Angular response of dye solar cells to solar and spectrally resolved light

Daniele DErcole, Lorenzo Dominici, Thomas M. Brown, Francesco Michelotti, Andrea Reale et al. Citation: Appl. Phys. Lett. 99, 213301 (2011); doi: 10.1063/1.3663973 View online: http://dx.doi.org/10.1063/1.3663973 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v99/i21 Published by the American Institute of Physics.

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APPLIED PHYSICS LETTERS 99, 213301 (2011)

Angular response of dye solar cells to solar and spectrally resolved light
1 Department of Electronic Engineering, Centre for Hybrid and Organic Solar Energy (CHOSE), University of Rome Tor Vergata, Via del Politecnico 1, 00133 Roma, Italy 2 Molecular Photonics Laboratory, Department of Basic and Applied Sciences for Engineering, Sapienza University of Rome, Via A. Scarpa 16, 00161 Roma, Italy

Daniele DErcole,1 Lorenzo Dominici,1,2 Thomas M. Brown,1,a) Francesco Michelotti,2 Andrea Reale,1 and Aldo Di Carlo1

(Received 27 September 2011; accepted 4 November 2011; published online 23 November 2011) The power conversion efciency (g) of a dye solar cell (DSC) with a 13 lm thick TiO2 layer increases with solar AM1.5 lights angle of incidence by 10% at 55 6 5 and then decreases at higher angles due to Fresnel reection at the front air/glass interface. For cells with thin TiO2 (3 lm), the enhancement in g is substantially larger (16%). We show, also through spectral quantum efciency measurements, that the angular enhancement for thin cells is mainly due to optical path lengthening, quantifying the relevant parameters useful for photon management C strategies and for understanding the productivity of DSC modules outdoors. V 2011 American Institute of Physics. [doi:10.1063/1.3663973] Standard characterization of photovoltaic (PV) devices is performed at normal incidence. However, PV devices outdoors receive photons that rarely hit their surface at normal incidence, due to differing placement upon installation and daily and seasonal variations of the suns position. Angular measurements of power conversion efciency (g) have been carried out for different PV technologies.14 Recently,5,6 a strong enhancement of short circuit current ISC with angle of incidence of a laser beam was shown for dye solar cells (DSCs).7 DSCs possess intriguing properties such as transparency and color tunability and good performance retention at different conditions of illumination.8,9 Thus, it becomes important to carry out systematic angular studies of g and incident photon-to-current conversion efciency (IPCE) of DSCs given their potential in yielding good performance under diffuse light and in terms of daily and yearly collected energy rather than just at peak power.8,9 DSCs were fabricated utilizing uorine-doped tin oxide (FTO) coated glass substrates, a semitransparent TiO2 layer (T/SP Solaronix), N719 dye (Solaronix) and HSE electrolyte (Dyesol) as described in reference.10 The active area of the TiO2 lm was 10 10 mm.2 Around the TiO2, on the same plane (important for angular measurements), an opaque black paint with an internal perimeter of 12 12 mm was applied to avoid any internal/back reections and perimeter effects.11 Two types of DSCs were investigated: thick and thin cells with d 13 lm and d 3 lm thick TiO2 layers, respectively. Current/voltage (I/V) curves were extracted under solar simulator at air mass AM1.5G and 1 kW/m2 (2000 Abet Technologies calibrated with a Skye SKS 1110 sensor). The tilt angle h of the cell was implemented with a rotation stage. Normal incidence corresponds to h 0 . The background due to diverging/diffuse light in the measurement chamber, taken at h 90 , was subtracted from each data point. The vertical variation of optical power density when tilting the device was negligible.
a)

IPCE measurements were carried out on a dedicated setup. A 100 W mercury lamp (Osram HBO) was coupled with a Horiba Jobin Yvon monochromator (MC) (1220 lines/ mm). The beam was collimated to a spot size of 2 4 mm2 wholly contained inside the DSCs active area (10 10 mm2) for all angles (0 to 70 ). Since the lamp/MC system introduces a wavelength-dependent partial degree of polarization and since angular factors (such as reectances/transmittances) depend on the polarization, a linear polarizer was placed in front of the exit slit. The apparatus was calibrated to the intermediate sp state (%50% s, %50% p) simulating the case of unpolarized light (like that of the sun). A beam splitter and a calibrated photodiode were used for the simultaneous normalization of the signal. Measurements were also performed by using two laser beams at k 543 nm and k 633 nm in place of the lamp/MC. Figure 1 shows that the maximum output power Pmax of the thick dye solar cell decreases with angle of incidence h

Electronic mail: thomas.brown@uniroma2.it.

