Category Archives: BACKGROUND

Minimized Absorptance

Figure 2 shows spectral absorptance A(A) calculated from

A(A) = 1 — T(A) — R(A).

The data in panel (a) represent the bleached state for the nickel-based oxides mentioned before. Prior to the measurements, the films were cycled ten times in a 1 M KOH solution to stabilize the properties. A significant decrease of A(A) was found at short wavelengths for additives being Mg, Al, Si, Zr, Nb, and Ta, whereas the films containing V and Ag did not show any improvement in their optical properties compared to those of pure nickel oxide.

(a) (b)

The strong absorptance at A < 350 nm is due to the semiconductor band-gap, which appears to be widened as a consequence of the addition of Mg, Al, Si, Zr, Nb, or Ta. On the other hand, the addition of V or Ag narrowed the band-gap. Some weak absorption features can be discerned in the spectral data; they are possibly associated with crystal-field effects [16,17]. Alternatively, the additives may affect
optical absorption caused by defects such as vacancies, over-stoichiometry, grain boundaries, etc. Thermodynamically stable nickel oxide is a p-type conductor due to excess oxygen [18,19]. It is then plausible that the p-type conductivity and the residual optical absorption in the bleached state originate from the same electron states, and this may explain why films of pure Ni oxide cannot be made completely colorless. When Al is added, for example, it can act as a donor of electrons and fill the electron (hole) states on Ni, thereby reducing the residual absorption. The addition of V, on the other hand, may provide acceptor states whose effect would be to enhance the residual absorption.

Figure 2(b) reports comparative data for iridium-based films, cycled in 1 M propionic acid. It is found that additives of Mg, Al, Ta, and Zr tend to lower the absorption, as may be understood by the same arguments as those applicable to the nickel-based oxides.

Novel TI wall system and application demonstration

The optimized small-celled TI structure was tested on a demonstration object. The demonstration object was an ultra-low energy solar single family house with office unit in Graz, Austria (planning and implementation: Planungs — und Bauges. m.b. H. HEGEDYS — HAAS). The objective of the building owner was to explore in practice the technological possibilities and potentials of a full-fledged solar energy supply relying on the innovative use of plastics and polymer materials based on renewable raw materials. Ecological and biological criteria were taken into account during the building design and construction and the material selection process. The building for the application demonstration consists of two main wings: a main wing in a countryhouse style and a south oriented “solar” wing (s. Fig. 2). The “solar” wing features the TI facade with summer shading through the roof, a thermal collector with a steep tilt angle for high winter yields as well as roof-mounted
photovoltaic modules with ventilation at the back. While the concept of the building does not follow the usual compact design of a passive house, energy efficiency criteria set forth for the passive house standard (space heating demand < 15 kWh/(m2a)) were nevertheless achieved.

Concerning the TI facade of the building (Fig. 2) an optimized frame and facade structure based on timber profiles with minimized material fraction and shading of the absorber was developed and realized. A sketch through the TI facade is shown in Fig. 3. A 3.5 cm thick timber profile is mounted onto the 25 cm thick concrete filled brick wall and integrated into the plaster. The plaster is painted with a black solar collector absorber. The Fig. 2. Solar wing of the demonstration object featuring 13.5 cm thick TI structure the TI facade with summer shading through the roof is in close contact with the

absorber. At the outside an

6.5 cm thick air gap was realized between TI structure and a 6 mm thick structured low iron glass pane. The outer timber profile carrying the glass panes was connected to the inner profile by plywood. However, only about 30% of the area between inner and outer timber profile are covered by plywood.

The TI facade elements have a width of 0.72 m at the edge and 1.05 m in-between. The heights of the elements varies between 0.51 and 5.04 m depending on the windows of the TI facade. Due to the fact that a transparent insulation material with a relatively high moisture uptake is used, a diffusion open TI facade system was realized. Fig. 4 reveals the openings (air-holes) of the TI facade. The openings with a thickness of 3 cm are positioned at the bottom and at the top of the air gap between the glass pane and the TI structure of each element. The air-holes span the whole element width. To prevent insects and infiltration of polluted air into the TI facade the openings are covered by a perforated metal plate and a fleece.

