Impacts of KF Post-Deposition Treatment on the Band Alignment of Epitaxial Cu(In,Ga)Se2 Heterojunctions.

In this study, we investigated band alignments at CdS/epitaxial CuInxGa1-xSe2 (epi-CIGSe) and epi-CIGSe/GaAs heterointerfaces for solar cell applications using ultraviolet, inverse, and X-ray photoemission spectroscopy (UPS, IPES, and XPS) techniques. We clarified the impacts of KF postdeposition treatment (KF-PDT) at the CdS/epi-CIGSe front heterointerfaces. We found that KF-PDT changed the conduction band alignment at the CdS/epi-CIGSe heterointerface from a cliff to flat configuration, attributed to an increase in the electron affinity (EA) and ionization potential (IP) of the epi-CIGSe surface because of a decrease in Cu and Ga contents. Herein, we discuss the correlation between the impacts of KF-PDT and the solar cell performance. Furthermore, we also investigated the band alignment at the epi-CIGSe/GaAs rear heterointerface. Electron barriers were formed at the epi-CIGSe/GaAs interface, suppressing carrier recombination as the back surface field. Contrarily, a hole accumulation layer is formed by the valence band bending, which is like Ohmic contact.

Optical and Structural Properties of High-Efficiency Epitaxial Cu(In,Ga)Se2 Grown on GaAs.

Photovoltaic devices based on Cu(In,Ga)Se2 (CIGS) typically employ polycrystalline thin films as the absorber layer. This is because, to date, the highest conversion efficiencies have been attained with polycrystalline CIGS films. Recently, Nishinaga et al. presented an epitaxial CIGS thin-film solar cell grown on a GaAs (100) substrate with a conversion efficiency of 20.0%. In this contribution, we study the optical and structural properties of this high-efficiency epitaxial film, along with others with different compositions using cathodoluminescence spectrum imaging and transmission electron microscopy. A comparison of the high-efficiency epitaxial film and a traditional polycrystalline film with a similar global composition reveals significant differences in microstructure and uniformity of emission properties despite similar performance. The analysis of epitaxial films with a higher gallium concentration indicates that the emission characteristics and nature of extended defects in epitaxial CIGS films are strongly dependent on the gallium content. The results presented here provide evidence that, with further optimization, photovoltaic conversion efficiencies of epitaxial CIGS films could exceed those of polycrystalline CIGS.

Improving the Open Circuit Voltage through Surface Oxygen Plasma Treatment and 11.7% Efficient Cu2ZnSnSe4 Solar Cell.

The photovoltaic performance of Cu2ZnSnSe4 (CZTSe) solar cells subjected to surface oxygen plasma treatments is investigated. The observed improvements are related to an enhancement of the open circuit voltage VOC, that is, the suppression of the VOC deficit. The VOC monotonically increases with treatment time up to 0.460 V. The origin of this improvement is discussed, and it is concluded that the effectiveness of the surface treatment is not due to oxygen-related alloying but instead to the homogeneous oxidation and removal of the oxidized CZTSe surface layer. The surface oxygen content increases with surface treatment time, although surface oxides are fully removed after ammonia treatment, which is conducted in a similar manner to CdS buffer deposition. The reduction of surface recombination is confirmed by time-resolved photoluminescence measurements, and the minority carrier lifetime deduced using the fast decay component increases with increasing treatment time. The relationship between photovoltaic properties and lifetime is clearly demonstrated. The best-performing CZTSe solar cell obtained using surface oxygen treatment demonstrates a conversion efficiency of 11.7%, which is higher than those of previous reports on CZTSe cells.

Band Alignment of the CdS/Cu2Zn(Sn1- xGe x)Se4 Heterointerface and Electronic Properties at the Cu2Zn(Sn1- xGe x)Se4 Surface: x = 0, 0.2, and 0.4.

The surface electronic properties of the light absorber and band alignment at the p/n heterointerface are key issues for high-performance heterojunction solar cells. We investigated the band alignment of the heterointerface between cadmium sulfide (CdS) and Ge-incorporated Cu2ZnSnSe4 (CZTGSe), with Ge/(Ge + Sn) ratios ( x) between 0 and 0.4, by X-ray photoelectron, ultraviolet, and inversed photoemission spectroscopies (XPS, UPS, and IPES, respectively). In particular, we used interface-induced band bending in order to determine the conduction band offset (CBO) and valence-band offset (VBO), which were calculated from the core-level shifts of each element in both the CdS overlayer and the CZTGSe bottom layer. Moreover, the surface electronic properties of CZTGSe were also investigated by laser-irradiated XPS. The CBO at the CdS/CZTGSe heterointerface decreased linearly, from +0.36 to +0.20 eV, as x was increased from 0 to 0.4; in contrast, the VBO at the CdS/CZTGSe heterointerface was independent of Ge content. Both UPS and IPES revealed that the Fermi level at the CZTGSe surface is located near the center of the band gap. The hole concentration at the CZTGSe surface was on the order of 1011 cm-3, which is much smaller than that of the bulk (∼1016 cm-3). We discuss the differences in hole deficiencies near the surface and in the bulk on the basis of laser-irradiated XPS and conclude that hole deficiencies are due to defects distributed near the surface with densities that are lower than in the bulk, and the Fermi level is not pinned at the CZTGSe surface.

