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We investigate magnetron-sputtered In2(OxS1−x)3 compounds acting as an alternative buffer system to the solution-grown CdS or Zn(O,S) buffer layers in Cu(In,Ga)Se2 (CIGS) thin-film solar cells. The influence of the oxygen content on the solar cell performance, microstructure of the mixed systems, bandgap, and band offsets to CIGS is investigated experimentally and also characterized by calculations based on density functional theory. Samples in a series with different chemical compositions ranging from In2S3 to In2O3 are either directly deposited from ceramic targets or from a pure In2S3 target by reactive sputtering by adding O2 in the Ar sputtering gas. The binary compounds In2S3 and In2O3 sputtered at 220 °C substrate temperature from ceramic targets exhibit a crystalline structure, whereas the ternary In2(O,S)3 compounds are either nanocrystalline in the case of In2(O0.25S0.75)3 or amorphous for In2(O0.5S0.5)3 and In2(O0.75S0.25)3. For [O]/([O] + [S]) ratios above 0.25, the cell efficiencies decrease drastically, mainly due to lower open-circuit voltages (VOC). This behavior can be explained by an increase of the negative conduction band offset between the CIGS absorber and the oxygen-rich In2(OxS1−x)3 or In2O3 buffer, resulting in pronounced VOC losses. Adding oxygen to In2S3 with optical bandgap energies of around 2 eV results in a bowing of the values to below 2 eV and finally reaching values of around 2.7 eV for In2O3 if an indirect band transition is assumed. In summary, our results reveal that pronounced oxygen incorporation in In2S3 is not beneficial in terms of CIGS device efficiency because oxygen is electronically inactive and poorly miscible. [ABSTRACT FROM AUTHOR]

The chemical and electronic structures in the near-surface region of Cu(In,Ga)Se2 thin-film solar cell absorbers are investigated using nondestructive soft and hard X-ray photoelectron spectroscopy. In addition to a pronounced surface Cu-depletion, the [Ga]/([In]+[Ga]) composition indicates that the topmost surface is Ga-poor (or In-rich). For the studied depth region, common depth profiling techniques generally fail to provide reliable information and, thus, the near-surface chemical and electronic structure profiles are often overlooked. The relation between the observed near-surface elemental compositions and the derived electronic properties of the absorber material is discussed. It is found that the surface band gap energy crucially depends on the Cu-deficiency of the absorber surface and suggests that it is, in this region, only secondarily determined by the [Ga]/([In]+[Ga]) ratio.

The design of a Cd‐free and wider‐bandgap buffer layer is stringent for future Cu(In,Ga)Se2 (CIGSe) thin‐film solar cell applications. For that, an In2S3 buffer layer alloyed with a limited amount of O (well below 25 mol%) has been proposed as a pertinent alternative solution to CdS or Zn(O,S) buffers. However, the chemical stability of the In2S3/CIGSe heterointerface when O is added is not completely clear. Therefore, in this work, the buffer/absorber interface for a series of sputter‐deposited In2S3 buffers with and without O is investigated. It is found that the solar cell with the highest open‐circuit voltage is obtained for the O‐free In2S3 buffer sputtered at 220 °C. This improved open‐circuit voltage could be explained by the presence of a 20 nm‐thick ordered vacancy compound (OVC) at the absorber surface. A much thinner OVC layer (5 nm) or even the absence of this layer is found for the cell with In2(O0.25S0.75)3 buffer layer where O is inserted. The volume fraction of the OVC layer is directly linked with the magnitude of Cu diffusion from the CIGSe surface into the In2(OxS1−x)3 buffer layer. The O addition strongly reduces the Cu diffusion inside the buffer layer up to complete suppression for very high O contents in the buffer. Finally, it is discussed that the presence of the OVC layer may lower the valence band maximum, thereby forming a hole barrier, suppressing charge carrier recombination at the In2(OxS1−x)3/CIGSe interface, which could result in an increased open‐circuit voltage. [ABSTRACT FROM AUTHOR]

