Tunability of the bandgap of SnS by variation of the cell volume by alloying with A.E. elements.

We clarified that the bandgap of inorganic materials is strongly correlated with their effective coordination number (ECoN) via first-principles calculations and experimental confirmations. Tin mono-sulphide (Pnma) and germanium mono-sulphide (Pnma) were selected as model cases since these materials successively alter the ECoN as the cell volume changes and show an uncommon relationship between cell volume and bandgap. Contrary to the common semiconductors, the bandgaps of SnS (Pnma) and GeS (Pnma) have a positive relationship with respect to cell volume. This unique phenomenon was explained by incorporating the concept of ECoN into the theoretical studies. The theory proposed in this study is widely applicable to semiconductors with low-symmetry structures. Further, we experimentally demonstrated that the bandgap of SnS (Pnma) can be broadly tuned by changing the unit cell volume via alloying with alkali-earth (A.E.) metals, which could allow SnS to be applied to Si-based tandem photovoltaics. Alloying with A.E. elements also stabilised Cl as an n-type donor, which enabled n-type conduction in the bandgap-widened SnS film in the SnS-based semiconductors.

New Route for "Cold-Passivation" of Defects in Tin-Based Oxides.

Transparent conductive oxides (TCOs) are essential in technologies coupling light and electricity. For Sn-based TCOs, oxygen deficiencies and undercoordinated Sn atoms result in an extended density of states below the conduction band edge. Although shallow states provide free carriers necessary for electrical conductivity, deeper states inside the band gap are detrimental to transparency. In zinc tin oxide (ZTO), the overall optoelectronic properties can be improved by defect passivation via annealing at high temperatures. Yet, the high thermal budget associated with such treatment is incompatible with many applications. Here, we demonstrate an alternative, low-temperature passivation method, which relies on cosputtering Sn-based TCOs with silicon dioxide (SiO2). Using amorphous ZTO and amorphous/polycrystalline tin dioxide (SnO2) as representative cases, we demonstrate through optoelectronic characterization and density functional theory simulations that the SiO2 contribution is twofold. First, oxygen from SiO2 passivates the oxygen deficiencies that form deep defects in SnO2 and ZTO. Second, the ionization energy of the remaining deep defect centers is lowered by the presence of silicon atoms. Remarkably, we find that these ionized states do not contribute to sub-gap absorptance. This simple passivation scheme significantly improves the optical properties without affecting the electrical conductivity, hence overcoming the known transparency-conductivity trade-off in Sn-based TCOs.

Si-Doping Effects in Cu(In,Ga)Se2 Thin Films and Applications for Simplified Structure High-Efficiency Solar Cells.

We found that elemental Si-doped Cu(In,Ga)Se2 (CIGS) polycrystalline thin films exhibit a distinctive morphology due to the formation of grain boundary layers several tens of nanometers thick. The use of Si-doped CIGS films as the photoabsorber layer in simplified structure buffer-free solar cell devices is found to be effective in enhancing energy conversion efficiency. The grain boundary layers formed in Si-doped CIGS films are expected to play an important role in passivating CIGS grain interfaces and improving carrier transport. The simplified structure solar cells, which nominally consist of only a CIGS photoabsorber layer and a front transparent and a back metal electrode layer, demonstrate practical application level solar cell efficiencies exceeding 15%. To date, the cell efficiencies demonstrated from this type of device have remained relatively low, with values of about 10%. Also, Si-doped CIGS solar cell devices exhibit similar properties to those of CIGS devices fabricated with post deposition alkali halide treatments such as KF or RbF, techniques known to boost CIGS device performance. The results obtained offer a new approach based on a new concept to control grain boundaries in polycrystalline CIGS and other polycrystalline chalcogenide materials for better device performance.

Carrier Compensation Induced by Thermal Annealing in Al-Doped ZnO Films.

This study investigated carrier compensation induced by thermal annealing in sputtered ZnO:Al (Al2O3: 0.25, 0.5, 1.0, and 2.0 wt %) films. The films were post-annealed in a N2 atmosphere at low (1 × 10-23 atm) and high (1 × 10-4 atm) oxygen partial pressures (PO2). In ZnO:Al films with low Al contents (i.e., 0.25 wt %), the carrier density (n) began to decrease at annealing temperatures (Ta) of 600 °C at low PO2. At higher PO2 and/or Al contents, n values began to decrease significantly at lower Ta (ca. 400 °C). In addition, Zn became desorbed from the films during heating in a high vacuum (i.e., <1 × 10-7 Pa). These results suggest the following: (i) Zn interstitials and Zn vacancies are created in the ZnO lattice during post-annealing treatments, thereby leading to carrier compensation by acceptor-type Zn vacancies; (ii) The compensation behavior is significantly enhanced for ZnO:Al films with high Al contents.

Cu(In,Ga)Se2 Solar Cells with Amorphous In2O3-Based Front Contact Layers.

Amorphous (a-) In2O3-based front contact layers composed of transparent conducting oxide (TCO) and transparent oxide semiconductor (TOS) layers were proved to be effective in enhancing the short-circuit current density (Jsc) of Cu(In,Ga)Se2 (CIGS) solar cells with a glass/Mo/CIGS/CdS/TOS/TCO structure, while maintaining high fill factor (FF) and open-circuit voltage (Voc). An n-type a-In-Ga-Zn-O layer was introduced between the CdS and TCO layers. Unlike unintentionally doped ZnO broadly used as TOS layers in CIGS solar cells, the grain-boundary(GB)-free amorphous structure of the a-In-Ga-Zn-O layers allowed high electron mobility with superior control over the carrier density (N). High FF and Voc values were achieved in solar cells containing a-In-Ga-Zn-O layers with N values broadly ranging from 2 × 1015 to 3 × 1018 cm-3. The decrease in FF and Voc produced by the electronic inhomogeneity of solar cells was mitigated by controlling the series resistance within the TOS layer of CIGS solar cells. In addition, a-In2O3:H and a-In-Zn-O layers exhibited higher electron mobilities than the ZnO:Al layers conventionally used as TCO layers in CIGS solar cells. The In2O3-based layers exhibited lower free carrier absorption while maintaining similar sheet resistance than ZnO:Al. The TCO and TOS materials and their combinations did not significantly change the Voc of the CIGS solar cells and the mini-modules.