Optical Measurement of the Stoichiometry of Thin-Film Compounds Synthetized From Multilayers: Example of Cu(In,Ga)Se2.

The properties of centimeter-sized thin-film compound semiconductors depend upon the morphology and chemical composition of the multiple submicrometer-thick elemental and alloy precursor layers from which they are synthesized. The challenge is to characterize the individual precursor layers over these length scales during a multistep synthesis without altering or contaminating them. Conventional electron and X-ray-based morphological and compositional techniques are invasive, require preparation, and are thus incompatible with in-line synthesis processes. In a proof-of-concept study, we applied confocal laser scanning microscopy (CLSM) as a noninvasive optical imaging technique, which measures three-dimensional surface profiles with nanoscale resolution, to this challenge. Using an array of microdots containing Cu(In,Ga)Se2 semiconductor layers for solar cells as an example, we performed CLSM correlative studies to quantify morphological and layer thickness changes during four stages of a thin-film compound synthesis. Using simple assumptions, we measured the micrometer-scale spatially resolved chemical composition of stacked precursor layers to predict the final material phases formed and predict relative device performance. The high spatial resolution, coupled with the ability to measure sizeable areas without influencing the synthesis at high speed, makes CLSM an excellent prospect for research and quality control tool for thin films.

Over 16% Efficient Solution-Processed Cu(In,Ga)Se2 Solar Cells via Incorporation of Copper-Rich Precursor Film.

Solution processing of Cu(In,Ga)Se2 (CIGS) absorber is a highly promising strategy for a cost-effective CIGS photovoltaic device. However, the device performance of solution-processed CIGS solar cells is still hindered by the severe non-radiative recombination resulting from deep defects and poor crystal quality. Here, a simple and effective precursor film engineering strategy is reported, where Cu-rich (CGI >1) CIGS layer is incorporated into the bottom of the CIGS precursor film. It has been discovered that the incorporation of the Cu-rich CIGS layer greatly improves the absorber crystallinity and reduces the trap state density. Accordingly, more efficient charge generation and charge transfer are realized. As a result of systematic processing optimization, the champion solution-processed CIGS device delivers an improved open-circuit voltage of 656 mV, current density of 33.15 mA cm-2 , and fill factor of 73.78%, leading to the high efficiency of 16.05%.

Refractive indices of layers and optical simulations of Cu(In,Ga)Se2 solar cells.

Cu(In,Ga)Se2 based solar cells have reached efficiencies close to 23%. Further knowledge-driven improvements require accurate determination of the material properties. Here, we present refractive indices for all layers in Cu(In,Ga)Se2 solar cells with high efficiency. The optical bandgap of Cu(In,Ga)Se2 does not depend on the Cu content in the explored composition range, while the absorption coefficient value is primarily determined by the Cu content. An expression for the absorption spectrum is proposed, with Ga and Cu compositions as parameters. This set of parameters allows accurate device simulations to understand remaining absorption and carrier collection losses and develop strategies to improve performances.

Alkali-templated surface nanopatterning of chalcogenide thin films: a novel approach toward solar cells with enhanced efficiency.

Concepts of localized contacts and junctions through surface passivation layers are already advantageously applied in Si wafer-based photovoltaic technologies. For Cu(In,Ga)Se2 thin film solar cells, such concepts are generally not applied, especially at the heterojunction, because of the lack of a simple method yielding features with the required size and distribution. Here, we show a novel, innovative surface nanopatterning approach to form homogeneously distributed nanostructures (<30 nm) on the faceted, rough surface of polycrystalline chalcogenide thin films. The method, based on selective dissolution of self-assembled and well-defined alkali condensates in water, opens up new research opportunities toward development of thin film solar cells with enhanced efficiency.

Employing Si solar cell technology to increase efficiency of ultra-thin Cu(In,Ga)Se2 solar cells.

