Dye-sensitized solar cells based on ZnO nanotetrapods

doi:10.1007/s12200-011-0207-0

Front Optoelec Chin

2011, Vol. 4

Issue (1) : 24-44 https://doi.org/10.1007/s12200-011-0207-0

REVIEW ARTICLE

Dye-sensitized solar cells based on ZnO nanotetrapods

Wei CHEN^1,2, Shihe YANG¹(

)

1. Department of Chemistry, The Hong Kong University of Science and Technology, Hong Kong, China; 2. Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074, China

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Abstract

In this paper, we reviewed recent systematic studies of using ZnO nanotetrapods for photoanodes of dye-sensitized solar cells (DSSCs) in our group. First, the efficiency of power conversion was obtained by more than 3.27% by changes of conditions of dye loading and film thickness of ZnO nanotetrapod. Short-circuit photocurrent densities (J_sc) increased with the film thickness, J_sc would not be saturation even the film thickness was greater than 35 μm. The photoanode architecture had been charactered by good crystallinity, network forming ability, and limited electron-hopping interjunctions. Next, DSSCs with high efficiency was devised by infiltrating SnO₂ nanoparticles into the ZnO nanotetrapods photoanodes. Due to material advantages of both constituents described as above, the composite photoanodes exhibited extremely large roughness factors (RFs), good charge collection, and tunable light scattering properties. By varying the composition of the composite photoanodes, we had achieved an efficiency of 6.31% by striking a balance between high efficiency of charge collection for SnO₂ nanoparticles rich films and high light scattering ability for ZnO nanotetrapods rich films. An ultrathin layer of ZnO was found to form spontaneously on the SnO₂ nanoparticles, which primarily was responsible for enhancing open-circuit photovoltage (V_oc). We also identified that recombination in SnO₂/ZnO composite films was mainly determined by ZnO shell condition on SnO₂, whereas electron transport was greatly influenced by the morphologies and sizes of ZnO crystalline additives. Finally, we applied the composite photoanodes of SnO₂ nanoparticles/ZnO nanotetrapods to flexible DSSCs by low temperature technique of “acetic acid gelation-mechanical press-ammonia activation.” The efficiency has been achieved by 4.91% on ITO-coated polyethylenenaphtalate substrate. The formation of a thin ZnO shell on SnO₂ nanoparticles, after ammonia activation, was also found to be critical to boosting V_oc and to improving inter–particles contacts. Mechanical press, apart from enhancing film durability, also significantly improved charge collection. ZnO nanotetrapods had been demonstrated to be a better additive than ZnO particles for the improvement of charge collection in SnO₂/ZnO composite photoanodes regardless of whether they were calcined.

Keywords dye-sensitized solar cell (DSSC) metal oxides nanostructure ZnO nanotetrapod photoanode flexible solar cell

Corresponding Author(s): YANG Shihe,Email:chsyang@ust.hk

Issue Date: 05 March 2011

Cite this article:

Wei CHEN,Shihe YANG. Dye-sensitized solar cells based on ZnO nanotetrapods[J]. Front Optoelec Chin, 2011, 4(1): 24-44.

URL:

https://academic.hep.com.cn/foe/EN/10.1007/s12200-011-0207-0
https://academic.hep.com.cn/foe/EN/Y2011/V4/I1/24

Fig.1 Structural characteristics of 30 μm thick ZnO nanotetrapod film. SEM images viewed from top (a), at high resolution (b), in cross-section (c), and at detailed inter-tetrapod connections (d); (e) schematic showing a possible electron transport pathway across the ZnO nanotetrapod film. Sample in (d) was from residue left on FTO-glass substrate after scratching away nanotetrapods film. (Ref. [], published with permission)

Fig.2 (a) - characteristic curve of typical ZnO nanotetrapod cell with film thickness of 31.1 μm; (b) dependence of dye loading amount on film thickness (∝ ); dependence of cell performance on film thickness including overall solar conversion efficiency and short-circuit photocurrent density (c) and open-circuit photovoltage and fill factor (d). Open symbols and solid symbols in (c), (d) correspond to nonclacined and calcined photoanodes, respectively (Ref. [], published with permission)

Fig.3 Impedance spectra of DSSCs based on ZnO nanotetrapods photoanodes with different film thicknesses, at applied potential of -0.3 V under 0.1 sun illumination. Inset shows enlarged portion of circled area, dotted line highlights Warburg-like diffusion lines (Ref. [], published with permission)

Fig.4 Diffuse reflectance spectra of pure SnO nanoparticles film, pure ZnO nanotetrapods film and three SnO nanoparticles/ZnO nanotetrapods composite films. All films are prepared with same thicknesses of around 6 μm on glass slides (Ref. [], published with permission)

Fig.5 Sn 3d XPS spectra of pure SnO nanoparticles film and the three composite films (Ref. [], published with permission)