Ag alloying of Cu(In,Ga)Se2 (CIGSe) absorbers in thin‐film solar cells leads to improved crystallization of these absorber layers at lower substrate temperatures than for Ag‐free CIGSe thin films as well as to enhanced cation interdiffusion, resulting in reduced Ga/In gradients. However, the role of Ag in the microscopic structure–property relationships in the (Ag,Cu)(In,Ga)Se2 thin‐film solar cells as well as a correlation between the various microscopic properties of the polycrystalline ACIGSe absorber and open‐circuit voltage of the corresponding solar cell device has not been reported earlier. In the present work, we study the effect of Ag addition by analyzing the differences in the various bulk, grain‐boundary, optoelectronic, emission, and absorption‐edge properties of ACIGSe absorbers with that of a reference CIGSe absorber. By comparing thin‐film solar cells with similar band‐gap energies ranging from about 1.1 to about 1.2 eV, we were able to correlate the differences in their absorber material properties with the differences in the device performance of the corresponding solar cells. Various microscopic origins of open‐circuit voltage losses were identified, such as strong Ga/In gradients and local compositional variations within individual grains of ACIGSe layers, which are linked to absorption‐edge broadening, lateral fluctuations in luminescence‐energy distribution, and band tailing, thus contributing to radiative VOC losses. A correlation established between the effective electron lifetime, average grain size, and lifetime at the grain boundaries indicates that enhanced nonradiative recombination at grain boundaries is a major contributor to the overall VOC deficit in ACIGSe solar cells. Although the alloying with Ag has been effective in increasing the grain size and the effective electron lifetime, still, the Ga/In gradients and the grain‐boundary recombination in the ACIGSe absorbers must be reduced further to improve the solar‐cell performance. [ABSTRACT FROM AUTHOR]

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.

Thin-film solar cells with Cu(In,Ga)Se2 (CIGS) absorber layers have been intensively studied due to their high power conversion efficiencies. CIGS solar cells with Zn(O,S) buffer layers achieved record efficiencies due to their reduced parasitic absorption compared with the more commonly used CdS buffer. Accordingly, we have studied solution-grown Zn(O,S) buffer layers on polycrystalline CIGS absorber layers by complementary techniques. A bandgap energy Eg of 2.9 eV is detected by means of angle-resolved electroreflectance spectroscopy corresponding to Zn(O,S), whereas an additional Eg of 2.3 eV clearly appeared for a post-annealed CIGS solar cell (250 °C in air) compared with the as-grown state. To identify the chemical phase that contributes to the Eg of 2.3 eV, the microstructure and microchemistry of the Zn(O,S) buffer layers in the as-grown state and after annealing were analyzed by different transmission electron microscopic techniques on the submicrometer scale and energy-dispersive x-ray spectroscopy. We demonstrate that the combination of these methods facilitates a comprehensive analysis of the complex phase constitution of nanoscaled buffer layers. The results show that after annealing, the Cu concentration in Zn(O,S) is increased. This observation indicates the existence of an additional Cu-containing phase with Eg close to 2.3 eV, such as Cu2Se (2.23 eV) or CuS (2.36 eV), which could be one possible origin of the low power conversion efficiency and low fill factor of the solar cell under investigation. [ABSTRACT FROM AUTHOR]

Partial substitution of Cu by Ag in Cu(In,Ga)Se2 (CIGS) solar cells is advantageous as it allows lower temperature growth while maintaining high performance. To understand the role of Ag on device performance, we present a comprehensive analysis of (Ag,Cu)(In,Ga)Se2 (ACIGS) samples with an [Ag]/([Ag]+[Cu]) (AAC) ratio varying from 7% to 22%. The analysis involves a set of material and device characterization techniques as well as numerical simulations. Multiple electrical and material properties show a systematic dependence on the increased Ag content. These include a carrier-density decrease, a grain-size increase, and a flattened [Ga]/([Ga] + [In]) (GGI) profile leading to a higher minimum band gap energy and a reduced back grading. Although the best performing device (PCE = 18.0%) in this set has an AAC = 7%, cells with higher Ag contents have an advantage of a smoother absorber surface which is attractive for tandem applications, despite their slightly inferior conversion efficiencies (PCE = 16.4% for 22% Ag).