Reducing absorber layer thickness below 500 nm in regular Cu(In,Ga)Se2 (CIGS) solar cells decreases cell efficiency considerably, as both short-circuit current and open-circuit voltage are reduced because of incomplete absorption and high Mo/CIGS rear interface recombination. In this work, an innovative rear cell design is developed to avoid both effects: a highly reflective rear surface passivation layer with nano-sized local point contact openings is employed to enhance rear internal reflection and decrease the rear surface recombination velocity significantly, as compared with a standard Mo/CIGS rear interface. The formation of nano-sphere shaped precipitates in chemical bath deposition of CdS is used to generate nano-sized point contact openings. Evaporation of MgF2 coated with a thin atomic layer deposited Al2O3 layer, or direct current magnetron sputtering of Al2O3 are used as rear surface passivation layers. Rear internal reflection is enhanced substantially by the increased thickness of the passivation layer, and also the rear surface recombination velocity is reduced at the Al2O3/CIGS rear interface. (MgF2/)Al2O3 rear surface passivated ultra-thin CIGS solar cells are fabricated, showing an increase in short circuit current and open circuit voltage compared to unpassivated reference cells with equivalent CIGS thickness. Accordingly, average solar cell efficiencies of 13.5% are realized for 385 nm thick CIGS absorber layers, compared with 9.1% efficiency for the corresponding unpassivated reference cells.

Expanding the Notch Region by Adjusting the Copper Growth Profile for High-Efficiency Flexible Cu(In,Ga)Se2 Solar Cells.

Flexible CIGS solar cells, with their adjustable band gap for future flexible tandem solar cells and flexibility for roll-to-roll manufacturing, have the potential to be used in a wide range of applications. However, flexible CIGS solar cells are always manufactured at relatively low temperatures, where Cu diffusion has a substantial impact on the CIGS surface state and defect formation. To address these issues, we designed a new CIGS growth profile in this work by carefully examining the effects of different locations of excess Cu in the third stage of the CIGS deposition profile. The results showed that adding more Cu to the middle part of the third stage can enhance the crystal quality, expand the GGI grading notch region, move the GGI minimum to the CdS side, cause a JSC rise, achieve proper band alignment at the interface, and then enhance the FF. By taking advantage of these advantages, the photoelectric conversion efficiency (PCE) is significantly raised. An impressive improvement of 32.6% over the initial efficiency of 13.8% has been attained, yielding a high efficiency of 18.3% and providing a strong basis for the development of flexible CIGS solar cells.

Alkali Metal Pretreatment for Precise Na Doping and Voc Improvement in CIGS Thin-Film Solar Cells.

The pretreatment of the Cu(In,Ga)Se2 (CIGS) absorption layer using an alkali element can effectively improve the photoelectric conversion efficiency (PCE) of CIGS solar cells. Here, we propose using NaF layer pretreatment below the CIGS absorption layer deposited by a three-stage process. Sodium ions in NaF can effectively suppress the diffusion of Ga elements and form a steep gradient backscatter layer on the back of the CIGS absorption layer, thereby passivating solar cell defects, inhibiting carrier recombination, promoting carrier transmission and collection, improving open circuit voltage (VOC), short circuit current (Jsc), and filling factor (FF), and further improving the PCE.

Towards All-Non-Vacuum-Processed Photovoltaic Systems: A Water-Based Screen-Printed Cu(In,Ga)Se2 Photoabsorber with a 6.6% Efficiency.

During the last few decades, major advances have been made in photovoltaic systems based on Cu(In,Ga)Se2 chalcopyrite. However, the most efficient photovoltaic cells are processed under high-energy-demanding vacuum conditions. To lower the costs and facilitate high-throughput production, printing/coating processes are proving to be effective solutions. This work combined printing, coating, and chemical bath deposition processes of photoabsorber, buffer, and transparent conductive layers for the development of solution-processed photovoltaic systems. Using a sustainable approach, all inks were formulated using water and ethanol as solvents. Screen printing of the photoabsorber on fluorine-doped tin-oxide-coated glass followed by selenization, chemical bath deposition of the cadmium sulfide buffer, and final sputtering of the intrinsic zinc oxide and aluminum-doped zinc oxide top conductive layers delivered a 6.6% maximum efficiency solar cell, a record for screen-printed Cu(In,Ga)Se2 solar cells. On the other hand, the all-non-vacuum-processed device with spray-coated intrinsic zinc-oxide- and tin-doped indium oxide top conductive layers delivered a 2.2% efficiency. The given approaches represent relevant steps towards the fabrication of sustainable and efficient Cu(In,Ga)Se2 solar cells.