FIG. 1. (Color online) Maximum output power Pmax (h), the cosine curve of the device cross section (solid line), the power conversion efciency g Pmax =cosh4, the transmittance T at the front air/glass interface (dashed), the inner active layer efciency factor fg g/T of Eq. (1) (), as a function of the solar simulator lights angle of incidence h for a thick dye solar cell (dTiO2 13 lm). Quantities are normalized to their value at normal incidence (h 0 ). The cell parameters at h 0 are open-circuit voltage V0 0:58V, ll factor FF0 0.53, J0 7:38mA=cm2 , g0 2.3% OC SC (AM1.5G 1 kW/m2 light).
C V 2011 American Institute of Physics

0003-6951/2011/99(21)/213301/3/$30.00

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of the solar simulator light. For a uniform collimated beam like that of the sun, the power incident on the active area decreases proportionally to its cross section as cos(h). As it can be noticed, however, the measured normalized output power Pmax is larger than simply cos(h). The angular dependence of the power efciency g, obtained as the ratio of the normalized Pmax over cos(h), increases with angle up to a relative maximum of 10% at h 55 6 5 . If one considers that the reectance R at the front air/glass interface increases with angle according to Fresnel laws (depending also on polarization), the enhancement is even more signicant. The calculated transmittance through the glass is T 1 R % 95% at 0 and diminishes (like the light reaching the active layers) to T % 80% at 70 in the case of unpolarized light. To clear-out the effects due to T, we introduce the parameter representing the inner "active layer efciency (g/T),
h fg

1 T0 Ph T0 gh gh max norm : h cosh Th P0 Th g0 Tnorm max

(1)

h We observe a monotonic increase of fg g=T with angle up  to %20% in relative terms at 70 for the thick cell. Thus the dip in efciency at angles greater than 50 60 is due to a rapid decrease in T at the front glass surface. In Fig. 2(a), we report measurements under solar simulator on a thin cell. We note a larger increase compared to the

thick cell in both the efciency g (16% in relative terms at h its maximum at %60 ) and fg g=T (monotonic increase  %30% at 70 ). When one tilts the cell two major effects come into play: an oblique and longer propagation of the optical beam inside the titania layer and a change of light power density. The latter also inuences the temperature the cell reaches as would occur under outdoor sunlight (the temperature reached by the cells we measured was 7  C lower at h 60 compared to 0 ). We calculated that the power density on the active area of the cells at h 60 is about 0.45 of that at normal incidence due to the change in cross section and transmittance at the glass/air interface. To gauge this effect, we performed independent I/V measurements at different sun levels at normal incidence. When passing from 1 to %0.45 suns, measurements showed a relative positive (negative) variation in g (due to the combined effects of intensity and associated temperature variations) of %20% (<5%) for thick (thin) cells. Thus whereas for the thick cell the effect of the decrease in the incident power density in angle is key (variations in ll factor FF are more signicant), for the thin cell, the lengthening of the optical path in the titania layer plays an important role in the observed angular h increase in g and fg . The improvement margins for photon absorption are superior in the case of a thin active layer compared to its thicker counterpart. Since these margins depend also on the absorption coefcient a(k), we investigated the angular spectral response of the IPCE of DSCs by retrieving the monochromatic photocurrent angular factor which is analogous to Eq. (1) with ISC in place of Pmax and IPCE instead of g,   h;k 1 T0 ISC T0 IPCEh;k h;k ; (2) fIPCE 0;k cosh Th ISC Th IPCE0;k where the variations in T with k can be neglected in our wavelength range. The 1/cos(h) factor encompassing the reduction in cross section only applies to beams larger than the active area (e.g., solar simulator) but not to our IPCE setup since the beam spot is always fully contained inside the active area. h;k The fIPCE spectra for the thin cell are plotted in Fig. 2(b). There is a clear enhancement with h at every single k. Note that the monotonic increase with h is due to the normalization to T, whilst direct IPCE spectra fall above %50 (Fig. 3). h;k We note that fIPCE has a shape that is complementary to the 0 basic IPCE spectrum at normal incidence. Indeed, there is a local maximum corresponding to the IPCE valley at about 450 nm and a local minimum in correspondence to the IPCE h;k peak at 520 nm. The enhancement of fIPCE is largest at longer wavelengths although it dips around 700 nm. In this region, though, the absolute values of the IPCE are almost comparable to the backgorund noise. IPCE can be decomposed in IPCE LHE APCE, where LHE and APCE stand for light harvesting and absorbed photon-to-current conversion efciencies.12,13 Here, the focus is on the direct effect of angle on LHE. We veried through further experiments at normal incidence that the IPCE is not directly affected by the power density variations14 in the range associated to the varying h in our setup. Any effects of photogenerating electrons closer to the FTO at large angles were

