Fabrication and centeracterization of ordered CuIn(1−x)Ga x Se2 nanopore films via template-based electrodeposition
© Li et al.; licensee Springer. 2012
Received: 13 October 2012
Accepted: 24 November 2012
Published: 17 December 2012
Ordered CuIn(1−x)Ga x Se2 (CIGS) nanopore films were prepared by one-step electrodeposition based on porous anodized aluminum oxide templates. The as-grown film shows a highly ordered morphology that reproduces the surface pattern of the substrate. Raman spectroscopy and X-ray diffraction pattern show that CIGS nanopore films had ideal chalcopyrite crystallization. Energy dispersive spectroscopy reveals the Cu-Se phases firstly formed in initial stage of growth. Then, indium and gallium were incorporated in the nanopore films in succession. Cu-Se phase is most likely to act as a growth promoter in the growth progress of CIGS nanopore films. Due to the high surface area and porous structure, this kind of CIGS films could have potential application in light-trapping CIGS solar cells and photoelectrochemical water splitting.
KeywordsCuIn(1−x)Ga x Se2 nanopore films electrodeposition anodic aluminumoxide annealing 82.45.Yz 81.05.Rm 81.15.Pq 81.40.Ef
In recent years, solar cells attract people’s attention for its clean and renewable properties . Chalcopyrite CuInSe2/CuIn(1−x)Ga x Se2 (CIS/CIGS) thin films are considered as a promising candidate for solar cells since they have a high light absorption coefficient (about 105 cm−1), good radiation, and thermal stability [2–7]. Also, CIGS has a direct and tunable bandgap range from 1.04 to 1.72 eV owing to the components of indium and gallium. Moreover, photoelectrochemical water splitting property of CIGS has been discussed in works in recent years [8, 9]. Several methods have been reported to fabricate CIGS thin films such as co-evaporation, electrode position, selenization of sequentially stacked precursors, etc. [3, 10–12]. A high conversion efficiency of 19.9% at laboratory scale was reported via a three-stage co-evaporation with a modified surface termination . Also, the new record has been reported to achieving 20.3% last year . Both of them have high conversion efficiency, but they all have the same disadvantages that the method is sophisticated and needs an expensive vacuum technology. However, electrodeposition is a competitive method that is economic and convenient. It also has high deposition speed and can prepare large area films . Though the conversion efficiency of one-step electrodeposition is much lower than that of co-evaporation method, it can be improved by annealing and selenization.
As is well known, nanostructures can mostly improve properties of materials at a certain aspect [15–20]. In recent years, much effort has been devoted to fabricating CIS/CIGS nanowires and nanotubes, trying to improve cell properties through changing their microstructures [21–24]. Herein, we firstly fabricated CIGS nanopore films using one-step electrodeposition method based on anodized aluminum oxide (AAO) templates. Due to the high specific surface area and the porous structure, the ordered CIGS nanopore films could be used in light-trapping solar cells and photoelectrochemical water splitting. AAO templates are used to confine the structure of the film during the process of growth. The film, after being annealed at 550°C, shows a better performance in crystallization through analyzing by Raman spectroscopy and X-ray diffraction. Mechanism of deposition has also been discussed.
The morphology of as-prepared and annealed CIGS films was observed by field emission scanning electron microscopy (FE-SEM; Philips Sirion 200, Philips, Netherlands). The composition was investigated by energy-dispersive X-ray spectrometer (EDS) system attached to FE-SEM. The Raman spectra were measured by LabRam HR 800 UV system (Jobin Yvon, France). The crystallographic structure was determined by X-ray diffraction (XRD; D8 DISCOVER X-ray diffractometer, Bruker, Germany) with Cu Kα radiation (λ = 1.54Å).
Results and discussion
Process of growth
Elementary component of Cu, In, Ga, and Se in the as-grown CIGS nanopore films
Se (at.% )
In summary, we firstly fabricated highly ordered CIGS nanopore films. The deposited film reproduced the morphology of the AAO substrate. With heat treatment, the CIGS nanopore films present an almost pure chalcopyrite nanocrystal. Moreover, Cu-Se phases firstly occur during growth of the film. Then, In and Ga incorporated in the films through reactions with Cu-Se phases. This large-scale ordered CIGS nanopore films could be used in light-trapping CIGS solar cells and photocatalytic hydrogen generation.
Anodized aluminum oxide
CuInSe2/CuIn(1−x)Ga x Se2
Energy-dispersive X-ray spectrometer
Field emission scanning electron microscopy
Full width at half maximum
Saturated calomel electrode
This work was supported by the Natural Science Foundation of China (grant no. 11174197), National Major Basic Research Project of 2012CB934302, National 863 Program 2011AA050518.
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