Rb Diffusion and Oxide Removal at the RbF-Treated Ga2O3/Cu(In,Ga)Se2 Interface in Thin-Film Solar Cells.

We report on the chemical structure of Cu(In,Ga)Se2 (CIGSe) thin-film solar cell absorber surfaces and their interface with a sputter-deposited Ga2O3 buffer. The CIGSe samples were exposed to a RbF postdeposition treatment and an ammonia-based rinsing step, as used in corresponding thin-film solar cells. For a detailed chemical analysis of the impact of these treatments, we employed laboratory-based X-ray photoelectron spectroscopy, X-ray-excited Auger electron spectroscopy, and synchrotron-based hard X-ray photoelectron spectroscopy. On the RbF-treated surface, we find both Rb and F, which are then partly (Rb) and completely (F) removed by the rinse. The rinse also removes Ga-F, Ga-O, and In-O surface bonds and reduces the Ga/(Ga + In) ratio at the CIGSe absorber surface. After Ga2O3 deposition, we identify the formation of In oxides and the diffusion of Rb and small amounts of F into/onto the Ga2O3 buffer layer but no indication of the formation of hydroxides.

SnS2 Nanoparticles and Thin Film for Application as an Adsorbent and Photovoltaic Buffer.

Energy consumption and environmental pollution are major issues faced by the world. The present study introduces a single solution using SnS2 for these two major global problems. SnS2 nanoparticles and thin films were explored as an adsorbent to remove organic toxic materials (Rhodamine B (RhB)) from water and an alternative to the toxic cadmium sulfide (CdS) buffer for thin-film solar cells, respectively. Primary characterization tools such as X-ray photoelectron spectroscopy (XPS), Raman, X-ray diffraction (XRD), and UV-Vis-NIR spectroscopy were used to analyze the SnS2 nanoparticles and thin films. At a reaction time of 180 min, 0.4 g/L of SnS2 nanoparticles showed the highest adsorption capacity of 85% for RhB (10 ppm), indicating that SnS2 is an appropriate adsorbent. The fabricated Cu(In,Ga)Se2 (CIGS) device with SnS2 as a buffer showed a conversion efficiency (~5.1%) close to that (~7.5%) of a device fabricated with the conventional CdS buffer, suggesting that SnS2 has potential as an alternative buffer.

Influence of the Al-Doped ZnO Sputter-Deposition Temperature on Cu(In,Ga)Se2 Solar Cell Performance.

Heterojunction Cu(In,Ga)Se2 (CIGS) solar cells comprise a substrate/Mo/CIGS/CdS/i-ZnO/ZnO:Al. Here, Al-doped zinc oxide (AZO) films were deposited by magnetron sputtering, and the substrate temperature was optimized for CIGS solar cells with two types of CIGS light absorbers with different material properties fabricated by three-stage co-evaporation and two-step metallization followed by sulfurization after selenization (SAS). The microstructure and optoelectronic properties of the AZO thin films fabricated at different substrate temperatures (150-550 °C) were analyzed along with their effects on the CIGS solar cell performance. X-ray diffraction results confirmed that all the deposited AZO films have a hexagonal wurtzite crystal structure regardless of substrate temperature. The optical and electrical properties of the AZO films improved significantly with increasing substrate temperature. Photovoltaic performances of the two types of CIGS solar cells were influenced by changes in the AZO substrate temperature. For the three-stage co-evaporated CIGS cell, as the sputter-deposition temperature of the AZO layer was raised from 150 °C to 550 °C, the efficiencies of CIGS devices decreased monotonically, which suggests the optimum AZO deposition temperature is 150 °C. In contrast, the cell efficiency of CIGS devices fabricated using the two-step SAS-processed CIGS absorbers improved with increasing the AZO deposition temperature from 150 to 350 °C. However, the rise in AZO deposition temperature to 550 °C decreased the cell efficiency, indicating that the optimum AZO deposition temperature was 350 °C. The findings of this study provide insights for the efficient fabrication of CIGS solar cells considering the correlation between CIGS absorber characteristics and AZO layer deposition temperature.

Tailored Band Structure of Cu(In,Ga)Se2 Thin-Film Heterojunction Solar Cells: Depth Profiling of Defects and the Work Function.

