We report on the fabrication of heterojunction solar cells made by deposition of transparent conducting oxide (TCO) films on Cu2O substrates. The TCO films have been grown by ion beam sputtering on good quality Cu2O sheets prepared by oxidizing copper at a high temperature. The best solar cell has reached an open-circuit voltage of 0.595V, a short-circuit current density of 6.78mA∕cm2, a fill factor of 50%, and a conversion efficiency of 2% under simulated AM1.5G illumination, which is the highest efficiency value reported for this kind of heterojunction devices. These devices represent a good starting point for the development of very low cost solar cells.

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We review the present state-of-the-art within back and front contacts in kesterite thin film solar cells, as well as the current challenges. At the back contact, molybdenum (Mo) is generally used, and thick Mo(S, Se) 2 films of up to several hundred nanometers are seen in record devices, in particular for selenium-rich kesterite. The electrical properties of Mo(S, Se) 2 can vary strongly depending on orientation and indiffusion of elements from the device stack, and there are indications that the back contact properties are less ideal in the sulfide as compared to the selenide case. However, the electronic interface structure of this contact is generally not well-studied and thus poorly understood, and more measurements are needed for a conclusive statement. Transparent back contacts is a relatively new topic attracting attention as crucial component in bifacial and multijunction solar cells. Front illuminated efficiencies of up to 6% have so far been achieved by adding interlayers that are not always fully transparent. For the front contact, a favorable energy level alignment at the kesterite/CdS interface can be confirmed for kesterite absorbers with an intermediate [S]/([S]+[Se]) composition. This agrees with the fact that kesterite absorbers of this composition reach highest efficiencies when CdS buffer layers are employed, while alternative buffer materials with larger band gap, such as Cd 1−x Zn x S or Zn 1−x Sn x O y , result in higher efficiencies than devices with CdS buffers when sulfurrich kesterite absorbers are used. Etching of the kesterite absorber surface, and annealing in air or inert atmosphere before or after buffer layer deposition, has shown strong impact on device performance. Heterojunction annealing to promote interdiffusion was used for the highest performing sulfide kesterite device and air-annealing was reported important for selenium-rich record solar cells. Cu 2 ZnSnS 4 (CZTS) absorbers for solar cell applications was first reported by Ito and Nakazawa [1]. Early results on CZTS device performance were reported by Friedlmeier et al [2], Seol et al [3], and Katagiri et al [4]. Later a group at IBM reached record performances with power conversion efficiencies (PCEs) above 10% for CZTSSe devices in 2010 [5] and the current record PCE of 12.6% in 2013 [6]. In 2018, researchers from DGIST reached the same performance, 12.6%, but for a larger device area [7]. The device structure used for kesterite solar cells was originally copied from that of Cu(In, Ga)Se 2 , (CIGSe) TFSCs, and is formed by sequential deposition, upon a soda lime glass substrate, of a Mo back contact, the absorber, a CdS buffer layer, and a ZnO/ZnO:Al bi-layer window (i.e. transparent top contact). This structure, schematically shown for CZTSSe in figure 1, is not necessarily ideal for kesterite solar cells, and extensive work has been invested into studies of alternative backand front contacts and related deposition processes. In this paper, the state-of-the-art and current open questions related to the back and front c...

The effect of the order-disorder transition on the band gap of kesterite Cu2ZnSnS4, an interesting material for solar cells, has been investigated by optical spectroscopy. The band gap energy (Eg) decreases continuously with increasing annealing temperature, Ta, and reaches its minimum at Ta ∼ 273 °C. Eg is about 200 meV higher in the most ordered state, than in the fully disordered state. Its value and the transition kinetic depend on the sample stoichiometry. A simplified model able to explain the order degree and stoichiometry effects on the Eg value is developed. Ordering results in narrower Raman peaks without affecting the shape of the photoluminescence spectrum—except for the change in Eg—or the characteristic energy of the exponential tail below the fundamental absorption edge. Although a prolonged annealing increases the order degree, the material properties are still influenced by residual disorder as well as by defects related to the off-stoichiometry composition.

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