Cu(In,Ga)Se2 superstrate solar cells: prospects and limitations

Superstrate solar cells were prepared by thermal evaporation of Cu(In,Ga)Se2 onto ZnO coated glass substrates. For the first time, photo‐conversion efficiencies above 11% were reached without the necessity of additional light soaking or forward biasing of the solar cell. This was achieved by modifying the deposition process as well as the sodium doping. Limitations of the superstrate device configuration and possible ways to overcome these were investigated by analyzing the hetero‐interface with electron microscopy and X‐ray photoemission spectroscopy measurements, combined with capacitance spectroscopy and device simulations. A device model was derived that explains how on the one hand the GaO_x, which forms at the CIGSe/ZnO interface, reduces the interface recombination. On the other hand how it limits the efficiency by acting as an electron barrier at the hetero‐interface presumably because of a high density of negatively charged acceptor states like Cu_Ga. The addition of sodium enhances the p‐type doping of the absorber but also increases the net doping within the GaO_x. Hence, a trade‐off between these two effects is required. The conversion efficiency was found to decrease over time, which can be explained in our model by field‐induced diffusion of sodium cations out from the GaO_x layer. The proposed device model is able to explain various effects frequently observed upon light soaking and forward biasing of superstrate devices. Copyright © 2014 John Wiley & Sons, Ltd.     

A Near‐Infrared cis‐Configured Squaraine Co‐Sensitizer for High‐Efficiency Dye‐Sensitized Solar Cells

A cis‐configured squaraine dye (HSQ1), synthesized by incorporation of a strongly electron‐withdrawing dicyanovinyl group into the central squaric acid moiety, is employed in dye‐sensitized solar cells (DSCs). In solution, HSQ1 displays an intense absorption in the near‐infrared region with a maximum at 686 nm and when the dye is adsorbed on a TiO₂ surface, the absorption spectrum broadens in both the blue and the near‐infrared regions, which is favorable for efficient light harvesting over a broad wavelength range. A solar cell sensitized with HSQ1 shows a broader incident photon‐to‐current conversion efficiency (IPCE) spectrum (from 400 to 800 nm) and a higher IPCE in the long‐wavelength region (71% at 700 nm) than a cell sensitized with squaraine dye SQ1. Furthermore, a solar cell co‐sensitized with HSQ1 and N3 dye shows remarkably improved short‐circuit current density and open‐circuit voltage compared to those of a DSC based on N3 alone and fabricated under the same conditions. The energy‐conversion efficiency of the co‐sensitized DSC is 8.14%, which is the highest reported efficiency for a squaraine dye–based co‐sensitized DSC without using Al₂O₃ layer.     

Influence of Mo back contact porosity on co‐evaporated Cu(In,Ga)Se2 thin film properties and related solar cell

The present study aims at investigating the influence of Ar sputtering gas pressure on the properties of molybdenum back contact (deposited on soda‐lime glass) and consequences on co‐evaporated Cu(In,Ga)Se₂ (CIGSe) absorber layer and related solar cell. Films 300 nm thick have been grown with argon pressure between 0·75 and 11·25 mTorr; these films have been characterized by several techniques showing that the increase of the sputtering pressure yields wider amorphous areas, containing oxygen and sodium, between the molybdenum grains, thus higher sheet resistance. The volume ratio of these amorphous areas is referenced to as “porosity”. The structural and morphological properties of co‐evaporated CIGSe have not been reliably observed influenced by the molybdenum porosity; the only noticeable change is the sodium content of the absorber, which increases with the porosity of the back contact. The impact of the amount of sodium on the device performance has been observed to be very important. On the one hand, as already reported, sodium is beneficial for the open‐circuit voltage. On the other hand, a too high amount of sodium is detrimental for the fill factor (hindered shunt resistance), thus the cell efficiency; this latter observation is interpreted as a change in the grain boundary electrical properties. Copyright © 2011 John Wiley & Sons, Ltd.     

