-systems, which can be used both in synthetic chemistry and as high temperature hydrogen storage materials, have been studied at the Max-Planck-Institut für Kohlenforschung in Mülheim-Ruhr, West Germany, since 1978. The original preparative procedure was based on the hydrogenation of magnesium under mild conditions (20–60°C. 1–80 bar) in an organic solvent and in the presence of a soluble organo transition metal catalyst. This process yields a MgH₂ storage material with outstanding kinetic properties (w.r.t. the release and take-up of H₂ at normal pressure and 230–350°C), a high specific surface area (100–130 m²g⁻¹) and a high storage capacity for hydrogen (7 wt%). It suffers, however, from the disadvantage of being pyrophoric. Subsequently, MgH₂-Mg---H₂-storage materials have been developed using magnesium powder doped with small quantities of transition metal complexes or organotransition metal compounds and these can be safely handled in air. The new MgH₂---Mg-systems can be used for hydrogen storage, hydrogen purification and separation and heat storage, provided a 300–350°C heat source is available to release the hydrogen. Their main features include low material and production costs, highly satisfactory kinetics, high hydrogen and heat capacity, relative insensitivity toward impurities in hydrogen (H₂O, O₂, CO, etc.) and stability toward air.     

Four-equation turbulence model for prediction of the turbulent boundary layer affected by buoyancy force over a flat plate

Turbulent convective heat transfer with appreciable buoyancy effect over a heated or cooled horizontal flat plate is numerically analyzed by solving four equations for mean square temperature variance , its rate of destruction _θ, turbulent kinetic energy κ and the rate of kinetic energy dissipation . Turbulent time-scale ratio R of temperature fluctuations relative to velocity fluctuations defined by is found to vary widely across the boundary layer. For both highly stable and highly unstable conditions, the ‘four-equation’ model yields better results for mean temperature profile and surface heat flux than the two-equation model. It is also found that the magnitude of thermal von Karman constant κ_θ is not a universal constant but it depends on the thermal stratification of the boundary layer.     

Stability of Cu(In,Ga)Se2 solar cells and evaluation by C–V characteristics

To confirm the long-term reliability of Cu(In,Ga)Se₂, (CIGS) solar cells, we investigated the I–V and C–V characteristics during tests under irradiation or dark condition. Under irradiation, the test samples showed a little increase in efficiency (η) and open-circuit voltage (V_oc) which showed their electrical durability to light irradiation. But the diode factor (n) and series resistance (R_s) showed large changes in value. Also, the built-in voltage (V_b) and density gradient (dN_A/d_x) in the CIGS layer calculated from the C–V characteristics showed distinct changes during the test. After 4 SUN irradiation, two samples in the same fabrication-lot showed new light absorption in the lower-energy range than sun the energy gap of CIGS. We explain the change of C–V characteristics for the samples under strong irradiation with a new model named “Junction retrograde” which can treat defect generation by irradiation to reduce the acceptor density in graded p-n junction. This model for C–V analysis can be used to investigate the long-term reliability of CIGS solar cells under irradiation.     

Natural convection from isothermal flat surfaces

Local heat-transfer coefficients along a flat plate in natural convection in air were measured using Boelter-Schmidt type heat flux meters. Experiments were carried out for different temperature differences in heating and cooling, and with inclinations varying from the horizontal “facing upwards” position, through the vertical position, to the horizontal “facing downwards” position.

The results are presented in terms of local Nusselt number as a function of the local Grashof number “tangential component”. All runs were in the range accepted as that of laminar boundary layer flow. However, under certain conditions when the normal velocity component of the air is directed away from the surface, separated flow is indicated along the trailing part of the surface, well before turbulence sets in in the boundary layer. Separation starts at a certain point along the surface. This point is nearer to the leading edge the higher the temperature difference, and the larger the inclination of the surface to the vertical.

In a separation region, the flux density is uniform. In all other regions the results agreed closely with established theories of laminar boundary layer flow.

A leading adiabatic section, used in some of the experiments, did not affect the results. An appendix gives relations recommended for engineering calculations.     

Environmental assessment and extended exergy analysis of a “zero CO2 emission”, high-efficiency steam power plant

Aim of this paper is to analyze the performance of an innovative high-efficiency steam power plant by means of two “life cycle approach” methodologies, the life cycle assessment (LCA) and the “extended exergy analysis” (EEA).

