See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/3520492 Weathering degradation of EVA encapsulant and the effect of its yellowing on solar cell efficiency Conference Paper · November 1991 DOI: 10.1109/PVSC.1991.169275 · Source: IEEE Xplore CITATIONS READS 40 1,940 4 authors, including: Keith A. Emery National Renewable Energy Laboratory 310 PUBLICATIONS 27,975 CITATIONS SEE PROFILE Some of the authors of this publication are also working on these related projects: Daido Steel View project All content following this page was uploaded by Keith A. Emery on 04 June 2014. The user has requested enhancement of the downloaded file. WEATHERING DEGRADATION OF EVA ENCAPSULANT AND THE EFFECT OF ITS YELLOWING ON SOLAR CELL EFFICIENCY FJ. Pern, A.W. Czanderna, K.A. Emery, and R.G. Dhere National Renewable Energy Laboratory (formerly the Solar Energy Research Institute) Golden, Colorado ABSTRACT The encapsulant materials provide optical coupling, mechanical support, electrical isolation, physical isolatiod protection, and thermal conduction for the solar cell assembly (43). EVA copolymer (33% vinyl acetate) is extensively used for crystalline Si-based PV module encapsulation. EVA is formulated and processed to provide the desired mechanical strength and stability (43). The processed EVA contains a 65% to 70% gel content (degree of cross-linking), 0.30 wt % Cyasorb W 531 (a UV absorber identified as "Cyasorb" here), and two antioxidants(4-6). Upon weathering degradation, the EVA between the cover glass plate and solar cells in PV modules may become discolored. In previous papers, we studied the structuraleffects and relationship among the extent of degradation,gel content, and Cyasorb concentration in EVA (6,7). In this paper, we emphasize more the effect of EVA yellowing on the solar cell efficiency. After five or more years of weathering, the degradation of ethylene-vinyl acetate (EVA) encapsulant in photovoltaic (PV) modules resulted in a yellow to dark brown color. Degraded EVA shows a substantial increase in the gel content and a large to complete loss of the ultraviolet (UV) absorber, Cyasorb UV 531. The EVA discoloration is caused by the formation of polyconjugated (C=C), double bonds of various lengths. Acetic acid and other volatile organic components are also produced from the photothermal decomposition of the EVA. The solar cell efficiency was reduced by -9% by a light yellow brown EVA and -50% by a dark brown EVA. Weathered PV modules with dark brown EVA also show a -50% decrease in efficiency. EXPERIMENTAL INTRODUCTION EVA Materials and Analvtical Procedure In the past two decades, significant improvements in the efficiency and reliability of new semiconductor materials for PV devices and modules have resulted in PV becoming an increasingly viable energy alternative. While efficiency improvements in large-area CuInSq, CdTe, and a-Si-based thinfilm PV modules are increasingly promising, single-crystal (and polycrystalline) Si-based PV modules have been the most dominant products widely used. Typical efficiencies of these PV modules range from about 11% to 14% (1). A long-term stability of over 20-30 years for all types of PV modules is one of the requirements to be cost-competitive. The EVA materials we studied, our analytical procedures, and the analytical instruments we used are essentially the same as those reported previously (6,7). The laminated and cured EVA in PV modules that are stored in the dark for six years remains clear. Clear and discolored (degraded) EVA samples were cut from PV modules weathered outdoors for more than five years. The Cyasorb concentration (wt %) and gel content (%) are the two crucial measurements of EVA degradation (6). Measurement of the Effect of EVA Yellowing on Solar Cells Efficiencv However, some Si-based modules deployed outdoors for five years or more develop a light yellow, to yellow-brown, to dark brown color, depending on their locations, use temperature, and configuration. A common factor in these discolored modules is their use of EVA films as the encapsulant. The consequence of the EVA weathering degradation can be significant. For example, Gay and Berman reported that EVA browning resulted in a -30% loss in the annual energy output