High‐efficiency Cu2ZnSn(S,Se)4 solar cells fabricated through a low‐cost solution process and a two‐step heat treatment

A method for fabricating high‐efficiency Cu₂ZnSn(S,Se)₄ (CZTSSe) solar cells is presented, and it is based on a non‐explosive, low‐cost, and simple solution process followed by a two‐step heat treatment. 2‐Methoxyethanol was used as a solvent, and Cu, Zn, Sn, chloride salts, and thiourea were used as solutes. A CZTSSe absorber was prepared by sulfurising and then selenising an as‐coated Cu₂ZnSnS₄ (CZTS) film. Sulfurisation in a sulfur vapour filled furnace for a long time (2 h) enhanced the crystallisation of the as‐coated CZTS film and improved the stability of the CZTS precursor, and selenisation promoted further grain growth to yield a void‐free CZTSSe film. Segregation of Cu and S at the grain boundaries, the absence of a fine‐grain bottom layer, and the large grain size of the CZTSSe absorber were the main factors that enhanced the grain‐to‐grain transport of carriers and consequently the short‐circuit current (J_sc ) and efficiency. The efficiency of the CZTS solar cell was 5.0%, which increased to 10.1% after selenisation. For the 10.1% CZTSSe solar cell, the external quantum efficiency was approximately 80%, the open‐circuit voltage was 450 mV, the short‐circuit current was 36.5 mA/cm², and the fill factor was 61.9%. Copyright © 2016 John Wiley & Sons, Ltd.     

Improving the photovoltaic performance of co‐evaporated Cu2ZnSnS4 thin‐film solar cells by incorporation of sodium from NaF layers

We have investigated the influence of sodium (Na) on the properties of co‐evaporated Cu₂ZnSnS₄ (CZTS) layer microstructures and solar cells. The photovoltaic performance and diode properties were improved by incorporating Na from NaF layers into the CZTS layers, while Na had a negligible effect on the microstructural properties of the layer. The best cell fabricated by using an optimal CZTS layer (Cu/(Zn + Sn) = 0.70, Zn/Sn = 1.8) yielded an active area efficiency of 5.23%. The analysis of device properties suggests that charge‐carrier recombination at CZTS/CdS interface is suppressed by intentional Na incorporation from NaF layers. Copyright © 2016 John Wiley & Sons, Ltd.     

Novel Near‐Infrared Squaraine Sensitizers for Stable and Efficient Dye‐Sensitized Solar Cells

A new molecular design strategy for tuning the energy levels of cis‐configured squaraine sensitizers for dye‐sensitized solar cells is described. The Hammett substituent constant and the π‐conjugation length are used as quantitative indicators to modify the central squarate moiety of the sensitizer dyes; specifically, novel near‐infrared squaraine dyes HSQ3 and HSQ4 are synthesized by incorporation of an electron‐withdrawing and π‐extending ethyl cyanoacetate unit on the central squarate moiety. The solution absorption maximum of HSQ4 occurs at 703 nm, and the energy levels of the lowest unoccupied molecular orbital and the highest occupied molecular orbital are in the ideal range for energetically efficient electron injection and regeneration of the oxidized dye. A solar cell sensitized with HSQ4 exhibits a broad incident photo­n‐to‐current conversion efficiency spectrum, extending into the near‐infrared region with a maximum value of 80% at 720 nm, which is is the highest value reported for a squaraine dye–based dye‐sensitized solar cell. The HSQ4‐sensitized solar cell also exhibits excellent durability during light soaking, owing to the double anchors attaching the dye to the TiO₂ surface and to the long alkyl chains extending outward from the surface.     

