Chemical etching of Sb2Se3 solar cells: surface chemistry and back contact behaviour

The effect of (NH4)2S and CS2 chemical etches on surface chemistry and contacting in Sb2Se3 solar cells was investigated via a combination of x-ray photoemission spectroscopy (XPS) and photovoltaic device analysis. Thin film solar cells were produced in superstrate configuration with an absorber layer deposited by close space sublimation. Devices of up to 5.7% efficiency were compared via current–voltage measurements (J–V) and temperature-dependent current–voltage (J–V–T) analysis. XPS analysis demonstrated that both etching processes were successful in removing Sb2O3 contamination, while there was no decrease in free elemental selenium content by either etch, in contrast to prior work. Using J–V–T analysis the removal of Sb2O3 at the back surface in etched samples was found to improve contacting by reducing the potential barrier at the back contact from 0.43 eV to 0.26 eV and lowering the series resistance. However, J–V data showed that due to the decrease in shunt resistance and short-circuit current as a result of etching, the devices show a lower efficiency following both etches, despite a lowering of the series resistance. Further optimisation of the etching process yielded an improved efficiency of 6.6%. This work elucidates the role of surface treatments in Sb2Se3 devices and resolves inconsistencies in previously published works

Natural Band Alignments and Band Offsets of Sb2Se3 Solar Cells

Sb2Se3 is a promising material for use in photovoltaics, but the optimum device structure has not yet been identified. This study provides band alignment measurements between Sb2Se3, identical to that used in high-efficiency photovoltaic devices, and its two most commonly used window layers, namely, CdS and TiO2. Band alignments are measured via two different approaches: Anderson’s rule was used to predict an interface band alignment from measured natural band alignments, and the Kraut method was used in conjunction with hard X-ray photoemission spectroscopy to directly measure the band offsets at the interface. This allows examination of the effect of interface formation on the band alignments. The conduction band minimum (CBM) of TiO2 is found by the Kraut method to lie 0.82 eV below that of Sb2Se3, whereas the CdS CBM is only 0.01 eV below that of Sb2Se3. Furthermore, a significant difference is observed between the natural alignment- and Kraut method-determined offsets for TiO2/Sb2Se3, whereas there is little difference for CdS/Sb2Se3. Finally, these results are related to device performance, taking into consideration how these results may guide the future development of Sb2Se3 solar cells and providing a methodology that can be used to assess band alignments in device-relevant systems

Band alignment of Sb2O3 and Sb2Se3

Antimony selenide (Sb2Se3) possesses great potential in the field of photovoltaics (PV) due to its suitable properties for use as a solar absorber and good prospects for scalability. Previous studies have reported the growth of a native antimony oxide (Sb2O3) layer at the surface of Sb2Se3 thin films during deposition and exposure to air, which can affect the contact between Sb2Se3 and subsequent layers. In this study, photoemission techniques were utilized on both Sb2Se3 bulk crystals and thin films to investigate the band alignment between Sb2Se3 and the Sb2O3 layer. By subtracting the valence band spectrum of an in situ cleaved Sb2Se3 bulk crystal from that of the atmospherically contaminated bulk crystal, a valence band offset (VBO) of −1.72 eV is measured between Sb2Se3 and Sb2O3. This result is supported by a −1.90 eV VBO measured between Sb2O3 and Sb2Se3 thin films via the Kraut method. Both results indicate a straddling alignment that would oppose carrier extraction through the back contact of superstrate PV devices. This work yields greater insight into the band alignment of Sb2O3 at the surface of Sb2Se3 films, which is crucial for improving the performance of these PV devices

Sn 5 s 2 lone pairs and the electronic structure of tin sulphides: A photoreflectance, high-energy photoemission, and theoretical investigation

The effects of Sn 5 s lone pairs in the different phases of Sn sulphides are investigated with photoreflectance, hard x-ray photoemission spectroscopy (HAXPES), and density functional theory. Due to the photon energy-dependence of the photoionization cross sections, at high photon energy, the Sn 5 s orbital photoemission has increased intensity relative to that from other orbitals. This enables the Sn 5 s state contribution at the top of the valence band in the different Sn-sulphides, SnS, Sn 2 S 3 , and SnS 2 , to be clearly identified. SnS and Sn 2 S 3 contain Sn(II) cations and the corresponding Sn 5 s lone pairs are at the valence band maximum (VBM), leading to ∼ 1.0 –1.3 eV band gaps and relatively high VBM on an absolute energy scale. In contrast, SnS 2 only contains Sn(IV) cations, no filled lone pairs, and therefore has a ∼ 2.3 eV room-temperature band gap and much lower VBM compared with SnS and Sn 2 S 3 . The direct band gaps of these materials at 20 K are found using photoreflectance to be 1.36, 1.08, and 2.47 eV for SnS, Sn 2 S 3 , and SnS 2 , respectively, which further highlights the effect of having the lone-pair states at the VBM. As well as elucidating the role of the Sn 5 s lone pairs in determining the band gaps and band alignments of the family of Sn-sulphide compounds, this also highlights how HAXPES is an ideal method for probing the lone-pair contribution to the density of states of the emerging class of materials with n s 2 configuration