To evaluate the TI facade system, a measuring concept for solar irradiation, other climate data and the yields to be expected in the demonstration object was developed and realized in cooperation with the Arbeitsgemeinschaft ERNEUERBARE ENERGIE. A testing field of about 1 m2 was implemented, made of 25 cm thick concrete and insulated against the surrounding wall with 5 cm thick foam glass. The testing field was positioned in the middle of the TI fagade near the window at the bottom. Whereas for the testing field a stapled TI structure was used, in the other elements of the TI facade rolled structures were installed. The testing field was equipped with various temperature, solar irradiation, heat flux and humidity sensors. Temperature and heat flux sensors were positioned at the inside, the middle and the outside of the concrete wall. To record temperature and humidity within the TI facade element temperature and humidity sensors were installed in the TI structure, in the air gap and at the glass pane. The sensors were positioned in the middle of the testing element. Solar irradition was measured at the top of the testing field using various sensors (to detect shading effects).

Optical characterization

The optical reflectivity of a laser beam is measured continuously during the film deposition in order to determine the deposition rate and the optical constants n and k at one wavelength. The analysis of the data is performed using the reflectivity formula of a single layer on the substrate for the numerical fitting [15]. The experimental set up involves an incident laser beam at 532 nm and the detection of the reflected intensity with a synchronous modulator [16].

Spectroscopic ellipsometry is a non-destructive optical measurement of the polarization change occurring when the incident light interacts with layers. The two ellipsometric functions A and ‘Fare measured at each wavelength across the spectral range of interest of the reflected light. The optical constants n and k and the thicknesses of any individual thin films inside a multilayer coating are determined from a model-based regression limited to the experimental available data. For this reason, ellipsometry is performed at different angle of incidence. The films on silicon substrates with its native oxide are subjected to ellipsometry measurements, performed by ellipsometer (SENTECH SE 850) in the range of 300 — 850 nm with variable angle of incidence ranging between 40° and 70° by steps of 10°.

The total hemispherical reflectivity at 7° angle of incidence and transmission at 0° angle of incidence measurements in the UV, VIS and NIR are performed on a Varian Cary 5 spectrophotometer.

Silicon wafers have been used as a substrate for in-situ real-time laser reflectometry and ex-situ ellipsometrywhile glass substrates have been used forex-situ spectrophotometry.

STRUCTURE OPTIMIZATION ACCORDING TO A 3D MODEL APPLIED ON EPITAXIAL Si SOLAR CELLS

K. Kotsovos

Institute of Microelectronics, NCSR Demokritos, 153 10, Athens, Greece V. Perraki

Department of Electrical and Computer Engineering, University of Patras, GR 26110 Patras, Greece, email:perraki@ee. upatras. gr

ABSTRACT

This paper presents a three-dimensional (3D) theoretical model of n+pp+ type epitaxial solar cells, illuminated on the n+side. The solution, by the Green’s Function method, is 3D analytical expressions in form of convergent series. The final aim is determination of the best device parameters through a computer program, in order to obtain cell performance as close to the optimum as possible. A number of cells made from upgraded metallurgical grade polycrystalline substrates, boron doped and free from transition metal impurities have been studied and their spectral response is interpreted in terms of this model. To optimize such polycrystalline Si solar cells the influence of certain parameters such as the thickness of the diffusion region and the variation of grain size and grain boundary recombination velocity on spectral response and white light photocurrent are crucial. A comparison, among one­dimensional and three-dimensional results is shown. Further elaboration is needed in order to investigate other characteristic parameters such as the open — circuit voltage and the fill factor.

1. INTRODUCTION

Efforts made for increasing the conversion efficiency and reducing the fabrication cost of solar cells have necessitated the study of the influence of certain parameters on the performance of solar cells.

We have already [1] introduced a simplified three-dimensional (3D) analytical model in order to simulate the effect of grain size, grain boundary recombination velocity and epilayer thickness on spectral response and photocurrent of epitaxial solar cells.