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.

Interfacial alkali diffusion control in chalcopyrite thin-film solar cells.

Alkali elements, specifically sodium (Na), are key materials to enhance the energy conversion efficiencies of chalcopyrite and related thin-film photovoltaic solar cells. Recently, the effect of potassium (K) has also attracted attention because elemental K has unique effects different from Na as well as a similar beneficial effect in improving device performance. In this study, the control of selective alkali K and Na diffusion into chalcopyrite thin-films from soda-lime glass substrates, which serve as the monolithic alkali source material and contain both K and Na, is demonstrated using ternary CuGaSe2. Elemental K is found to be incorporated in the several ten nanometer thick Cu-deficient region, which is formed on the CuGaSe2 film surface, while Na is ejected, although both K and Na diffuse from the substrate to the CuGaSe2 film surface during growth. The alkali [K]/[Na] concentration ratio in the surface region of CuGaSe2 films strongly depends on the film structure and can be controlled by growth parameters under the same substrate temperature conditions. The results we present here offer new concepts necessary to explore and develop emerging new chalcopyrite and related materials and optimize their applications.

Formation of ionic bonds between a fatty-acid Langmuir-Blodgett monolayer and a zinc oxide substrate.

A fatty-acid Langmuir-Blodgett (LB) monolayer ionically adsorbed to the substrate has been prepared by adopting ZnO-based conductor and pure water respectively as the substrate and subphase. Ionization of the fatty-acid molecules has been detected by infrared reflection-absorption spectroscopy (IR-RAS), which is enabled by the condensed free electrons in the doped ZnO substrate. On the contrary, IR-RAS measurements have indicated that fatty-acid molecules transferred onto Au and indium-tin-oxide substrates from a pure-water surface are not ionized. In addition, it has been demonstrated that these ionically bonded fatty-acid monolayers protect the ZnO transparent electrode from chemical attack by NH(3) gas. Since the LB technique is a simple method applicable to a wide variety of materials, the present results may lead to a new way of obtaining functional organic-inorganic nanosystems.

Direct observation of nitrogen location in molecular beam epitaxy grown nitrogen-doped ZnO.

ZnO is a wide band gap, naturally n-type semiconductor with great promise for optoelectronic applications; the main obstacle yet to be overcome is p-type doping. Nitrogen, the most promising candidate currently being pursued as a dopant, has been predicted to preferentially incorporate into the ZnO lattice in the form of a N-2 molecule at an O site when a plasma source is used, leading to compensation rather than p-type doping. We demonstrate this to be incorrect by using N K-edge x-ray absorption spectra and comparing them with first-principles calculations showing that nitrogen, in fact, incorporates substitutionally at O sites where it is expected to act as an acceptor. We also detect the formation of molecular nitrogen upon annealing. These results suggest that effective p-type doping of ZnO with N may be possible only for low-temperature growth processes.

Microstructural evolution of ZnO by wet-etching using acidic solutions.

The characteristics of the wet-etching of ZnO thin films were investigated using hydrochloric and phosphoric acid solutions as etchants. The etch rate of ZnO films, using a highly diluted hydrochloric acid solutions at a concentration of 0.25% in deionized water, was determined to be about 120 nm/min, and linearly increased with increasing the acid concentration. The surface of ZnO(0001) etched by an HCl solution, observed by scanning electron microscopy, showed a rough morphology with a high density of hexagonal pyramids or cones with sidewall angles of about approximately 45 degrees. Moreover, the sidewall angles of the masked area were similar to those of the pyramids on the surface. In comparison, the surface of ZnO(0001) etched by a phosphoric acid had a smooth surface morphology. The origin of this difference is from the very initial stage of etching, indicating that the etch-mechanism is different for each solution. Furthermore, when H3PO4 was added to the HCl aqueous solution, the morphology of the etched surface was greatly enhanced and the sidewall angle was also increased to about 65 degrees.