from the six-megawatt PV systems at the Carrisa, California, power plant (2). A detailed study on the module performance of the Canisa PV systems revealed that the EVA degradation is highly nonuniform from module to module, and that the aveme module power output is 35.9%below that of the initial rating (3). The mismatch between neighboring modules, caused by nonuniform EVA degradation, contributed an additional power loss of 11.1%. The effect of EVA discoloration on solar cell efficiency was evaluated as before (6), using a calibrated SpectrolabX-25 solar simulator. Quantum efficiency (spectral response) was measured on a computerized system with periodic (440 Hz) monochromatic light directed through one of an array of 10nm band-pass interferencefilters. The lower wavelength limit was 290 nm. In both cases, the virgin or degraded EVA films were pressed above the reference solar cells with or without adding a cover glass above the film. Similar measurements were also performed for a solar cell specimen (26 cm2) taken from a broken PV module. The I-V performance of three large PV modules was measured on a Spire Model 240A solar simulator. 557 CH2953-8/91/0000-0557$1.00 0 1991 IEEE Authorized licensed use limited to: National Renewable Energy Laboratory. Downloaded on February 10, 2010 at 15:17 from IEEE Xplore. Restrictions apply. RESULTS AND DISCUSSION Virgin cured EVA Exposed EVA & t t unexposed, clear + clear + light-yellow- yellow-brown (acetic acid+) + EVA Degradation and Discoloration I Figure 1 shows the results obtained from analyzing a large number of non-degraded and field-degraded EVA samples. The gel content increased substantially from 65%70% in virgin EVA to 85%-88%in clear degraded EVA, to 90%-92% in light yellow EVA, to 96%-97% in yellow-brown and dark brown EVA, while the Cyasorb concentration decreased concomitantly during the degradation process. No Cyasorb was observed in the extensively degraded EVA. When the Cyasorb concentration dropped below about 0.21 wt %, the EVA films became discolored (6). As the extent of degradation increased, the color darkened from light yellow, to yellow, to yellow-brown, and to dark brown. The EVA degradation across each solar cell unit on weathered PV modules was not uniform. The Cyasorb concentration was much lower and the gel content was higher in EVA from over the central region than from over the cell edges (6,7). No noticeable change in either the gel content or the Cyasorb concentration was observed in EVA samples taken from unweathered modules from similar locations. The EVA mostly remained clear around the cell edges and in the areas between neighboring solar cells. In addition to the discoloration,acetic acid and volatile organics were present in the degraded EVA. I - 100 - 90 - 80 K/ , ,I I \ \ -I Clear Yellow , \ \ - 70 Figure 1. The Cyasorb UV 531 concentration, gel content, and EVA color at different extents of degradation, summarized from the results of analyzing a large number of undegraded and field-degraded EVA samples. The actual degradation is not known except for the virgin EVA. Figure 2 compares the transmission spectra for virgin and degraded (to various degrees) EVA samples. As the color on the EVA darkens, more UV and visible light is absorbed. The yellow-browning of degraded EVA is caused by the formation of polyconjugated carbon-carbon double bonds (polyenes) (6,7). The discoloredEVA luminesces strongly upon illumination by UV and visible light. In fact, the extent of EVA degradation can be detected directly using fluorescence analysis from the shift in the emission peak position (from shorter to longer wavelengths in the 500-650 nm region) and the increase in peak intensity (6,7). Intense acetic acid odors and other volatile organic components were detected when the weathered PV modules were cut open. The presence of acetic acid is significant. In various simulated degradation experiments, acetic acid was produced from EVA exposed to UV light at 45°C or heated in the dark at 130°C. Acetic acid has been found to catalyze EVA yellow-browning from 85" to 130°C. A detailed discussion will be given elsewhere (7). Wavelength (nm) In summary, weathering degradation of the EVA encapsulant in PV modules results in