8% Efficient thin‐film polycrystalline‐silicon solar cells based on aluminum‐ induced crystallization and thermal CVD

A considerable cost reduction could be achieved in photovoltaics if efficient solar cells could be made from polycrystalline‐silicon (pc‐Si) thin films on inexpensive substrates. We recently showed promising solar cell results using pc‐Si layers obtained by aluminum‐induced crystallization (AIC) of amorphous silicon in combination with thermal chemical vapor deposition (CVD). To obtain highly efficient pc‐Si solar cells, however, the material quality has to be optimized and cell processes different from those applied for standard bulk‐Si solar cells have to be developed. In this work, we present the different process steps that we recently developed to enhance the efficiency of pc‐Si solar cells on alumina substrates made by AIC in combination with thermal CVD. Our present pc‐Si solar cell process yields cells in substrate configuration with efficiencies so far of up to 8·0%. Spin‐on oxides are used to smoothen the alumina substrate surface to enhance the electronic quality of the absorber layers. The cells have heterojunction emitters consisting of thin a‐Si layers that yield much higher V_oc values than classical diffused emitters. Base and emitter contacts are on top of the cell in interdigitated finger patterns, leading to fill factors above 70%. The front surface of the cells is plasma textured to increase the current density. Our present pc‐Si solar cell efficiency of 8% together with the fast progression that we have made over the last few years indicate the large potential of pc‐Si solar cells based on the AIC seed layer approach. Copyright © 2007 John Wiley & Sons, Ltd.     

Impact of silicon quantum dot super lattice and quantum well structure as intermediate layer on p‐i‐n silicon solar cells

The photovoltaic effect of the silicon (Si)/silicon carbide (SiC) quantum dot super lattice (QDSL) and multi‐quantum well (QW) strucutres is presented based on numerical simulation and experimental studies. The QDSL and QW structures act as an intermediate layer in a p‐i‐n Si solar cell. The QDSL consists of a stack of four 4‐nm Si nano disks and 2‐nm SiC barrier layers embedded in a SiC matrix fabricated with a top‐down etching process. The Si nano disks were observed with bright field‐scanning transmission electron microscopy. The simulation results based on the 3D finite element method confirmed that the quantum effect on the band structure for the QDSL and QW structures was different and had different effects on solar cell operation. The effect of vertical wave‐function coupling to form a miniband in the QDSL was observed based on the solar‐cell performance, showing a dramatic photovoltaic response in generating a high photocurrent density J_sc of 29.24 mA/cm², open circuit voltage V_oc of 0.51 V, fill factor FF of 0.74, and efficiency η of 11.07% with respect to a i‐QW solar cell with J_sc of 25.27 mA/cm², V_oc of 0.49 V, FF of 0.69, and η of 8.61% and an i‐Si solar cell with J_sc of 27.63 mA/cm², V_oc of 0.55 V, FF of 0.61, and η of 10.00%. A wide range of photo‐carrier transports by the QD arrays in the QDSL solar cell is possible in the internal quantum efficiency spectra with respect to the internal quantum efficiency of the i‐QW solar cell. Copyright © 2015 John Wiley & Sons, Ltd.     

8.2% pure selenide kesterite thin‐film solar cells from large‐area electrodeposited precursors

Cu₂ZnSnSe₄ solar cell absorbers are synthesized by large‐area electrodeposition of metal stack precursors followed by selenization. A champion solar cell exhibits 8.2% power conversion efficiency, a new record for Cu₂ZnSnSe₄ solar cells prepared from electrodeposited metallic precursors. Significant improvements of device performance are achieved by the application of two etching procedures and buffer layer optimization. These results validate electrodeposition as a credible alternative to vacuum processes (sputtering, co‐evaporation) for earth‐abundant thin‐film solar cell fabrication at low cost. Copyright © 2015 John Wiley & Sons, Ltd.     

Interconnection of busbar‐free back contacted solar cells by laser welding

We are presenting the module integration of busbar‐free back‐junction back‐contact (BJBC) solar cells. Our proof‐of‐concept module has a fill factor of 80.5% and a conversion efficiency on the designated area of 22.1% prior to lamination. A pulsed laser welds the Al metallization of the solar cells to an Al foil carried by a transparent substrate. The weld spots electrically contact each individual finger to the Al foil, which serves as interconnect between different cells. We produce a proof‐of‐concept module using busbar‐free cell strips of 25 × 125 mm². These are obtained by laser‐dicing of a 125 × 125 mm² BJBC solar cell. The fill factor of this module is increased by 3.5% absolute compared with the initial cell before laser‐dicing. This is achieved mainly by omitting the busbars and reduction of the finger length. The improvement of the module fill factor results in an increase in the module performance of 0.9% absolute before lamination in comparison with the efficiency of the initial 125 × 125 mm² BJBC solar cell. Hence, this interconnection scheme enables the transfer of high cell efficiencies to the module. Copyright © 2014 John Wiley & Sons, Ltd.     

