Thin-film Solar Cell Interface Research Articles

Chemical and electronic structure of the heavily intermixed (Cd,Zn)S:Ga/CuSbS2 interface.

The interface formation and chemical and electronic structure of the (Cd,Zn)S:Ga/CuSbS2 thin-film solar cell heterojunction were studied using hard X-ray photoelectron spectroscopy (HAXPES) of the bare absorber and a buffer/absorber sample set for which the buffer thickness was varied between 1 and 50 nm. We find a heavily intermixed interface, involving Cu, Zn, and Cd as well as significant Ga and Cu profiles in the buffer. The valence band (VB) offset at the buffer/absorber interface was derived as (-1.3 ± 0.1) eV, which must be considered an upper bound as the Cu diffused into the buffer might form a Cu-derived VB maximum located closer to the Fermi level. The estimated conduction band minimum was 'cliff'-like; a situation made more severe considering the Cu-deficiency found for the CuSbS2 surface. The complex interface structure's effect on the performance of (Cd,Zn)S:Ga/CuSbS2-based solar cells and its limitation is discussed together with possible mitigation strategies.

Reactively sputtered Zn(O,S) buffer layers for controlling band alignment of Cu(In,Ga)Se2 thin-film solar cell interface

Abstract Buffer layers in Cu(In,Ga)Se2 (CIGS) solar cells are highly preferable to be vacuum-compatible and use non-toxic materials not only for the film but also for the manufacturing process. Moreover, high controllability for the energy levels of buffer layers is greatly desirable for achieving higher solar cell efficiency because the buffer layer is formed directly onto the absorber layer which generates carriers. In this study, the S/(O + S) composition ratio of the Zn(O,S) thin films was finely controlled by varying O2/(Ar + O2) gas flow ratio using a reactive sputtering method including an Ar/O2 mixture gas and a single ZnS sputter target. The structural, electrical, and photovoltaic performance properties of the Zn(O,S) thin films and their CIGS solar cells were investigated at varied S/(O + S) composition ratios. As the S/(O + S) composition ratio of the Zn(O,S) films increased, bandgap bowing occurred with the increase of the conduction band and valence band energy levels. The photovoltaic performance was greatly influenced by the difference of the conduction band energies between the Zn(O,S) buffer and the CIGS absorber. When the conduction band energy of the Zn(O,S) was too high or too low compared to that of the CIGS, it increased the carrier recombinations or series resistance, respectively, which induced losses of the open-circuit voltage and the fill factor. The controlling and optimizing the energy levels at the Zn(O,S)/CIGS interface were crucial for improved solar cell performances.

Rubidium Fluoride Post-Deposition Treatment: Impact on the Chemical Structure of the Cu(In,Ga)Se2 Surface and CdS/Cu(In,Ga)Se2 Interface in Thin-Film Solar Cells.

We present a detailed characterization of the chemical structure of the Cu(In,Ga)Se2 thin-film surface and the CdS/Cu(In,Ga)Se2 interface, both with and without a RbF post-deposition treatment (RbF-PDT). For this purpose, X-ray photoelectron and Auger electron spectroscopy, as well as synchrotron-based soft X-ray emission spectroscopy have been employed. Although some similarities with the reported impacts of light-element alkali PDT (i.e., NaF- and KF-PDT) are found, we observe some distinct differences, which might be the reason for the further improved conversion efficiency with heavy-element alkali PDT. In particular, we find that the RbF-PDT reduces, but not fully removes, the copper content at the absorber surface and does not induce a significant change in the Ga/(Ga + In) ratio. Additionally, we observe an increased amount of indium and gallium oxides at the surface of the treated absorber. These oxides are partly (in the case of indium) and completely (in the case of gallium) removed from the CdS/Cu(In,Ga)Se2 interface by the chemical bath deposition of the CdS buffer.

Reducing the Schottky barrier height at the MoSe2/Mo(110) interface in thin-film solar cells: Insights from first-principles calculations

We report on first-principles calculations of the properties of the MoSe2/Mo(110) interface. Due to mismatch between the lattice parameters of the two structures, different patterns can form at the interface. We have studied the formation energy and the band alignment of six patterns for the MoSe2 (0001)/Mo(110) interface and one pattern for the MoSe2 (112̅0)/Mo(110) interface. The MoSe2 (112̅0)/Mo(110) interface is more stable than the MoSe2 (0001)/Mo(110) interface and in contrast to MoSe2 (0001)/Mo(110), no Schottky barrier forms at MoSe2 (112̅0)/Mo(110). Doping with Na modifies the band alignment at the interfaces. The Schottky barrier height decreases, provided that a Na atom occupies a Mo atom site in MoSe2 films.