an increased gel content, a loss of the UV absorber, a yellow-browning of the EVA, and the production of acetic acid and volatile organic components (6). Figure 2. Transmission spectra measured for (1) a clear EVA film, (2) a light yellow-brown EVA film,(3) a darker yellow-brown EVA film, (4) a brown EVA film, and (4) a darker brown EVA film. Samples #1, #4, and #5 were laminated in two glass plates and exposed to an RS4 sun lamp at Effects of EVA Discoloration on Solar Cell Efficiency 90°C for 1600 h. Samples #2 and #3 were taken from weathered PV modules. The effect of yellow-browning on the light transmission is shown in Figure 2 for samples that are clear to dark brown EVA. The effect of EVA yellow-browning on the electrical performance and quantum efficiency (spectral response) was obtained using single-crystal Si reference cells with and without a degraded EVA sample laid over them. The results are given in Tables 1 and 2(A), respectively. Table 1 gives short-circuit current the measured open-circuit voltage (V,), density (J%), maximum power (PmJ, and calculated loss (%) for two virgin clear and two degraded yellow-brown EVA films. When covered with a virgin clear EVA film, the Si cell However, the loss lost about 6.7% in J, and 0.8% in P,. increased to 12%-14% in J, and 14%-16% in P, with the 558 Authorized licensed use limited to: National Renewable Energy Laboratory. Downloaded on February 10, 2010 at 15:17 from IEEE Xplore. Restrictions apply. are 67%-77% lower than the typical 13%-14% efficiency of new 4"x4" mini-modules made by the same manufacturer. The decrease is 17%-27% greater than the changes measured with dark brown EVA films alone (see Table 2A), suggesting that other factors such as increased series resistance may have also contributed to the efficiency drop. This argument seems to be supported by a f i i factor of about 0.50 as compared to a fill factor of about 0.70 for new mini-modules. The relative spectral responses measured for the variously degraded EVA samples are compared in Figure 4. yellow-brown EVA films. The loss in V, was relatively small. In effect, the Si cell's 11.6% efficiency changed to 10.7% with the virgin EVA and 9.7% with the yellow-brown EVA; this corresponds to a net loss of 9.3% of its original efficiency when the EVA color changed from clear to yellowbrown. These effects also appear clearly in the relative quantum efficiency ratios to the bare Si reference cell, as shown in Figure 3. The spectral responses for the two virgin cured EVA films are virtually identical, with a cutoff below 360 nm from the absorption of Cyasorb. For the two degraded yellowbrown EVA films that differ slightly in color, the spectral responses begin at about 290 nm because of the absence of Cyasorb. Because of light absorption by polyenes, the spectral response is lower between 360 and about 900 nm than that of the virgin EVA (Figure 2, curves 3 and 4). Table 1. Effect of EVA Yellowing on the I-V Performance of a Single-Crystal Si Reference Solar Cell' As the EVA color became dark brown, the change in measured cell efficiency increased. Table 2(A) shows the results obtained for two dark brown EVA samples with or without a 7059 glass plate pressed tightly onto the EVA over the reference Si cell. For comparison, a solar cell specimen taken from a broken PV module with dark brown EVA was also similarly analyzed. With the dark brown EVA, a nearly 50% loss in PmUwas observed; this is -35% greater than that for the yellow-brown EVA seen in Table 1. The large difference is simply because the dark brown EVA absorbs more UV and visible light (Figure 2) than does the yellow-brown EVA (6,7). The presence of a cover glass plate reduced the P,, an additional 2%. For the solar cell specimen, the measured efficiency for the three tape-defied areas ranged from 3.0% to 4.4% (see Table 2B), further supporting our earlier conclusion that the degradation of EVA is non-uniform across the cell surface (6). More importantly, the measured efficiencies Sample EVA (VI No EVA 0.474 A9918 V, PIU, Jffi' Loss (%) in Jffi pm, (mw) vcc 39.87 4.06 -_- --- --_ 0.470 37.21 3.74 0.84 6.67 0.79 15295P 0.471 37.28 3.75 0.63 6.50 o.m Yellow-1 0.466 35.00 3.48 1.69 12.21 1428 Yellow-2 0.465 34.51 3.41 