All Solution‐Processed Chalcogenide Solar Cells – from Single Functional Layers Towards a 13.8% Efficient CIGS Device

Solution processing of inorganic thin films has become an important thrust in material research community because it offers low‐cost and high‐throughput deposition of various functional coatings and devices. Especially inorganic thin film solar cells – macroelectronic devices that rely on consecutive deposition of layers on large‐area rigid and flexible substrates – could benefit from solution approaches in order to realize their low‐cost nature. This article critically reviews existing deposition approaches of functional layers for chalcogenide solar cells with an extension to other thin film technologies. Only true solutions of readily available metal salts in appropriate solvents are considered without the need of pre‐fabricated nanoparticles. By combining three promising approaches, an air‐stable Cu(In,Ga)Se₂ thin film solar cell with efficiency of 13.8% is demonstrated where all constituent layers (except the metal back contact) are processed from solutions. Notably, water is employed as the solvent in all steps, highlighting the potential for safe manufacturing with high utilization rates.     

Core/Shell PbSe/PbS QDs TiO2 Heterojunction Solar Cell

Quasi type‐II PbSe/PbS quantum dots (QDs) are employed in a solid state high efficiency QD/TiO₂ heterojunction solar cell. The QDs are deposited using layer‐by‐layer deposition on a half‐micrometer‐thick anatase TiO₂ nanosheet film with (001) exposed facets. Theoretical calculations show that the carriers in PbSe/PbS quasi type‐II QDs are delocalized over the entire core/shell structure, which results in better QD film conductivity compared to PbSe QDs. Moreover, PbS shell permits better stability and facile electron injection from the QDs to the TiO₂ nanosheets. To complete the electrical circuit of the solar cell, a Au film is evaporated as a back contact on top of the QDs. This PbSe/PbS QD/TiO₂ heterojunction solar cell produces a light to electric power conversion efficiency (η) of 4% with short circuit photocurrent (J_sc) of 17.3 mA/cm². This report demonstrates highly efficient core/shell near infrared QDs in a QD/TiO₂ heterojunction solar cell.     

Design of Multilayered Nanostructures and Donor–Acceptor Interfaces in Solution‐Processed Thin‐Film Organic Solar Cells

Multilayered polymer thin‐film solar cells have been fabricated by wet processes such as spin‐coating and layer‐by‐layer deposition. Hole‐ and electron‐transporting layers were prepared by spin‐coating with poly(3,4‐ethylenedioxythiophene) oxidized with poly(4‐styrenesulfonate) (PEDOT:PSS) and fullerene (C₆₀), respectively. The light‐harvesting layer of poly‐(p‐phenylenevinylene) (PPV) was fabricated by layer‐by‐layer deposition of the PPV precursor cation and poly(sodium 4‐styrenesulfonate) (PSS). The layer‐by‐layer technique enables us to control the layer thickness with nanometer precision and select the interfacial material at the donor–acceptor heterojunction. Optimizing the layered nanostructures, we obtained the best‐performance device with a triple‐layered structure of PEDOT:PSS|PPV|C₆₀, where the thickness of the PPV layer was 11 nm, comparable to the diffusion length of the PPV singlet exciton. The external quantum efficiency spectrum was maximum (ca. 20%) around the absorption peak of PPV and the internal quantum efficiency was estimated to be as high as ca. 50% from a saturated photocurrent at a reverse bias of ?3 V. The power conversion efficiency of the triple‐layer solar cell was 0.26% under AM1.5G simulated solar illumination with 100 mW cm^?2 in air.     