FIG. 2. (Color online) (a) Maximum output power Pmax (h), the cosine curve of the device cross section (solid line), the power conversion efciency g Pmax =cosh4, the transmittance T at the front air/glass (dashed), the inner active layer efciency factor fg g/T dened in Eq. (1) (), normalized to their values at h 0 , as a function of the solar simulator lights angle of incidence h for a thin dye solar cell (dTiO2 3 lm). The cell electrical parameters at normal incidence are V0 0:72 V, FF0 0.63, J0 3:54 mA=cm2 , OC SC g0 1.64%. (b) Photocurrent angular factor fIPCE spectra for different angles (from 10 to 70 , bottom to top curve, with a step of 10 ) (left axis). The fIPCE are obtained from the measured IPCEh, normalizing each to the IPCE0 spectrum at h 0 (solid line, right axis) and to T as in Eq. (2).

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FIG. 3. (Color online) Angular measurements (in step of 1 ) on a thin dye solar cell with two laser sources. The reported quantities are normalized to their values at h 0 . The IPCE at 543 nm () and 633 nm (n) and the anguh lar factors fIPCE (* 543 nm, h 633 nm) computed dividing the IPCEh/ IPCE0 curves by the transmittance at the cells front air/glass interface Th/T0 h (bottom solid line). The ts to fIPCE are obtained by means of the refractive model.

In conclusion, we have shown and quantied a systematic increase of power (g) and quantum (IPCE) conversion efciencies when the light is incident at oblique angles on DSCs. For cells with thinner TiO2 layers, the effect is more signicant and is mainly due to optical path lengthening of the incoming photons. For thicker cells, the inuence of the light power density on device performance plays a more prominent role. Spectra show that the enhanced IPCE in angle gets larger at wavelengths where the dye absorbs less, in agreement with an ARP model considering Fresnel transmittance, Snell refraction, and Lambert-Beer absorption. The results can help quantify how DSCs work well under diffuse illumination and in terms of daily/yearly outdoor harvested energy, also giving hints and data for design of photon management structures. This work was nancially supported by a grant from Regione Lazio Polo Solare Organico Regione Lazio.
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2 1

neglected.12 The enhancement of the IPCE in angle can be simulated with an angular refractive path (ARP) model, based on Fresnel transmittance, Snell angle of refraction, and Lambert-Beer absorption. Neglecting the glass refractive index dispersion and multiple reections, LHE T(h) (1 exp(aL(h)), where a is the absorption coefcient, L d/ cos(heff) the total path length of the light inside the TiO2, and heff asin(sin(h)/neff) the angle inside the TiO2 which depends on the refractive index neff of the mesoporous layer (dyed titania lled with electrolyte) and on the angle of incidence h. L grows with h, leading to a larger LHE. Note that for thin devices (small d) and at the low absorption wavelengths (a), there is more room for increase at disposal in agreement with our experimental observations. Also, a lower neff would yield a larger inner heff for a given h. Figure 3 shows that the IPCEh/IPCE0 ratios on a thin cell present a maximum at h % 50 55 , with relative enhancements of about 6% and 10% for green (k 543 nm) and red (633 nm) light, respectively. To gauge the effect on the active layer, we normalized IPCEh/IPCE0 to the transmittance curve through the front glass/air interface Th/T0 (bottom solid line) of the devices, obtaining the angular fach;k tors fIPCE . These increase monotonically with angle up to 9% (k 543 nm) and 16% (k 633 nm) at 70 . The t with the ARP model permits us to retrieve neff of the mesoporous layer at the two k, in addition to the absorption coefcient a. The extracted values are n543 nm 2:06, a543 nm 1720 cm1 , eff n633 nm 1:81, and a633 nm 400 cm1 . The retrieval of these eff optical properties for such a diversely structured material inside the DSCs and the associated estimation of the path lengthening and LHE can be key for calculating and designing a variety of photon management structures, based on scattering layers, photonic crystals, V-shaped folding, 3D-PVs, waveguide, optical ber, plasmonics, and nanogratings, which enhance g by raising the optical path through the active layers.1524

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