The plant object of the analysis is a hydrogen-fed steam power plant in which the H₂ is produced by a “zero CO₂ emission” coal gasification process (the ZECOTECH^© cycle). The CO₂ capture system is a standard humid-CaO absorbing process and produces CaCO₃ as a by-product, which is then regenerated to CaO releasing the CO₂ for a downstream mineral sequestration process.

The steam power plant is based on an innovative combined-cycle process: the hydrogen is used as a fuel to produce high-temperature, medium-pressure steam that powers the steam turbine in the topping section, whose exhaust is used in a heat recovery boiler to feed a traditional steam power plant.

The environmental performance of the ZECOTECH^© cycle is assessed by comparison with four different processes: power plant fed by H₂ from natural gas steam reforming, two conventional coal- and natural gas power plants and a wind power plant.     

The hydrogen evolution reaction in acid medium on nickel electrodeposited with PW12O40

The hydrogen evolution reaction (h.e.r.) was performed in acid medium at room temperature on nickel electrodeposited cathodes with and without PW₁₂O⁴⁻₄₀ (the later electrodes are named here by NiPW₁₂). An important increase of the exchange current density (i_o) and a significant decrease of the overvoltage (η) was obtained for NiPW₁₂. These results were attributed to an activation of the electrodes due to the active species of the reduction of PW₁₂O³⁻₁₀. A model involving these reduced species for the h.e.r. was proposed. These species sensitized the proton reduction for the h.e.r. It has been shown that the exchange current density can effectively be used as an electrochemical parameter for the h.e.r. rate due to the electrocatalytic properties of different interfaces involving these electrodes. The NiPW₁₂ cathodes showed stable overpotentials during electrolysis of water in acid medium more than 1500 h, and were not adversely affected by extended open circuit exposure. They showed high resistance to common electrocatalyst poisons. Scanning electron microscopy showed that this was due to a good resistance of the material to electrochemical decomposition.     

Performance and economics of annual storage solar heating systems

Annual storage is used with active solar heating systems to permit storage of summer-time solar heat for winter use. This paper presents the results of a comprehensive computer simulation study of the performance of active solar heating systems with long-term hot water storage. A unique feature of this study is the investigation of systems used to supply backup heat to passive solar and energy-conserving buildings, as well as to meet standard heating and hot water loads.

Findings show that system performance increases linearly as storage volume increases, up to the point where the storage tank is large enough to store all heat collected in summer. This point, the point of “unconstrained operation”, is the likely economic optimum. In contrast to diurnal storage systems, systems with annual storage show only slightly diminishing returns as system size increases. Annual storage systems providing nearly 100% solar space heat may cost the same or less per unit heat delivered as a 50 per cent diurnal solar system. Also in contrast to diurnal systems, annual storage systems perform efficiently in meeting the load of a passive or energy-efficient building. A breakeven cost 4¢–10¢/kWh is estimated for optimal 100 per cent solar heating in the U.S.A.     

PL and PLE studies of KMgF3:Sm crystal and the effect of its wavelength conversion on CdS/CdTe solar cell

We studied the effect on conversion efficiency of a CdS/CdTe solar cell by applying a wavelength conversion of a rare earth ion. Both photoluminescence (PL) and photoluminescence excitation (PLE) spectra of the Sm-doped KMgF₃ crystal were investigated. As a result, we found that both the divalent and the trivalent Sm ions coexist in the grown KMgF₃ crystals. Also, all the PLE spectra below 500 nm were effectively converted to PL spectra above 540 nm and the solar cell possessed a high spectral response. The quantum efficiency of Sm ions was estimated to be 0.84 from the comparison of the experimental curve with the calculated one for the increased spectral response below 500 nm. When a thin disc crystal of KMgF₃:Sm was placed on the top of CdS/CdTe solar cell as a precursor for wavelength conversion, both the maximum output power and the conversion efficiency increased by 5% as compared with the case of a pure KMgF₃ crystal.     

Studies on the reduction of iron oxide with hydrogen

Kinetic studies have been carried out on the hydrogen reduction of pure -Fe₂O₃ doped with foreign metal oxides employing a sensitive micro-gravimetric technique. The results show that the reduction of pure Fe₂O₃ proceeds by a consecutive two-step mechanism via Fe₃O₄, the overall rate being controlled by the topochemical reduction of Fe₃O₄ while that of doped oxides and hematite ore takes place by a different mechanism involving the mixed ferrite formed. In addition, the reduction of pure Fe₂O₃ is catalysed by metal additives in the presence of water vapour. This enhancement in reduction rate is attributed to a “hydrogen spill-over” effect.