Annealing-Induced Effects on the Chemical Structure of the In2S3/CuIn(S,Se)2 Thin-Film Solar Cell Interface

We have investigated the impact of heat treatments on the chemical structure of the In2S3/CuIn(S,Se)2 thin-film solar cell interface using X-ray photoelectron and soft X-ray emission spectroscopy. As-grown, we find the formation of a sulfur-poor (indium-rich) In2S3 surface, an abrupt interface, and sulfur atoms in both In2S3 and CuIn(S,Se)2 chemical environments (as expected for an abrupt interface and a thin overlayer). After a heat treatment at 200 °C to simulate subsequent process steps, a strong copper and sodium diffusion into the In2S3 layer is observed. This diffusion extends throughout the layer, indicating the formation of a copper–indium–sulfide phase.

Intermixing at the absorber-buffer layer interface in thin-film solar cells: The electronic effects of point defects in Cu(In,Ga)(Se,S)2 and Cu2ZnSn(Se,S)4 devices

We investigate point defects in the buffer layers CdS and ZnS that may arise from intermixing with Cu(In,Ga)(S,Se)2 (CIGS) or Cu2ZnSn(S,Se)4 (CZTS) absorber layers in thin-film photovoltaics. Using hybrid functional calculations, we characterize the electrical and optical behavior of Cu, In, Ga, Se, Sn, Zn, Na, and K impurities in the buffer. We find that In and Ga substituted on the cation site act as shallow donors in CdS and tend to enhance the prevailing n-type conductivity at the interface facilitated by Cd incorporation in CIGS, whereas they are deep donors in ZnS and will be less effective dopants. Substitutional In and Ga can favorably form complexes with cation vacancies (A-centers) which may contribute to the “red kink” effect observed in some CIGS-based devices. For CZTS absorbers, we find that Zn and Sn defects substituting on the buffer cation site are electrically inactive in n-type buffers and will not supplement the donor doping at the interface as in CIGS/CdS or ZnS devices. Sn may also preferentially incorporate on the S site as a deep acceptor in n-type ZnS, which suggests possible concerns with absorber-related interfacial compensation in CZTS devices with ZnS-derived buffers. Cu, Na, and K impurities are found to all have the same qualitative behavior, most favorably acting as compensating acceptors when substituting on the cation site. Our results suggest one beneficial role of K and Na incorporation in CIGS or CZTS devices is the partial passivation of vacancy-related centers in CdS and ZnS buffers, rendering them less effective interfacial hole traps and recombination centers.

Impact of Na on MoSe2 formation at the CIGSe/Mo interface in thin-film solar cells on polyimide foil at low process temperatures

The aim of this work is to study the effect of Na on the formation of MoSe2 at the absorber/Mo back contact interface of Cu(In,Ga)Se2 (CIGSe) thin-film solar cells at low process temperatures using polyimide foil as substrate material. As reported previously, the presence of Na has been observed to modify the formation of the back interface, which may in part explain the different electronic properties of the completed device, as was determined by admittance spectroscopy and I–V–T measurements. In order to further study this interface formation, break-off experiments are performed and a lift-off technique is used to enable investigation of the different surfaces via X-ray photoelectron spectroscopy and Raman scattering. Both techniques confirm the dependence of the MoSe2 layer formation at the back interface on the presence of Na. The experiments also reveal the relevance of the composition of the absorber layer to the development of the MoSe2 layer during the Cu(In,Ga)Se2 deposition process. Hence this work describes routines that may be employed to develop an “appropriate” CIGSe/Mo back interface for high-efficiency solar cells.

Chemical interaction at the buried silicon/zinc oxide thin-film solar cell interface as revealed by hard X-ray photoelectron spectroscopy

Hard X-ray photoelectron spectroscopy (HAXPES) is used to identify chemical interactions (such as elemental redistribution) at the buried silicon/aluminum-doped zinc oxide thin-film solar cell interface. Expanding our study of the interfacial oxidation of silicon upon its solid-phase crystallization (SPC), in which we found zinc oxide to be the source of oxygen, in this investigation we address chemical interaction processes involving zinc and aluminum. In particular, we observe an increase of zinc- and aluminum-related HAXPES signals after SPC of the deposited amorphous silicon thin films. Quantitative analysis suggests an elemental redistribution in the proximity of the silicon/aluminum-doped zinc oxide interface – more pronounced for aluminum than for zinc – as explanation. Based on these insights the complex chemical interface structure is discussed.