The cells have been fabricated by CVD (Chemical Vapour Deposition) [2] on wafers from impure polycrystalline silicon with columnar grains. The generated strong BSF by the low/high junction is taken into account and expressions for the photocurrent densities are obtained, resulting from solutions of the diffusion equation solved in 3D. The model is based on the superposition principle and the variables’ separation technique applied on the minority carrier transport equations. Taking into account the action of the grain boundaries, the back contact recombination velocity, bulk recombination, grain size and the illumination level we optimize cell thickness. A computer program has been developed in order to perform optimization of cell parameters during a procedure in which the parameters considered are adjusted through a systematic method, respecting their interaction.

Finally a comparison, among 1D [3], 3D and previous extracted experimental results [2] of photocurrent, is performed.

2. MODEL

The epitaxial n+pp+ type solar cell (figure 1) is divided in four main regions (front layer, SCR, epilayer, and substrate). According to this model the thicknesses of these regions are d1-wn, wn+wp, d2-wp, d3, respectively.

The following considerations have been introduced, in the framework of a realistic approach, in order to simplify our model:

i) The polycrystalline silicon grains are assumed as columnar and perpendicular to the n+/p junction (as a result of the ingot preparing technique). They have homogeneous physical and electrical properties (doping, mobility and diffusion length of minority carriers) along the three dimensions, for each region and the grain boundaries are considered as surfaces of a very small width compared to the grain size, characterized by a distribution of interface states.

ii) The effects of other imperfections of the crystal structure are ignored.

iii) The absorption coefficient a(A) is given by Runyan [4] for this type of material, while the reflection coefficient R(A) is calculated [5] for a single layer TiO2 anti reflective coating of optimal thickness 77 nm. There is a metal coverage coefficient of 13.1%, corresponding to the front metal grid.

iv) The p/p+ junction is considered a low/high junction, incorporating a strong BSF, assuming that the p+ region’s contribution to the total photocurrent is negligible [6].

v) The front and the back surface recombination velocity SF and SB respectively and the series resistance Rs, are the same as in [1]. The effective grain boundary recombination velocity is assumed constant all over the surface of the grain and has been estimated to vary from 102 to 106 cm/sec [7] depending on the interface states density at the grain boundary and the doping concentration of the semiconductor material.

The excess minority carrier density is obtained by solving the three-dimensional diffusion equation in each region. The steady state continuity equation for the front layer is expressed by

where pn-pn0 is the hole concentration, Lp is the minority carrier diffusion length, Dp is the corresponding diffusion coefficient and F is the light generation rate. The previous equation is subjected to the following boundary conditions

d(P"rl Pn0 } = D^(Pn — Pno ),z = 0

dz Dp

(2)

Pn — Pno = 0,z = di — wn

(3)

8(Pn~xPn0) = + D4Pn — Pno ),x = ±Xg

(4)

d(Pn~Pn0) = + Dl(Pn — Pno ),y = ±Yg

dy DP я

(5)

where SF is the front surface recombination velocity and Spg the grain boundary recombination velocity in the front region.

The diffusion equation for the base region is formulated in a similar form as in the front layer:

where Sng is the grain boundary recombination velocity in this layer and Seff is the effective back surface recombination velocity due to the low high junction as described previously. Since the substrate is considered heavily doped, the following relation gives the expression for Seff

where Nr is the substrate doping, Dn* and its minority carrier diffusion coefficient and diffusion length respectively.

In order to simplify the calculations the grain boundary recombination velocity in the front and active layer is considered the same and symbolized as Sgb.

Using the mathematical treatment previously described in [8], the analytical expressions of Jp, Jn representing the photocurrent density of the front and the active layer are calculated in the model, while the contribution from the Space Charge Region is calculated from the 1D model [3].