1.90 13.44 16D1 * An aperture of 0.35 cm2was used over a single-crystal Si reference solar cell for the measurements. The EVA film was placed beneath the aperture. No cover @ass was used on top of the cell or EVA. The loss (%) would be slightly larger if a cover glass were used. The P,, loss (%) would be about 7% less than the values shown if they were corrected for the light scattering (see text). Data for Yellow-1 and Yellow-2 are identified as samples #2 and #3 in Figure 3 and Yellow-2 as sample #3 in Figure 4. -1.oo 1 I E f 0.00U 250 450 650 850 1050 1250 Wavelength (nm) 250 Figure 3. Relative quantum efficiency measured for a single-crystal Si reference solar cell covered with virgin clear (curves #1 and #2) and degraded yellow-brown (curves #3 and #4) EVA films. The spectral responses are ratioed to that for the bare Si reference cell. The virgin EVA films are EVA A9918 (curve #1) and EVA 15295P (curve #2). The two degraded EVA films differ slightly in color. 450 850 Wavelength (nm) 650 1050 1250 Figure 4. Quantum efficiency measured for (1) a singlecrystal Si reference solar cell, (2) the cell in (1) covered with virgin cured EVA A9918, (3) the cell in (1) covered with yellow-brown EVA, and (4) a solar cell specimen with dark brown EVA. Curves #1 and #4 are normalized to 100%. Curves #2 and #3 are normalized to curve #1. 559 Authorized licensed use limited to: National Renewable Energy Laboratory. Downloaded on February 10, 2010 at 15:17 from IEEE Xplore. Restrictions apply. Table 2. Effect of Dark Brown EVA on the I-V Performance of (A) a Single-Crystal Si Reference Solar Cell' and (B) a Solar Cell Specimen (A) Two dark brown EVA films peeled from degraded PV modules Loss (%) in (mA/cm2) Pinax (mW) V, J, P, 0.398 22.54 3.54 ---- ---- ---- Brown-1 + slideb 0.347 0.341 13.15 12.64 1.80 1.70 12.81 41.66 49.15 14.32 43.92 5198 Brown-2 0.345 0.343 13.21 12.76 1.79 1.72 13.32 41.39 49.44 13.82 43.39 51.41 Sample EVA V, (V) Si Cell + slideb Jw (B) A solar cell specimen with dark brown EVA' Efficiency P, Fill J, (%) (mA/cm2) (mW) Factor Spot No. Area (cm') (V) 1 0.170 0.330 26.62 0.746 0.50 4.4 2 0.190 0.325 21.62 0.665 0.50 3.5 3 0.163 0.308 20.16 0.489 0.48 3.0 V, ' The results shown in the table are not adjusted for the loss of light transmission through the EVA film due to light scattering from the come Si-side surface. See text for details. Data for Brown-1 are identified as sample #3 in Figure 5(a). A glass plate was pressed tightly on top of the EVA film. An active aperture area of 0.967 cmz was used for the measurements. The solar cell specimen (26 cm2) was taken from a broken PV module with dark brown EVA and the superstrates and substrates intact. The three areas were defmed by black tape. Contacts were made by soldering wires to the front and back buslines. One concem in our measurements of efficiency and spectral response is the accuracy offset by light scattering from the textured surface of EVA films, and the extent of noncoupling between the EVA and the reference Si cell. This concem is particularly important for the dark brown EVA films (used for measurements in Table 2A) that have a coarse surface side after being forcefully removed from the micro-pyramidically etched surface of the Si solar cells. The light-scattering effect was assessed from the integrated reflectance measurements from 250 to 1250 nm for a virgin clear EVA sample, a yellowbrown EVA sample, two dark brown EVA samples (one of them with a coarse Si-side surface as described above and the other with a smoother Si-side surface), and the solar cell specimen. The results are shown in Figure 5. Figure 5(a) shows that the integrated reflectances are nearly identical for the virgin clear and yellow-brown EVA films (about 7%), and double that for the dark brown EVA with a coarse Si-side surface. Therefore, the measured solar cell performance parameters in Tables 1 and 2(A) should be corrected by 7% and 14%-15% of their listed values, respectively. Accordingly, the corrected decrease in solar cell efficiency is -8.6% when EVA changed from clear to yellow-brown and -42% when it changed to dark brown. While the integrated reflectance measured for the solar cell specimen is about 35% lower than that for a dark brown