Rational Design of Small Molecular Donor for Solution‐Processed Organic Photovoltaics with 8.1% Efficiency and High Fill Factor via Multiple Fluorine Substituents and Thiophene Bridge

A series of tetrafluorine‐substituted small molecules with a D₁‐A‐D₂‐A‐D₁ linear framework based on indacenodithiophene and difluorobenzothiadiazole is designed and synthesized for application as donor materials in solution‐processed small‐molecule organic solar cells. The impacts of thiophene π‐bridge and multiple fluorinated modules on the photophysical properties, the energy levels of the highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO), charge carrier mobility, the morphologies of blend films, and their photovoltaic properties as electron donor material in the photoactive layer are investigated. By incorporating multiple fluorine substituents of benzothiadiazole and inserting two thiophene spacers, the fill factor (FF), open‐circuit voltage, and short‐circuit current density are dramatically improved in comparison with fluorinated‐free materials. With the solvent vapor annealing treatment, further enhancement in charge carrier mobility and power conversion efficiency (PCE) are achieved. Finally, a high PCE of 8.1% with very‐high FF of 0.76 for BIT‐4F‐ T/PC₇₁BM is achieved without additional additive, which is among one of the highest reported for small‐molecules‐based solar cells with PCE over 8%. The results reported here clearly indicate that high PCE in solar cells based small molecules can be significantly increased through careful engineering of the molecular structure and optimization on the morphology of blend films by solvent vapor annealing.     

Excellent Cycling Stability of Sodium Anode Enabled by a Stable Solid Electrolyte Interphase Formed in Ether‐Based Electrolytes

Sodium‐ion batteries have been considered one of the most promising power sources beyond Li‐ion batteries. Although the Na metal anode exhibits a high theoretical capacity of 1165 mAh g^?1, its application in Na batteries is largely hindered by dendrite growth and low coulombic efficiency. Herein, it is demonstrated that an electrolyte consisting of 1 m sodium tetrafluoroborate in tetraglyme can enable excellent cycling efficiency (99.9%) of a Na metal anode for more than 1000 cycles. This high reversibility of a Na anode can be attributed to a stable solid electrolyte interphase formed on the Na surface, as revealed by cryogenic transmission electron microscopy and X‐ray photoelectron spectroscopy (XPS). These electrolytes also enable excellent cycling stability of Na||hard‐carbon cells and Na||Na_2/3Co_1/3Mn_2/3O₂ cells at high rates with very high coulombic efficiencies.     

Reduced Defects of MAPbI3 Thin Films Treated by FAI for High‐Performance Planar Perovskite Solar Cells

Organolead trihalide perovskite films with a large grain size and excellent surface morphology are favored to good‐performance solar cells. However, interstitial and antisite defects related trap‐states are originated unavoidably on the surfaces of the perovskite films prepared by the solution deposition procedures. The development of post‐growth treatment of defective films is an attractive method to reduce the defects to form good‐quality perovskite layers. Herein, a post‐treatment tactic is developed to optimize the perovskite crystallization by treating the surface of the one‐step deposited CH₃NH₃PbI₃ (MAPbI₃) using formamidinium iodide (FAI). Charge carrier kinetics investigated via time‐resolved photoluminescent, open‐circuit photovoltage decay, and time‐resolved charge extraction indicate that FAI post‐treatment will boost the perovskite crystalline quality, and further result in the reduction of the defects or trap‐states in the perovskite films. The photovoltaic devices by FAI treatment show much improved performance in comparison to the controlled solar cell. As a result, a champion solar cell with the best power conversion efficiency of 20.25% is obtained due to a noticeable improvement in fill factor. This finding exhibits a simple procedure to passivate the perovskite layer via regulating the crystallization and decreasing defect density.     