P-type conductivity in Sn-doped Sb2Se3

Antimony selenide (Sb2Se3) is a promising absorber material for thin-film photovoltaics. However, certain areas of fundamental understanding of this material remain incomplete and this presents a barrier to further efficiency gains. In particular, recent studies have highlighted the role of majority carrier type and extrinsic doping in drastically changing the performance of high efficiency devices [1]. Herein, Sndoped Sb2Se3 bulk crystals are shown to exhibit p-type conductivity using Hall effect and hot-probe measurements. The measured conductivities are higher than those achieved through native defects alone, but with a carrier density (up to 7.4 × 1014 cm−3) several orders of magnitude smaller than the quantity of Sn included in the source material. Additionally, a combination of ultraviolet, X-ray and hard X-ray photoemission spectroscopies are employed to obtain a non-destructive depth profile of the valence band maximum, confirming p-type conductivity and indicating a majority carrier type inversion layer at the surface. Finally, these results are supported by density functional theory calculations of the defect formation energies in Sn-doped Sb2Se3, showing a possible limit on the carrier concentration achievable with Sn as a dopant. This study sheds light on the effectiveness of Sn as a p-type dopant in Sb2Se3 and highlights avenues for further optimisation of doped Sb2Se3 for solar energy devices

How the amount of copper influences the formation and stability of defects in CdTe solar cells

With a 22.1% efficiency record and the successful results in terms of production yield, CdTe based thin film solar cells are today a competing technology with traditional silicon solar cells. Despite different copper-free back contacts have been applied, Cu is present in all the most performing CdTe devices. On the other hand, it is well known that Cu is a fast diffuser in CdTe, and it heavily influences the devices degradation; thus controlling its concentration is very important. In this paper a study of the influence of copper quantity on the performance of the devices and stability at the back contact is presented. CdTe cells fabricated with a 0.1 nm thick Cu layer are compared to devices fabricated with 2.0, 1.0 and 0.5 nm thick Cu layers. The amount of copper affects the performance and aging of the samples. Moreover an inversion of the bias dependency (solar cells in open circuit or in short circuit under current flow), during the aging, occurs in samples containing a copper layer below a certain thickness, suggesting that another degradation mechanism predominates

Position of Carbonyl Group Affects Tribological Performance of Ester Friction Modifiers

The tribological properties of lubricants can be effectively improved by the introduction of amphiphilic molecules, whose performance is largely affected by their polar head groups. In this work, the tribological performance in steel-steel contacts of two isomers, glycerol monostearate (GMS) and stearyl glycerate (SG), a glyceride and a glycerate, were investigated as organic friction modifiers (OFM) in hexadecane. SG exhibits a much lower friction coefficient and wear than GMS despite their similar structures. The same applies when comparing the performance of oleyl glycerate (OG) and its isomer, glycerol monooleate (GMO). Surface chemical analysis shows that SG forms a polar, carbon-based, tribofilm of around tens of nanometers thick, while GMS does not. This tribofilm shows low friction and robustness under nanotribology test, which may contribute to its superior performance at the macro-scale. The reason for this tribofilm formation can be due to the stronger adsorption of SG on the steel surface than that of GMS. The tribofilm formation can be stress-activated since lower friction and higher tribofilm coverage can be obtained under high load. This work offers insights into the lubrication mechanism of a novel OFM and provides strategies for OFM design.</p

How Oxygen Exposure Improves the Back Contact and Performance of Antimony Selenide Solar Cells

The improvement of antimony selenide solar cells by short-term air exposure is explained using complementary cell and material studies. We demonstrate that exposure to air yields a relative efficiency improvement of n-type Sb2Se3 solar cells of ca. 10% by oxidation of the back surface and a reduction in the back contact barrier height (measured by J–V–T) from 320 to 280 meV. X-ray photoelectron spectroscopy (XPS) measurements of the back surface reveal that during 5 days in air, Sb2O3 content at the sample surface increased by 27%, leaving a more Se-rich Sb2Se3 film along with a 4% increase in elemental Se. Conversely, exposure to 5 days of vacuum resulted in a loss of Se from the Sb2Se3 film, which increased the back contact barrier height to 370 meV. Inclusion of a thermally evaporated thin film of Sb2O3 and Se at the back of the Sb2Se3 absorber achieved a peak solar cell efficiency of 5.87%. These results demonstrate the importance of a Se-rich back surface for high-efficiency devices and the positive effects of an ultrathin antimony oxide layer. This study reveals a possible role of back contact etching in exposing a beneficial back surface and provides a route to increasing device efficiency