An efficient carrier transport is essential for enhancing the performance of thin-film solar cells, in particular Cu(In,Ga)Se2 (CIGS) solar cells, because of their great sensitivities to not only the interface but also the film bulk. Conventional methods to investigate the outcoming carriers and their transport properties measure the current and voltage either under illumination or dark conditions. However, the evaluation of current and voltage changes along the cross-section of the devices presents several limitations. To mitigate this shortcoming, we prepared gently etched devices and analyzed their properties using micro-Raman scattering spectroscopy, Kelvin probe force microscopy, and photoluminescence measurements. The atomic distributions and microstructures of the devices were investigated, and the defect densities in the device bulk were determined via admittance spectroscopy. The effects of Ga grading on the charge transport at the CIGS-CdS interface were categorized into various types of band offsets, which were directly confirmed by our experiments. The results indicated that reducing open-circuit voltage loss is crucial for obtaining a higher power conversion efficiency. Although the large Ga grading in the CIGS absorber induced higher defect levels, it effectuated a smaller open-circuit voltage loss because of carrier transport enhancement at the absorber-buffer interface, resulting from the optimized conduction band offsets.

Fingerprints Indicating Superior Properties of Internal Interfaces in Cu(In,Ga)Se2 Thin-Film Solar Cells.

Growth of Cu(In,Ga)Se2 (CIGS) absorbers under Cu-poor conditions gives rise to incorporation of numerous defects into the bulk, whereas the same absorber grown under Cu-rich conditions leads to a stoichiometric bulk with minimum defects. This suggests that CIGS absorbers grown under Cu-rich conditions are more suitable for solar cell applications. However, the CIGS solar cell devices with record efficiencies have all been fabricated under Cu-poor conditions, despite the expectations. Therefore, in the present work, both Cu-poor and Cu-rich CIGS cells are investigated, and the superior properties of the internal interfaces of the Cu-poor CIGS cells, such as the p-n junction and grain boundaries, which always makes them the record-efficiency devices, are shown. More precisely, by employing a correlative microscopy approach, the typical fingerprints for superior properties of internal interfaces necessary for maintaining a lower recombination activity in the cell is discovered. These are a Cu-depleted and Cd-enriched CIGS absorber surface, near the p-n junction, as well as a negative Cu factor (∆ß) and high Na content (>1.5 at%) at the grain boundaries. Thus, this work provides key factors governing the device performance (efficiency), which can be considered in the design of next-generation solar cells.

Study on the Performance of Oxygen-Rich Zn(O,S) Buffers Fabricated by Sputtering Deposition and Zn(O,S)/Cu(In,Ga)(S,Se)2 Interfaces.

We developed a novel process for fabricating oxygen-rich Zn(O,S) buffer layers by magnetron reactive sputtering with a single oxygen-rich Zn(O,S) target, suitable for industrial all-dry production. Then, we successfully fabricated Cd-free Cu(In,Ga)(S,Se)2 (CIGSSe) solar cells. By varying the oxygen partial pressure during sputtering from 0 to 20%, we precisely controlled the Zn(O,S) composition, then systematically investigated its effects on the quality of oxygen-rich Zn(O,S) films, the properties of formed p-n junctions, and the performance of CIGSSe solar cells with Zn(O,S) buffer. We demonstrated that reactive sputtering with a Zn(O,S) target can generate a homogeneous, high-quality oxygen-rich Zn(O,S) buffer on large-area substrates. We observed a unique and unusual phenomenon: the appropriate content of secondary phase ZnSO4 and ZnSO3 improved the band alignment for oxygen-rich Zn(O,S). Combining our proposed schematic diagram of band alignmentat the Zn(O,S)/CIGSSe interface, we established a crucial correlation between the device performance and the interfacial properties at the p-n junction. For the CIGSSe device performance, the band alignment matching at the heterojunction plays a primary role, and the quality of oxygen-rich Zn(O,S) films plays a secondary role. Consequently, an excellent oxygen-rich Zn(O,S) buffer can be obtained with 10% Zn(O,S) deposition oxygen partial pressure , and the optimized device shows a higher Voc (447 mV) and a similar conversion efficiency (11.2%) than conventional CIGSSe devices with CdS buffer.