New links with external programs: EES[5], Excel or Matlab

New Types that link TRNSYS with EES, Excel or Matlab are now available in TRNSYS 16. To allow for such models to be included in TRNSYS simulations it was necessary to create components in the TRNSYS code that explicitly link to the external programs, execute the models and provide some method of data transfer between the programs. These components work by having TRNSYS call the external program at each iteration. Especially the link to Excel is really a powerful feature cause it allows to communicate in a TRNSYS- Simulation quite easy with real system components like a controller over the Excel API — Interface like it was shown in [6].

Improved numerical precision and "time definition"

All variables in TRNSYS16 are now double precision numbers. This leads to an improved numerical accuracy, which is measurable for example by the very small time steps achievable in TRNSYS 16 (down to 1/100th of a second). This allows to simulate the real behavior of controllers Programming new Types is also easier thanks to the consistent use of double precision.

Enhancements to the TRNSYS solver

A new numerical solver has been added to TRNSYS. The new solver is intended to replace the default solver (successive substitution) in special cases with a strong feedback without a sufficient capacity in the system. A typical case is natural ventilation simulation, where a strong coupling exists between temperature and airflows. The new TRNSYS solver is hence similar to the solver implemented by EMPA in TRNFLOW, the extended Type 56 with integrated airflow modeling.

Other usability enhancements

The equations can now be declared in any order in a TRNSYS input file. New functions have also been added to TRNSYS equation processor The TRACE command can be used for equations

Equation solving can now be done to within a TOLERANCE instead of being absolute, aiding significantly in convergence.

A timer routine is available to identify the routines where TRNSYS spends most of the simulation time

Conclusions

TRNFLOW is a tool which allows an easy calculation of natural ventilation, passive night cooling, double facades and exhaust air shafts quite fast.

No new input file structure or user interface has to be learned. Using PREBID 5 simply the known user-friendly user interface has been expanded.

The newly-developed internal solver is featured with high stability. Due to integrated automatically optimization of convergence the user is no longer bothered with numerical questions.

In TRNSYS version 16, the capability of TRNSYS to adapt to new types of simulation problems has been pushed beyond new limits: Writing a component in any programming, copying the DLL provided by the model author onto the hard disk is sufficient to run it! Several new Types have been added, including a type for the link between TRNSYS and Matlab as well as a link to EXCEL. The window model of the building has been improved and treats now visible and nonvisible sunlight according to the spectral data of the window. A model for chilled ceilings has been added to the building.

Characterisation of the photoelectrochromic devices

To characterise the kinetics of the colouring and bleaching processes during illumination and bleaching in the dark, we needed to have an experimental set-up which measures the transmittance in the same way in both cases. For this purpose, we developed the set-up illustrated in fig. 2. A halogen lamp illuminates the photoelectrochromic sample, and the intensity of the transmitted light is detected by a silicon photodiode. The light intensity of the halogen lamp on the surface of the photoelectrochromic cell corresponds to 1 sun (1000W/m2), taking into account the mismatch factor of dye solar cells. The two electrodes of the photoelectrochromic device are connected via a variable shunt resistance and a switch. For all configurations, the TiO2 layer is always directed towards the lamp, so that the colouring of the Wo3 does not alter the light intensity on the TiO2.

Fig. 2: Experimental set-up to characterise the kinetics of the colouring and bleaching process. T: transmittance, U1: corresponds to the current with switch closed, U2 corresponds to voltage with switch open. The TiO2 layer faces toward the lamp. The filter is either in position 1 (cell illuminated) or in position 2 (cell in the dark).

The shunt resistance was chosen to be 10 Q, which is similar to the resistance of the TCO layer. With this construction, the voltage in the open circuit state and the current in the short circuit state were measured. For the dark state, an optical filter was placed between the lamp and the sample. This filter absorbs all the light with wavelengths below 715 nm. Above this wavelength, the dye is not sensitive and no electrons are excited, as we demonstrated by spectral response measurements. It was necessary to install several collimators in order to suppress scattered light from the environment. For the illuminated state, the filter was removed and placed between the sample and the photodiode detector. In this way, the optical signal is the same for both filter positions, and the transmittance signals for the dark and illuminated states are equivalent.