A new method for efficiently converting electron backscatter diffraction data obtained using serial sectioning by focused ion beam of a polycrystalline thin film into a computational, three-dimensional (3D) structure is presented. The reported data processing method results in a more accurate representation of the grain surfaces, reduced computer memory usage, and improved processing speed compared to traditional voxel methods. The grain structure of a polycrystalline absorption layer from a high-efficiency Cu(In,Ga)Se2 solar cell (19.5%) is reconstructed in 3D and the grain size and surface distribution is investigated. The grain size distribution is found to be best fitted by a log-normal distribution. We further find that the grain size is determined by the [Ga]/([Ga] + [In]) ratio in vertical direction, which was measured by glow discharge optical emission spectroscopy. Finally, the 3D model derived from the structural information is applied in optoelectronic simulations, revealing insights into the effects of grain boundary recombination on the open-circuit voltage of the solar cell. An accurate 3D structure like the one obtained with our method is a prerequisite for a detailed understanding of mechanical properties and for advanced optical and electronic simulations of polycrystalline thin films. [ABSTRACT FROM AUTHOR]

Big sets of experimental data are key to assess statistical device performance and to distill underlying trends. This insight, in turn, can then be used to improve on the fabrication process. We here describe a standardized and optimized inline fabrication process and present a statistical analysis of tens of thousands of cells with chalcopyrite‐type Cu(In,Ga)Se2 absorber. The large number of samples allows us to point out where Ag alloying into the absorber offers improvements, and how it couples with compositional and optoelectronic properties. Solar cell parameters as a function of chemical composition of the absorber highlight the importance of fill factor on overall cell performance. Finally, we calculate losses in open‐circuit voltage as a function of band gap energy and show that radiative losses can be reduced by increasing the amount of Cu and/or Ag. [ABSTRACT FROM AUTHOR]

Alkali-fluoride post-deposition treatments (PDTs) of Cu(In,Ga)Se2 (CIGS) absorbers have repeatedly resulted in device efficiency improvements, observed mainly due to an open-circuit voltage (Voc) enhancement. Replacement of the CdS buffer layer with a higher band gap alternative can increase the short-circuit current density (Jsc) and also eliminate the use of Cd. In many alternative-buffer attempts, however, the Jsc gain was accompanied by a Voc loss, resulting in some degree of performance loss. In order to better understand the impact of RbF-PDT, we analyze a combination of experimental devices produced in the same in-line CIGS run with and without RbF-PDT in combination with chemical-bath-deposited CdS and Zn(O,S) buffers. Low-temperature current–voltage curves indicate a difference in Rb impact on the CIGS/CdS and CIGS/Zn(O,S) p-n junctions. For example, the diode-current barrier which creates a rollover often observed in RbF-treated CIGS/CdS current–voltage curves is significantly reduced for the CIGS/Zn(O,S) junction. Although the RbF-PDT had a positive impact on both junction partner combinations, the CIGS/Zn(O,S) devices' Voc and fill factor (FF) benefited stronger from the RbF treatment. As a result, in our samples, the Jsc and FF gain balanced the Voc loss, thus reducing the efficiency difference between cells with CdS and Zn(O,S) buffers.

Polycrystalline Cu(In,Ga)Se2 (CIGSe) thin‐film solar cells exhibit gradual onset in their external quantum efficiency (EQE) spectra whose shape can be affected by various CIGSe material properties. Apart from influences on the charge‐carrier collection, a broadening of the EQE onset leads to enhanced radiative losses in open‐circuit voltage (Voc). In the present work, Gaussian broadening of parameters describing the EQE onset of thin‐film solar cells, represented by the standard deviation, 휎total, was evaluated to study the impacts of the effective band‐gap energy, the electron diffusion length, and the Ga/In gradient in the CIGSe absorber. It is shown that 휎total can be disentangled into contributions of these material properties, in addition to a residual component 휎residual. Effectively, 휎total depends only on a contribution related to the Ga/In gradient as well as on 휎residual. The present work highlights the connection of this compositional gradient, the microstructure in the polycrystalline CIGSe absorber, and the luminescence emission with the residual component 휎residual. It is demonstrated that a flat band‐gap with no compositional gradient in the bulk of the CIGSe absorber is essential to obtain the lowest 휎total values and thus result in lower recombination losses and gains in Voc. [ABSTRACT FROM AUTHOR]