Large-Scale Synthesis of Semiconducting Cu(In,Ga)Se2 Nanoparticles for Screen Printing Application.

During the last few decades, the interest over chalcopyrite and related photovoltaics has been growing due the outstanding structural and electrical properties of the thin-film Cu(In,Ga)Se2 photoabsorber. More recently, thin film deposition through solution processing has gained increasing attention from the industry, due to the potential low-cost and high-throughput production. To this end, the elimination of the selenization procedure in the synthesis of Cu(In,Ga)Se2 nanoparticles with following dispersion into ink formulations for printing/coating deposition processes are of high relevance. However, most of the reported syntheses procedures give access to tetragonal chalcopyrite Cu(In,Ga)Se2 nanoparticles, whereas methods to obtain other structures are scarce. Herein, we report a large-scale synthesis of high-quality Cu(In,Ga)Se2 nanoparticles with wurtzite hexagonal structure, with sizes of 10-70 nm, wide absorption in visible to near-infrared regions, and [Cu]/[In + Ga] ≈ 0.8 and [Ga]/[Ga + In] ≈ 0.3 metal ratios. The inclusion of the synthesized NPs into a water-based ink formulation for screen printing deposition results in thin films with homogenous thickness of ≈4.5 µm, paving the way towards environmentally friendly roll-to-roll production of photovoltaic systems.

Analysis of Compositional Gradients in Cu(In,Ga)(S,Se)2 Solar Cell Absorbers Using Energy Dispersive X-ray Analysis with Different Acceleration Energies.

The efficiency of Cu(In,Ga)(S,Se)2 (CIGSSe) solar cell absorbers can be increased by the optimization of the Ga/In and S/Se gradients throughout the absorber. Analyzing such gradients is therefore an important method in tracking the effectiveness of process variations. To measure compositional gradients in CIGSSe, energy dispersive X-ray analysis (EDX) with different acceleration energies performed at both the front surface and the backside of delaminated absorbers was used. This procedure allows for the determination of compositional gradients at locations that are millimeters apart and distributed over the entire sample. The method is therefore representative for a large area and yields information about the lateral homogeneity in the millimeter range. The procedure is helpful if methods such as secondary ion-mass (SIMS), time-of-flight SIMS, or glow-discharge optical emission spectrometry (GDOES) are not available. Results of such EDX measurements are compared with GDOES, and they show good agreement. The procedure can also be used in a targeted manner to detect local changes of the gradients in inhomogeneities or points of interest in the µm range. As an example, a comparison between the compositional gradients in the regular absorber and above the laser cut separating the Mo back contact is shown.

Eco-friendly and cost-efficient inks for screen-printed fabrication of copper indium gallium diselenide photoabsorber thin films.

Given the societal concerns about the use of toxic chemicals and costly fabrication of functional materials and devices for photovoltaic applications, it is important to develop alternative sustainable methodologies. Previous studies have shown that cost-effective printing fabrication of Cu(In,Ga)Se2 thin film photovoltaics represents an interesting alternative to energy-demanding vacuum-based deposition methods, commonly used to produce Cu(In,Ga)Se2 photovoltaics. To enrich the field of printed Cu(In,Ga)Se2 photoabsorber thin films and to develop associated eco-friendly solutions, two novel inks, consisting of non-toxic reagents and readily available oxide materials, are reported. Screen printing of the inks over fluorine-doped tin oxide conductive substrates followed by swift selenization of the resultant patterns provides a straightforward route to phase-pure, uniform, and compact Cu(In,Ga)Se2 films with thickness and band gap energies ranging from 2.5 µm to 3.5 µm and from 0.97 eV to 1.08 eV, respectively. The present approach represents an important step forward in the sustainable fabrication of Cu(In,Ga)Se2 photovoltaics, where the physical properties of the photoabsorber can be easily adjusted by tuning the conditions of the screen printing process and the metal ratios in the inks.

Evolution of Morphological and Chemical Properties at p-n Junction of Cu(In,Ga)Se2 Solar Cells with Zn(O,S) Buffer Layer as a Function of KF Postdeposition Treatment Time.