Lateral inhomogeneity of the Mg/(Zn+Mg) composition at the (Zn,Mg)O/CuIn(S,Se)2 thin-film solar cell interface revealed by photoemission electron microscopy

Spatial variations in the chemical composition of the (Zn,Mg)O/CuIn(S,Se)2 thin-film solar cell interface were studied by photoemission electron microscopy (PEEM). Energy filtered PEEM images indicate significant differences in the magnesium and zinc distribution. Local photoemission measurements reveal a relative difference in the derived Mg/(Zn+Mg) composition of the (Zn,Mg)O material of up to (11.4 ± 0.7)%, which can be expected to induce band gap fluctuations of (60 ± 30) meV. Furthermore, local areas with significant accumulations of sodium could be observed.

Hard x-ray photoelectron spectroscopy study of the buried Si/ZnO thin-film solar cell interface: Direct evidence for the formation of Si–O at the expense of Zn-O bonds

The chemical structure of the interface between silicon thin films and the transparent conductive oxide ZnO:Al has been investigated by hard x-ray photoelectron spectroscopy. By varying the excitation energy between 2010 and 8040 eV, we were able to probe the Si/ZnO interface buried below 12 nm Si. This allowed for the identification of changes induced by solid phase crystallization (SPC). Based on in-situ SPC annealing experiments, we find clear indications that the formation of Si–O bonds takes place at the expense of Zn–O bonds. Hence, the ZnO:Al acts as the oxygen source for the interfacial Si oxidation.

Impact of solid-phase crystallization of amorphous silicon on the chemical structure of the buried Si/ZnO thin film solar cell interface

The chemical interface structure between phosphorus-doped hydrogenated amorphous silicon and aluminum-doped zinc oxide thin films is investigated with soft x-ray emission spectroscopy (XES) before and after solid-phase crystallization (SPC) at 600C. In addition to the expected SPC-induced phase transition from amorphous to polycrystalline silicon, our XES data indicates a pronounced chemical interaction at the buried Si/ZnO interface. In particular, we find an SPC-enhanced formation of Si-O bonds and the accumulation of Zn in close proximity to the interface. For an assumed closed and homogeneous SiO2 interlayer, an effective thickness of (5+2)nm after SPC could be estimated.

Sulfur gradient-driven Se diffusion at the CdS/CuIn(S,Se)2 solar cell interface

The diffusion behavior of Se at the CdS/Cu(In,Ga)(S,Se)2 thin film solar cell interface was investigated by x-ray photoelectron spectroscopy and x-ray excited Auger electron spectroscopy. Buffer/absorber structures with S/Se ratios between zero and three at the initial Cu(In,Ga)(S,Se)2 surface were analyzed. Samples from a high-efficiency laboratory process (NREL) as well as from an industrial large-area process (AVANCIS) were investigated. We find selenium diffusion into the CdS buffer layer, the magnitude of which strongly depends on the S content at the absorber surface. The associated modification of the heterojunction partners has significant impact on the electronic structure at the interface.

Spectroscopic investigation of the deeply buried Cu(In,Ga)(S,Se)2∕Mo interface in thin-film solar cells

The Cu(In,Ga)(S,Se)(2)Mo interface in thin-film solar cells has been investigated by surface-sensitive photoelectron spectroscopy, bulk-sensitive x-ray emission spectroscopy, and atomic force microscopy. It is possible to access this deeply buried interface by using a suitable lift-off technique, which allows us to investigate the back side of the absorber layer as well as the front side of the Mo back contact. We find a layer of Mo(S,Se)(2) on the surface of the Mo back contact and a copper-poor stoichiometry at the back side of the Cu(In,Ga)(S,Se)(2) absorber. Furthermore, we observe that the Na content at the Cu(In,Ga)(S,Se)(2)Mo interface as well as at the inner grain boundaries in the back contact region is significantly lower than at the absorber front surface.

Band alignment at the CdS∕Cu(In,Ga)S2 interface in thin-film solar cells

The band alignment at the CdS∕Cu(In,Ga)S2 interface in thin-film solar cells on a stainless steel substrate was investigated using photoelectron spectroscopy and inverse photoemission. By combining both techniques, the conduction and valence band offsets were independently determined. We find an unfavorable conduction band offset of −0.45 (±0.15) eV, accounting for the generally observed low open-circuit voltage and indicating the great importance of the buffer∕absorber conduction band offset for such devices. The surface band gap of the Cu(In,Ga)S2 absorber is 1.76 (±0.15) eV, being increased with respect to the expected bulk value by a copper depletion near the surface.