EVA with a smoother Si-side surface (Figure 5b), this small difference is not sufficient to adversely affect the interpretation of results in Table 2. Effect of EVA Discoloration on PV Module Performance The effect of EVA discoloration on module I-V performance was also evaluated for three PV modules of the same type (33 4"x4" cells). The EVA color ranged from light yellow to dark brown. The shunt and series resistances were determined from dark I-V measurements. Table 3 summarizes the results. The original data on the I-V performance and resistances are unavailable, which prevents an accurate interpretation of the data. However, the results seem to suggest that an increase in the EVA yellow-browning is related to a decrease in the shunt resistance and an increase in the series resistance, which in turn results in a corresponding decrease in the fill factor and hence the efficiency. The losses in fill factor and efficiency in the yellow-brown and dark brown EVA modules are about 50% when compared to a typical fill-factor value of about 0.70 and an efficiency of 210% for a new module of the Same configuration. Our results on three modules are in good agreement with the field results obtained at the Carrisa Plains power plant, where EVA yellow-browning caused an average 36% loss in power output (2) and where some modules with mirror-enhanced configuration lost nearly 70% more than average peak power (3). 0.20 t 0.00 250 (a) I I 450 I I 650 I I 850 I I 1050 I 1250 Wavelength (nm) Figure 5. Integrated reflectance measured for (a) a virgin EVA A9918 film (curve #1), a yellow-brown EVA film (curve #2), a dark brown EVA film (curve #3) with a coarse Si-side surface, and (b) a dark brown EVA with a smoother Si-side surface (curve #1) and a solar cell specimen (curve #2). Authorized licensed use limited to: National Renewable Energy Laboratory. Downloaded on February 10, 2010 at 15:17 from IEEE Xplore. Restrictions apply. Table 3. Electrical Performance Measured using a Spire Simulatorand ResistancesDetermined from Dark I-V Data for Three Weathered PV Modules' Mod. EVA ColoP A V, I, (V) (A) It ye1 6.755 7.217 The authors thank R. DeBlasio for his support in this work and S. Rummel and E. Beck for their technical contributions. This work is supported by the Department of Energy 34.0 0.70 9.34 1.35 0.109 yel-bm 6.733 6.428 16.35 0.38 4.49 0.577 0.508 C drk bm 6.137 ACKNOWLEDGMENT ,P Fill Eff. %h, %, (W) Factor (%) (kohm) (Ohm) B 7.047 to about 50%, depending on the extent of EVA discoloration from the degradation. 15.99 0.37 4.41 0.723 under Contract No. DE-AC02-83CH10093. 0.499 REFERENCES ' The three modules were of the same type, and each contains 33 4"x4" 1. J. P. Thomton, R. DeBlasio, and K. Zweibel, Energv Enpineerin& 87, 1990, pp. 63-79. 2. C. F. Gay and E. Berman, Chemtech, March 1990, pp. 182-186. 3. A. L. Rosenthal and C. G. Lane, Proc. PV Module Reliabilitv WorkshoD, Oct. 25-26, 1990, Lakewood, Colorado, SERI/CP-4079, pp. 217-229. 4. C.G. Gebelein, D.J. Williams, and R.D. Deanin, ed., polvmers in Solar Energy Utilization, ACS, Washington D.C., 1983, Ch. 22 and 23, pp. 353-385. 5. E. Cuddihy, C. Coulbert, A. Gupta and R. Liang, FlatPlate Solar Array Proiect Final ReDort. Vol. VII--Module Encapsulation, JPL publication 86-31, DOWJPL-1012-125, 1986. 6. F.J. Pem and A.W. Czandema, Solar Cells, in press. 7. F.J. Pem and A.W. Czandema, to be published. square solar cells. It ye1 = light yellow, yel-bm = yellow-brown, drk bm = dark brown. CONCLUSIONS We have reported that weathering degradation of the EVA encapsulant in PV modules results in an increase of copolymer cross-linking, a large decrease in W absorber concentration, the production of acetic acid, and a yellow to dark brown color. The discoloration results from the formation of polyenes of various lengths. The polyenes absorb UV and visible light and luminesce in the visible region; thus, they may partially compensate for the loss of solar cell efficiency due to reduced light transmission. The light-absorbing nature of polyenes reduces the net solar cell efficiency from about 9% 561 View publication stats Authorized licensed use limited to: National Renewable Energy Laboratory. 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