The measured value of the transmittance is a convolution of the spectra of the halogen lamp, the filter and the photodiode. In order to calculate the visible (or solar) transmittance from the measured value of the transmittance, the set-up was calibrated in the following way: A special PEC device was coloured to different extents by applying different voltages (0V, 0.3V, 0.4V, 0.5V, 0.6V, 0.7V) for 30 min, so that an equilibrium state was achieved. While holding this voltage with the potentiostat, the transmittance was measured with our set-up and immediately afterwards with the spectrometer which recorded the spectrum between 320 and 2000 nm. From these spectra, the visible (and solar) transmittance and
optical density were calculated. The visible (solar) optical density plotted versus the optical density determined with our set-up shows a linear dependence to a good approximation. A linear fit gave a simple equation to calculate the visible (solar) optical density from the values determined with our set-up.

These calibration measurements were made with a special PEC cell which was made without the dye. Coloured by an external voltage, this special cell has the same transmittance spectrum as the normal PEC cell coloured by illumination, because the amount of dye in the normal cell is very low. Using this special cell for the calibration had the advantage that the measured transmittance is not influenced by the different lighting conditions inside the spectrometer and in our set-up.

The condition for this calibration is that the form of the transmittance spectrum is independent of the depth of coloration. This condition is fulfilled because the dependence of the optical density on the charge is linear: The coloration efficiency is independent of the intercalation degree x [8]. On the other hand, the optical density OD represents the intercalation degree x (x: ratio of electrons and Li+ cations per W-atom in the Wo3):

Long-duration transmittance measurements of self-bleaching in the dark under open circuit conditions were made with a light-emitting diode with an intensity maximum at a wavelength of 655 nm without any filters. This light-emitting diode was switched on once every minute for a short measurement so that it did not influence the coloration of the photoelectrochromic device.

Transmittance spectra were measured with a Perkin-Elmer 330 Spectrometer.

Comparison of Heat and Mass Transfer. in Three Adsorption Solar Reactors

AROUDAM El Hassan

Department of Physics,

Faculty of Sciences B. P. 2121 — Tetouan — Morocco
Fax: (212) 39 99 45 00, E-mail: Aroudam_hass@Hotmail. com

Abstract

The performance evaluation of 1 m2 area of three type of adsorption solar reactors used in refrigeration are presented. The numerical computation results are obtained relatively for four typical sunshine days characterized by a maximal solar radiation measured locally and shows that both the cycled mass of refrigerant and the thermal performance coefficient of each machine are functions of the height of the porous medium and they are very depending on the meteorological data.

The effect of fins, the offered volume in the porous medium and the meteorological conditions are analysed and shows that the performance of machine is important for the month of April corresponding to some diurnal and nocturnal temperature and a solar radiation favourable for an application. A two-dimensional distribution of temperature and concentration of fluid inside the rectangular configuration is also presented along a daily cycle. The physical model adopted use the mass and heat balance equations and the Dubinin — Radushkevich formula for the determination of fluid desorbed fraction in each element of the discretised medium of the porous medium at a constant pressure.

Key Words: Adsorption — cooling machine — Solar reactor — Ammonia — Activated carbon

1. Introduction

The product of cooling energy by applying solar energy in the isolate site favoured by solar radiation present mainly a great interest. These are very important if the solar system used is very sample and not need a mechanical organ. An application suitable use the systems of adsorption phenomena between a solid and gas for ice production or refrigeration. They differ to other machine by the functioning mode of the collector, which represents the motor organ of the machine. The principle element which represents the thermal motor functioning by adsorption / desorption mode between a solid and a vapour under temperature — pressure variation, allowing to circulate a refrigerant fluid through tubes connecting different elements constituting the machine in the course of a daily cycle. The performance deduction of this machines type is very important by report to the case of absorption cooling machines. The efficiency depends strongly on the expressions of the produced energy quantity and that offered to the system. In the order to improve the performance, many researchers are developed and studies rigorously each component of the solar machines in the aims to enhanced the efficiency. Several experimental and theoretical works have been presented, they focus the objects on the heat transfer, thermal regeneration, the couples thermo physical characteristics, the effect on the environment, recourse to the new mixture, etc [1-12].