Achievement of 17.9% efficiency in 30 × 30 cm2 Cu(In,Ga)(Se,S)2 solar cell sub‐module by sulfurization after selenization with Cd‐free buffer

We have achieved 17.9% efficiency in a 30 × 30 cm² Cu(In,Ga)(Se,S)₂ solar cell sub‐module prepared by selenization and sulfurization processes with a Cd‐free buffer. The development of an absorber layer, transparent conducting oxide window layer, and module design was the key focus. This permitted 1.8% higher efficiency than our last experimental result. The quantity and the injection time of the sodium were controlled, resulting in higher open circuit voltage (V_oc) and short circuit current (J_sc). In order to increase J_sc, we changed the thickness of the window layer. Boron‐doped zinc oxide was optimized for higher transmittance without reducing the fill factor. The uniformity of each layer was improved, and patterns were optimized for each module. Therefore, V_oc, J_sc, and FF could be theoretically improved on the reported results of, respectively, 20 mV, 2 mA/cm², and 1.4%. The module's efficiency was measured at the Korea Test Laboratory to compare with the data obtained in‐house. Various analyses were performed, including secondary ion mass spectroscopy, photoluminescence, quantum efficiency, solar simulator, and UV–vis spectrometry, to measure the cell's depth profile, carrier lifetime, external quantum efficiency, module efficiency, and transmittance, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Effects of spectrum on the power rating of amorphous silicon photovoltaic devices

The effects of different spectra on the laboratory based performance evaluation of amorphous silicon solar cells is investigated using an opto‐electrical model which was developed specifically for this purpose. The aim is to quantify uncertainties in the calibration process. Two main uncertainties arise from the differences in the test spectrum and the standard spectrum. First, the mismatch between reference cells and the measured device, which is shown to be voltage dependent in the case of amorphous silicon devices. Second, the fill factor of the device is affected by different spectra. Different cell structures and states (specifically different i‐layer thickness and levels of degradation) for the different light sources are investigated in this work. These sources are different solar simulators, LED sources, Tungsten as well as the standard terrestrial AM1.5G radiation. It is shown that the performance cannot be evaluated by short circuit current alone. The voltage dependent quantum efficiency of p‐i‐n devices can introduce a mismatch in the P_MPP of 1% for 250 nm i‐layer devices in as prepared state, rising to up to 4% for the 600 nm i‐layer devices at degraded state. Copyright © 2011 John Wiley & Sons, Ltd.     

CdS/CdTe thin‐film solar cells with Cu‐free transition metal oxide/Au back contacts

Superstrate CdS/CdTe thin‐film solar cells with Cu‐free transition metal oxide (TMO)/Au and Au‐only back contacts have been fabricated. The TMOs include MoO_3‐x, V₂O_5‐x, and WO_3‐x. The incorporation of the TMO buffer layers at the back contacts resulted in significant improvement on open‐circuit voltage (V_OC) as compared with the cells with Cu‐free Au‐only back contacts. Among the cells using TMO buffer layers, the ones with MoO_3‐x buffer layers exhibited the best performance, yielding an efficiency of 14.1% under AM1.5 illumination with V_OC of 815 mV and a fill factor of 67.9%. Though the performance is slightly behind the best reference cell with a Cu/Au back contact fabricated in our lab with V_OC of 844 mV, fill factor of 76.3%, and efficiency of 15.7%, the use of Cu‐free back contacts may lead to improved long‐term cell stability. Copyright © 2013 John Wiley & Sons, Ltd.     

A Simple Electrode‐Level Chemical Presodiation Route by Solution Spraying to Improve the Energy Density of Sodium‐Ion Batteries

The formation of a solid electrolyte interface (SEI) on the surface of a carbon anode consumes the active sodium ions from the cathode and reduces the energy density of sodium‐ion batteries (SIBs). Herein, a simple electrode‐level presodiation strategy by spraying a sodium naphthaline (Naph‐Na) solution onto a carbon electrode is reported, which compensates the initial sodium loss and improves the energy density of SIBs. After presodiation, an SEI layer is preformed on the surface of carbon anode before battery cycling. It is shown that a large irreversible capacity of 60 mAh g^?1 is replenished and 20% increase of the first‐cycle Coulombic efficiency is achieved for a hard carbon anode using this presodiation strategy, and the energy density of a Na_0.9[Cu_0.22Fe_0.30Mn_0.48]O₂||carbon full cell is increased from 141 to 240 Wh kg^?1 by using the presodiated carbon anode. This simple and scalable electrode‐level chemical presodiation route also shows generality and value for the presodiation of other anodes in SIBs.