Al-/Ga-Doped ZnO Window Layers for Highly Efficient Cu2ZnSn(S,Se)4 Thin Film Solar Cells.

The successful use of Al-/Ga-doped ZnO (AGZO) thin films as a transparent conducting oxide (TCO) layer of a Cu2ZnSn(S,Se)4 (CZTSSe) thin film solar cell is demonstrated. The AGZO thin films were prepared by radio frequency (RF) sputtering. The structural, crystallographic, electrical, and optical properties of the AGZO thin films were systematically investigated. The photovoltaic properties of CZTSSe thin film solar cells incorporating the AGZO-based TCO layer were also reported. It has been found that the RF power and substrate temperature of the AGZO thin film are important factors determining the electrical, optical, and structural properties. The optimization process involving the RF power and the substrate temperature leads to good electrical and optical transmittance of the AGZO thin films. Finally, the CZTSSe solar cell with the AGZO TCO layer demonstrated a high conversion efficiency of 9.68%, which is higher than that of the conventional AZO counterpart by 12%.

Silicon nanodisk array design for effective light trapping in ultrathin c-Si.

The use of ultrathin c-Si (crystalline silicon) wafers thinner than 20 µm for solar cells is a very promising approach to realize dramatic reduction in cell cost. However, the ultrathin c-Si requires highly effective light trapping to compensate optical absorption reduction. Conventional texturing in micron scale is hardly applicable to the ultrathin c-Si wafers; thus, nano scale texturing is demanded. In general, nanotexturing is inevitably accompanied by surface area enlargements, which must be minimized in order to suppress surface recombination of minority carriers. In this study, we demonstrate using optical simulations that periodic c-Si nanodisk arrays of short heights less than 200 nm and optimal periods are very useful in terms of light trapping in the ultrathin c-Si wafers while low surface area enlargements are maintained. Double side texturing with the nanodisk arrays leads to over 90% of the Lambertian absorption limit while the surface area enlargement is kept below 1.5.

A facile and rapid process to fabricate platinum counter electrode in dye-sensitized solar cell using nanosecond pulsed laser sintering at room temperature.

To fabricate the platinum (Pt) counter electrode in dye-sensitized solar cells (DSSCs), rapid and low sintering process was carried out using nanosecond pulsed laser sintering (LS) method based on third harmonic (355 nm) of an Nd:YAG laser at room temperature. The surface morphology of LS-Pt on fluorine-doped tin oxide (FTO) electrode showed thin and compact structure, consisting of particles size of - 10-30 nm and thickness of below 30 nm. The DSSCs with the LS-Pt/FTO counter electrodes displayed the power conversion efficiency of 4.4% with short-circuit current = 9.07 mA/cm2, open-circuit voltage = 0.79 V and fill factor = 61.3.

Oxidation kinetics of nitrogen doped TiO(2-δ) thin films.

The oxidation kinetics of nitrogen doped, oxygen deficient titanium dioxide thin films has been studied in atmospheres of pure oxygen or nitrogen at 500 °C, 550 °C, and 600 °C, respectively, by means of in situ optical spectroscopy. The thin films show high electronic absorbance in the visible and NIR region, accompanied by a red shift of the absorption edge of about 0.4 eV, e.g., from about 2.9 to 2.5 eV at 600 °C. The time dependent decrease of absorbance due to oxidation is found to follow a parabolic rate law. An activation energy of about 1.96 eV can be obtained from the temperature dependence of the parabolic oxidation rate constant. In the framework of a microscopic oxidation model, this energy barrier is attributed to the diffusion of titanium interstitials in the re-oxidized part of the thin films as a rate-determining process. In addition, an attempt is made to evaluate the kinetics of nitrogen release from the time dependent blue shift of the absorption edge during re-oxidation.

Suppressed recombination in quantum dot-sensitized solar cells with blocking layers on FTO substrates.

The compact and thin TiO2 blocking layers (c-TiO2) were formed on F-doped SnO2 (FTO) substrate in quantum dots-sensitized solar cells (QSSCs) by chemical deposition. The c-TiO2 layers induced indirect contact between electrolyte and FTO electrode, which reduced leakage in QSSCs. The QSSCs showed power conversion efficiency (Eff) of 3.85% in the presence of c-TiO2 layers which leads to 21% improved compared to that without c-TiO2 layers (Eff = 3.18%). The presence of the c-TiO2 layers in QSSCs also improved the stability under illumination.