Fig.6 Thickness dependent characteristics of SnO nanoparticles/ZnO nanotetrapods composite films as well as pure SnO nanoparticles film and pure ZnO nanotetrapods film. (a) (denoted by solid symbols) and dye adsorbing amount (denoted by open symbols); (b) short-circuit photocurrent density ; (c) open-circuit photovoltage ; (d) a blown-up region highlights of three composite films; (e) fill factor and (f) overall energy conversion efficiency (Ref. [], published with permission)

Tab.1 Summary of performance parameters of DSSCs based on SnO nanoparticles/ZnO nanotetrapods composite photoanodes

Fig.7 IPCE of DSSCs based on three typical composite photoanodes with different weight ratios as listed in Table 1 (Ref. [], published with permission)

Fig.8 Incident light intensity dependent transport and recombination time constants for SnO ∶ ZnO nanotetrapods= 2 ∶ 1, 1 ∶ 1 and 1 ∶ 2 composite photoanodes (as listed in Table 1) (Ref. [], published with permission)

Fig.9 Cross section view SEM images showing structural differences between original SnO ∶ ZnO= 1 ∶ 1 composite film (Original) and corresponding HAc30 film. Note that corrosion of ZnO nanotetrapods leads to more porous structure with less continuity in SnO nanoparticles network (Ref. [], published with permission)

Fig.10 Incident light intensity dependent electron diffusion coefficient (a) and electron lifetime (b) of the SnO ∶ ZnO nanotetrapods= 2 ∶ 1 composite film and two reference films with the ZnO nanotetrapods being replaced by ZnO small particles (40 nm) or ZnO big particles (500 nm). Straight lines represent power-law fits. values are calculated from logarithmic slopes (1-) by least square fitting (Ref. [], published with permission)

Fig.11 Schematic showing low temperature technique of “AG-MP-NA” and its effects on films’ morphology, surface condition, as well as resulting electron transport and light scattering properties (Ref. [], published with permission)

Fig.12 SEM images of single-layer composite film before (a)–(c), after pressing procedure (d)–(f), and a double-layer-structured film (g)–(i). (a), (d) cross-section view: film thickness is decreased from 19.2 to 10.3 μm due to pressing procedure; (b), (e) cross-section view highlighting difference at active film/FTO-coated glass interface; (c), (f) top view showing different porosities; (g) cross-section view: top light scattering layer is 3.3 μm thick ZnO nanotetrapods network; (h), (i) top view showing the different packing densities of nanotetrapods before (h) and after pressing procedure (i) (Ref. [], published with permission)

Fig.13 (a) - characteristic curves of DSSCs based on “AG-MP-NA” processed films on FTO-coated glasses (solid symbols) and ITO/PEN flexible substrates (open symbols) (inset show photographs of dye sensitized films used to record - curves, from left to right, single-layer composite film (?) and double-layer-structured film (●) on FTO-coated glasses, and single-layer composite film (?) and double-layer-structured film (○) on flexible substrates); (b) IPCE spectra of DSSCs based on single-layer composite film and double-layer structured film on FTO-coated glasses in (a) (Ref. [], published with permission)

Tab.2 Performance parameters of best performance DSSCs on FTO-coated glasses (S1: single layer, D1: double layer) or ITO/PEN flexible substrates (S2: single layer, D2: double layer), corresponding to - characteristic curves in Fig. 13(a)

Fig.14 (a) - characteristic curves of composite films: black square, film treated by pressing and NH activation (film thickness ≈ 6.5 μm, cell 1); red circle, film treated by NH activation but without pressing (film thickness ≈ 12 μm, cell 2); blue up-triangle, as-deposited film without further treatment (cell 3). and highlight different slopes of the tangents at the open-circuit voltage; (b) EIS Nyquist plots from impedance spectra of the films together with the fitted results (solid line) based on the equivalent circuit model as shown in inset; (c) electron transport and recombination times of the films from IMPS/IMVS measurements. Straight lines are fitted results (Ref. [], published with permission)

Tab.3 Performance parameters of DSSCs corresponding to J-V characteristic curves in Fig. 13(a)

Fig.15 Dependences of and efficiency (charge collection efficiency) on film thickness for two kinds of nanocomposite films on FTO-coated glasses: black square, SnO nanoparticles/ZnO nanotetrapods; red circle, SnO nanoparticles/ZnO big particles. Charge collection efficiencies were calculated from data measured by IMPS/IMVS at 70 W·m (Ref. [], published with permission)

Fig.16 SEM images of composite films containing ZnO nanotetrapods (a) and ZnO big particles (b) as additives. Scale bar= 1 μm. Yellow arrow-lines highlight different lengths the localized electrons have to migrate from SnO nanoparticles to neighboring ZnO sites (Ref. [], published with permission)

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