We carried out KF postdeposition treatment (PDT) on a Cu(In,Ga)Se2 (CIGS) layer with a process time varying from 50 to 200 s. The highest CIGS solar-cell efficiency was achieved at a KF PDT process time of 50 s; in this condition, we observed the highest level of K element at the near-surface of the CIGS layer and the perfectly passivated pinholes on the CIGS surface. At process times above 150 s, the oversupplied KF agglomerated into large islands and was subsequently eliminated during the deposition of the chemical bath deposition (CBD)-Zn(O,S) buffer layer owing to the islands' water-soluble characteristics. As a result, the growth mechanism of the CBD-Zn(O,S) layer varied as a function of KF PDT process time. X-ray photoemission spectroscopy (XPS) measurements were used to examine the dependency of the chemical state on the KF PDT process time, and from the results, we formulated a chemical reaction model based on the shift in the elemental binding energy following deposition of the CBD-Zn(O,S) buffer layer. The chemical states of the K-In-Se phase, which have a beneficial effect on the solar-cell performance owing to the formation of durable and improved p-n junctions, are formed only at a KF PDT process time of 50 s. We derived band alignments from the XPS depth profiles by extracting the conduction- and valence-band offsets, and we used optical-pump-THz-probe spectroscopy to measure the ultrafast photocarrier lifetimes related to the defect states following KF PDT. Our key findings can be summarized as follows: (i) photocarrier transport is beneficial at a low barrier height, and (ii) the photocarrier lifetime increases when the K-In-Se phases are formed on the CIGS surface, which allows K+ ions to be effectively substituted into Cu vacancies.

Engineering a Ga-Gradient by One-Step Sputtering to Achieve Over 15% Efficiency of Cu(In,Ga)Se2 Flexible Solar Cells without Post-selenization.

A one-step sputtering process using a quaternary target has been demonstrated to be a simple route to form Cu(In,Ga)Se2 (CIGSe) absorber without post-selenization; however, the lack of a Ga-grading structure in the CIGSe absorber confines its efficiency. Here, we demonstrate a one-step cosputtering process to control the Ga profile in the CIGSe absorber on flexible stainless steel substrates. Special attention was paid to the formation of second phases and their effects on the cell performance. Although the normal Ga-grading and efficiency enhancement could be achieved by cosputtering of CIGSe and Ga2Se3 targets, high-energy ion bombardment during the sputtering process might cause the decomposition of the Ga2Se3 target, leading to the formation of Ga2O3 in the CIGSe absorber, which gradually degraded the device performance. We replaced the Ga2Se3 target with a stoichiometric CuGaSe2 target for cosputtering, which can further enhance the cell efficiency due to the elimination of Ga2O3. However, when the Ga content at the back side of CIGSe is further increased by raising the deposition power of the CuGaSe2 target, the phase separation of CuGaSe2 may take place, resulting in the formation of Cu2-XSe and CuGaSe2 at the back side of the CIGSe absorber; therefore, the recombination at the back side is increased. By cosputtering a CIGSe target with a Cu-deficient CuGaSe2 target, we can suppress the formation of second phases and achieve designable normal grading, leading to the highest efficiency of 15.63% without post-selenization on flexible substrates.

Influence of Sulfur Evaporation during or after KF-Post Deposition Treatment On Cu(In,Ga)Se2/CdS Interface Formation.

This work investigates the impact of the elemental sulfur evaporation during or after KF-post deposition treatment (KF-PDT) on the resulting Cu(In,Ga)Se2/chemical bath deposited(CBD)-CdS interface. Chemical composition of the various interfaces were determined through Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger spectroscopy (XAES). Cu(In,Ga)Se2 absorber which experienced KF-PDT in selenium atmosphere (KSe sample) exhibits the formation of the well-reported In-Se based topping layer. Additional exposure to elemental sulfur, resulting in KSe+S sample, induces the partial sulfurization of this overlayer and/or of the absorber. After short immersion into the CdS bath, the resulting In-rich surfaces of KSe and KSe+S are likely to turn into few atomic layers of Cd-In-(Se/S)-O whose [S]/[Se]+[S] ratio and O content depend on their respective post deposition treatment. In contrast, KF-PDT performed in S atmosphere does not show an In-rich surface, making the early stage of CdS growth similar to that observed on untreated CIGSe.