Expanding the spectral response of a dye-sensitized solar cell by applying a selective positioning method.

We have developed a facile method to position different dyes (N719 and N749) sequentially in a mesoporous TiO(2) layer through selective desorption and adsorption processes. From the selective removal of the only upper part of the first adsorbed dye, double-layered dye-sensitized solar cells have been successfully achieved without any damage to the dye. From the incident photon-to-current conversion efficiency (IPCE) measurement, the multi-layered dye-sensitized solar cell (MDSSC) was found to exhibit an expanded spectral response for the solar spectrum while maintaining the maximum IPCE value of each single-layered cell. The highest photocurrent density, 19.3 mA cm( - 2), was obtained from the MDSSC utilizing an N719/N749 bi-layered mesoporous TiO(2) film. The power conversion efficiency of 9.8% was achieved from the MDSSC, which is higher than that of single N719-or N749-based cells and cocktail-dyed (a mixture of N719 and N749) cells.

An EMF cell with a nitrogen solid electrolyte--on the transference of nitrogen ions in yttria-stabilized zirconia.

The mobility and electrochemical activity of nitrogen inside and/or at the surface of ionic compounds is of fundamental, as well as of possibly practical, relevance. In order to better understand the role of nitrogen anions in solid electrolytes, we measured the transference number of nitrogen in yttria-stabilized zirconia (YSZ) by a concentration cell technique as a function of oxygen activity at different temperatures in the range of 1023 ≤T/K≤ 1123. YSZ doped with 1.9 wt% of N (YSZ:N) turned out to have an appreciable nitrogen transference number, which increased from 0 to 0.1 with decreasing oxygen activity in the range of -20 < log a(O(2)) < -14. The stability of N in YSZ:N, however, has yet to be elucidated under oxidizing conditions.

Method to protect charge recombination in the back-contact dye-sensitized solar cell.

We prepared a back-contact dye-sensitized solar cell and investigated effect of the sputter deposited thin TiO2 film on the back-contact ITO electrode on photovoltaic property. The nanocrystalline TiO2 layer with thickness of about 11 µm formed on a plain glass substrate in the back-contact structure showed higher optical transmittance than that formed on an ITO-coated glass substrate, which led to an improved photocurrent density by about 6.3%. However, photovoltage was found to decrease from 817 mV to 773 mV. The photovoltage recovered after deposition of a 35 nm-thick thin TiO2 film on the surface of the back-contact ITO electrode. Little difference in time constant for electron transport was found for the back-contact ITO electrodes with and without the sputter deposited thin TiO2 film. Whereas, time constant for charge recombination increased after introduction of the thin TiO2 film, indicating that such a thin TiO2 film protected back electron transfer, associated with the recovery of photovoltage. As the result of the improved photocurrent density without deterioration of photovoltage, the back-contact dye-sensitized solar cell exhibited 13.6% higher efficiency than the ITO-coated glass substrate-based dye-sensitized solar cell.

Optimal CdS Buffer Thickness to Form High-Quality CdS/Cu(In,Ga)Se2 Junctions in Solar Cells without Plasma Damage and Shunt Paths.

CdS has been known to be one of the best junction partners for Cu(In,Ga)Se2 (CIGS) in CIGS solar cells. However, the use of thick CdS buffer decreases the short-circuit current density of CIGS solar cells. There are two obstacles that limit the use of ultrathin CdS. The first is plasma damage to CIGS during the preparation of transparent conducting windows and the second is a low shunt resistance due to the direct contact between the window and CIGS via pinholes in the thin CdS buffer. In other words, to avoid plasma damage and shunt paths, we may have to use a CdS buffer that is thicker than necessary to form a high-quality CdS/CIGS junction. This work aims to determine how thin the CdS buffer can be employed without sacrificing device performance while also eliminating the above two obstacles. We investigate the effect of CdS thickness on the performance of CIGS solar cells with silver nanowire-based window layers, which can eliminate both obstacles. An approximately 13 nm thick CdS buffer allows us to achieve high short-circuit current density and fill factor values. To attain an even high open-circuit voltage, an additional CdS buffer with a thickness of 13 nm is needed. The data from this study imply that an approximately 26 nm thick CdS buffer is sufficient to form a high-quality CdS/CIGS junction.