The interest of adsorption refrigerator application are increased when new other adsorbent are used such the active carbon fiber (ACF); substitute for activated carbon [13,15]. In this work, we focus on the numerical study of the daily evolution
of temperature, fluid mass and the pressure inside a solar reactor, submitted to real solar radiation data recorded locally. We propose to compute and compare the performances of three solar cooling machines considering rectangular and cylindrical reactors, with and without fins, in order to characterized the obtained cycles under real weather conditions.

We describe solar adsorption cooling machine using ammonia / activated carbon couples and the Dubinin-Raduskevich formula [16] for determination the adsorbed mass of ammonia, and to present a numerical distribution of temperature and adsorbed mass, versus time, inside a reactor heated by variable solar flow. A good design of elements of the compatible machine with the ambient medium, the heat source and the functioning mode allow to improve the efficiency of the refrigerator.

Chromaticity Coordinates

The perceived color is a very important property for architectural windows, including “smart” ones [9]. Quantitative assessments can be performed in several different ways; here we employ the CIE Colorimetric System [20,21]. The purpose of colorimetric analysis is to give color specifications for observers with normal vision in terms of tristimulus values or chromaticity coordinates. The ideal observer’s color matching functions are denoted x, y, and z, and represent red, green, and blue primaries, respectively. One can describe any color as an additive mixture of these. The y curve is chosen so that it coincides with the luminous efficiency of the light — adapted eye. The CIE 1964 tristimulus values corresponding to a certain color stimulus Ф(А) are obtained from

j" x (A W (A )dA *aE = j 7 (A)S (A )dA

and analogously for Vcie and Zcie. The color stimulus of present interest is

V(A) = S(A)T(A) (4)

where S(A) is the relative spectral irradiance function. Chromaticity coordinates, denoted x, y, and z, are then obtained from

X =——————— ^CIE——————— ^ (5)

XCIE + VCIE + ZCIE

and correspondingly for y and z. These formulas lead to the chromaticity diagram shown in the lower parts of the various panels of Figs. 3 and 4. Any color can be represented as a point within the shown boundary. The chromaticity coordinates for a colorless (achromatic) material are x = y = z = 0.333.

The chromaticity coordinates were calculated for four different standard illuminants representing a chosen set of light sources. Illuminant D65 signifies the average north sky daylight at 6500 K, illuminant A represents a tungsten halogen incandescent light

source at 2856 K (typical home or store accent lighting), illuminant F11 pertains to a commercial rare-earth-phosphor narrow-band fluorescent light source at 4000 K (used in Europe and the Pacific Rim for typical office or store lighting), and illuminant F2 represents a commercial wide-band-fluorescent cool white light source at 4150 K (typical office or store lighting in the U. S.A.).

Figure 3. CIE chromaticity diagrams representing the color of optimized electrochromic nickel-oxide-based films in fully bleached and colored states under daylight illumination (CIE D65; panel a), incandescent illumination (CIE A; panel b), narrow band fluorescent illumination (CIE F11; panel c), and cool white fluorescent illumination (CIE F2; panel d). Coordinates signifying the illuminant as well as colorlessness (i. e., the achromatic point) are plotted as a reference. The upper part of each panel is a magnification of the central region of the lower part. The designation NiXO (with X being Mg, Al, Si, V, Zr, Nb, Ag, or Ta) indicates that X is present in the oxide but does not specify the amount.

Figure 4. CIE chromaticity diagrams representing the color of optimized electrochromic iridium-oxide-based films in fully bleached and colored states under daylight illumination (CIE D65; panel a), incandescent illumination (CIE A; panel b), narrow band fluorescent illumination (CIE F11; panel c), and cool white fluorescent illumination (CIE F2; panel d). Coordinates signifying the illuminant as well as colorlessness (i. e., the achromatic point) are plotted as a reference. The upper region of each panel is a magnification of the central part of the lower part. The designation IrXO (with X being Mg, Al, Zr, or Ta) indicates that X is present in the oxide but does not specify the amount.

Figure 3 shows chromaticity coordinates for the optimized nickel-oxide-based thin films reported on in Fig. 2(a) under CIE standard illuminants D65 (panel a), A (panel b), F11 (panel c), and F2 (panel d), respectively. In panel (a), the data pertaining to the bleached state lie very close to the point representing colorlessness for illuminant D65. The data for the colored state are rather scattered, with the chromaticity depending on the specific additive. Also the trajectories in color space between the bleached and colored states are different for each of the additives. Another characteristic of the bleached state is that the dominant wavelengths are short so that the eye has less sensitivity. The chromaticity coordinates for the incandescent light, reported on in panel (b), indicate a light yellow color in the bleached state and a yellow-green color in the dark state. The data points for the bleached state appear less dispersed than the corresponding points for D65. For fluorescent lights, represented in panels (c) and (d) for narrow-band fluorescent and cool white fluorescent light sources, respectively, the data are similar and dispersed as regards the dark states. The films show a green-yellow color in the bleached state.

Figure 4 shows analogous chromaticity coordinates for the iridium-oxide-based films. From panel (a) it can be seen that the films, in both colored and bleached state, have chromaticity coordinates close to the achromatic point, and they are therefore almost colorless. Their dominant wavelength changes significantly from greenish blue to green, but the chromaticity remains close to the achromatic point. With the incandescent illuminant, for which panel (b) is appropriate, the color coordinates indicate that the films appear yellowish-orange to orange, and the color is more evident than for the daylight illuminant. In fluorescent light, panels (c) and (d) show that the films appear close to yellow. On the whole, it can be stated that the chromaticity coordinates for the iridium-based oxide films do not change to the same extent as the coordinates for the nickel-based oxide films. It can also be noticed that the iridium-based film that changes the most is the one containing Mg, while the film with the least change in color is comprised of pure iridium oxide.

Figure 5 shows Vqie, which corresponds to the luminous transmittance. The results in panel (a) are entirely consistent with those in Fig. 2(a). Films of nickel oxide mixed with Mg and Al show as much as 85 % luminous transmittance, whereas films containing Si and Zr yield up to ~83 %. For additives of Nb or Ta, the transmittance can be ~80 %. The case of the vanadium admixture is different, though, and shows a luminous transmittance not exceeding 75 %, i. e., lying ~4 % below the value for pure nickel oxide. Generally speaking, the luminous transmittance shows a rather weak dependence on the specific illuminant.

Panel (b) in Fig. 5 shows luminous transmittance of iridium oxide films mixed with Al, Mg, Ta, or Zr. Excepting the Zr-containing film, the additives lead to an improved luminous transmittance in the bleached state. Al and Mg rises the luminous transmittance to ~83 to 84 % from the initial 79 % of pure iridium oxide, while the Ta — containing film has a luminous transmittance of ~82 %. Zr, on the other hand, lowers the luminous transmittance by ~4 % due to a higher reflectance; thus such a film unsuited for applications requiring high transmittance.

Conclusions

We have shown that electrochromic nickel-oxide-based films can display enhanced short-wavelength transmittance in the bleached state when Mg, Al, Si, Zr, Nb, or Ta was added. However, admixtures of transition metals such as V and Ag did not improve the optical properties of the films. The colored state was not strongly affected by any of these additions. Larger admixtures are likely to change color, though, as one may infer from an analogy with mixed tungsten-based oxides [1,22]. Iridium-oxide-based films show improved transmittance in their bleached state when mixed with Al, Mg, or Ta, but not when mixed with Zr.

Acknowledgements

This work was supported by the Swedish Foundation for Strategic Environmental Research and the National Energy Administration of Sweden. E. Avendano gratefully acknowledges a scholarship from the University of Costa Rica to complete his Ph. D. work at Uppsala University.

Performance of the TI wall heating system

During the heating periods 2002/03 and 2003/04 excellent results were obtained for the realized TI facade. The maximum temperatures of the absorber and of the indoor wall surface were about 75 and 30°C, respectively. During a cold and sunny week in January 2002 heat gain fluxes of up to 50 W/m2 were measured. The evaluation of the optimized TI wall according to van Dijk et al. [6] is illustrated in Fig. 5, showing performance charts, on a weekly and 4-weekly (monthly) basis, obtained from August 2002 until April 2003 (2002/03) and from August 2003 until March 2004 (2003/04). The equivalent U-value (Ueq), which is the ratio of the net heat flux through the wall divided by the temperature difference between indoor and outdoor is plotted versus the degree-day related irradiation, which is the daily sum of irradiation on the wall divided by the degree-day. Only in December 2002 a small monthly heat loss was obtained. Due to relatively high solar irradiation in December 2003, for all months of the heating period 2003/04 monthly heat gains were obtained. The linear regression of the data points yielded a solar energy efficiency of about 43% and a U-value ranging from 0.74 to 0.79 W/(m2K), which are outstanding values compared to data of various TI walls given in [7]. Comparing the TI wall performance of the two successive heating periods it can be concluded, that the air-openings of the TI elements work properly and that no adverse pollution of the TI facade or material

2003/04 (right)

Special attention was given to the evaluation of the hygro-thermal performance of the TI wall system. Although CTA absorbs a high amount of water no adverse condensation phenomena within the TI facade was observed visually during the investigated heating periods. These findings may be attributed to the diffusion-open construction of the TI facade based on timber profiles with minimized material fraction, to the large airgap between glass pane and TI structure and to the fact, that the pre-painted wall was in use two years without transparent insulation, which enabled the wall to get dry.

Fig. 6 shows the weekly averaged values of the ambient and room temperature (top layer), the calculated weekly maximum values of the relative humidity at the glass pane (middle

layer) and the weekly averaged values of the ambient and air gap water vapour pressure (bottom

layer). The maximum weekly averaged values of the room temperature (28°C) were observed in August 2003. These findings are related to the fact, that efficient shading of the TI facade is provided from May to July. In August the shading effect is relatively poor. Furthermore, August 2003 was an unusual warm and sunny month. The calculated weekly maximum values of the relative humidity at the glass pane clearly indicate, that during the whole measuring period never 92% were exceeded. Thus, no adverse condensation was observeable. A detailled analysis showed, that the maximum values of the relative humidity at the glass pane (above 90%) mainly occur during clear and cold nights at the end of cloudy periods with very poor irradiation in winter time (e. g., December 2002). The plot of the weekly averaged ambient water vapour pressure and the water vapour pressure in the air gap of the diffusion-open TI facade indicates, that the moisture exchange with the environment is quite good. Furthermore, it can be seen, that the maximum values of ambient water vapour pressure exceed the vapour pressure in the air gap. This phenomenon can be related to the fact, that the testing field is positioned in the middle of the TI facade element. Humidity entering the TI element at the bottom is absorbed by the cellulose acetate TI structure at the bottom. Whereas in sunny periods the desorption of water vapour from the TI structure is rather quick, in periods without irradiation the water vapour adsorption takes a long time.

RESULTS AND DISCUSSION

3.1 LaserReflectometry

The reflectivity data at 532 nm were monitored as a function of time during the deposition of TiO2, SiO2and Al2O3 films on silicon substrates using the laser light polarization parallel to the incidence plane.

The obtained curves can be interpreted in a qualitative way. The experimental curves show oscillations with constant amplitude, indicating the transparency of the film. Hence, the extinction coefficient k at 532 nm is zero as expected. A quantitative determination of the optical constants is done by numerical fitting of the experimental data using the reflectivity formula of a one layer on substrate model. In a straightforward way, in-situ laser reflectometry fits provide the growth rate vd, the refractive and extinction indexes at one wavelength (532 nm) as summarized in table 1.

n

vd [nm/min]

TiO2

2.2

1.2

SiO2

1.47

7.6

A^O3

1.5

25

Table 1. Optical constants and deposition rate of TiO2, SiO2 and Al2O3 thin films using laser reflectometry.