Electrodeposited Silver Nanowire Transparent Conducting Electrodes for Thin-Film Solar Cells.

Silver nanowire (AgNW) networks have demonstrated high optical and electrical properties, even better than those of indium tin oxide thin films, and are expected to be a next-generation transparent conducting electrode (TCE). Enhanced electrical and optical properties are achieved when the diameter of the AgNWs in the network is fairly small, that is, typically less than 30 nm. However, when AgNWs with such small diameters are used in the network, stability issues arise. One method to resolve the stability issues is to increase the diameter of the AgNWs, but the use of AgNWs with large diameters has the disadvantage of causing a rough surface morphology. In this work, we resolve all of the aforementioned issues with AgNW TCEs by the electrodeposition of Ag onto as-spin-coated thin AgNW TCEs. The electrodeposition of Ag offers many advantages, including the precise adjustment of the AgNW diameter and wire-to-wire welding to improve the junction conductance while minimizing the increase in protrusion height because of the overlap of AgNWs upon increasing the diameter. In addition, Ag electrodeposition on AgNW TCEs can provide higher conductance than that of as-spin-coated AgNW TCEs at the same transparency because of the reduced junction resistance, which generates a superior figure of merit. We applied the electrodeposited (ED) AgNW network to a Cu(In,Ga)Se2 thin-film solar cell and compared the device performance to a device with a standard sputtered transparent conducting oxide (TCO). The cell fabricated by the electrodeposition method showed nearly equal performance to that of a cell with the sputtered TCO. We expect that ED AgNW networks can be used as high-performance and robust TCEs for various optoelectronic applications.

Random nanohole arrays and its application to crystalline Si thin foils produced by proton induced exfoliation for solar cells.

We report high efficiency cell processing technologies for the ultra-thin Si solar cells based on crystalline Si thin foils (below a 50 µm thickness) produced by the proton implant exfoliation (PIE) technique. Shallow textures of submicrometer scale is essential for effective light trapping in crystalline Si thin foil based solar cells. In this study, we report the fabrication process of random Si nanohole arrays of ellipsoids by a facile way using low melting point metal nanoparticles of indium which were vacuum-deposited and dewetted spontaneously at room temperature. Combination of dry and wet etch processes with indium nanoparticles as etch masks enables the fabrication of random Si nanohole arrays of an ellipsoidal shape. The optimized etching processes led to effective light trapping nanostructures comparable to conventional micro-pyramids. We also developed the laser fired contact (LFC) process especially suitable for crystalline Si thin foil based PERC solar cells. The laser processing parameters were optimized to obtain a shallow LFC contact in conjunction with a low contact resistance. Lastly, we applied the random Si nanohole arrays and the LFC process to the crystalline Si thin foils (a 48 µm thickness) produced by the PIE technique and achieved the best efficiency of 17.1% while the planar PERC solar cell without the Si nanohole arrays exhibit 15.6%. Also, we demonstrate the ultra-thin wafer is bendable to have a 16 mm critical bending radius.

Enhanced efficiency of crystalline Si solar cells based on kerfless-thin wafers with nanohole arrays.

Several techniques have been proposed for kerfless wafering of thin Si wafers, which is one of the most essential techniques for reducing Si material loss in conventional wafering methods to lower cell cost. Proton induced exfoliation is one of promising kerfless techniques due to the simplicity of the process of implantation and cleaving. However, for application to high efficiency solar cells, it is necessary to cope with some problems such as implantation damage removal and texturing of (111) oriented wafers. This study analyzes the end-of-range defects at both kerfless and donor wafers and ion cutting sites. Thermal treatment and isotropic etching processes allow nearly complete removal of implantation damages in the cleaved-thin wafers. Combining laser interference lithography and a reactive ion etch process, a facile nanoscale texturing process for the kerfless thin wafers of a (111) crystal orientation has been developed. We demonstrate that the introduction of nanohole array textures with an optimal design and complete damage removal lead to an improved efficiency of 15.2% based on the kerfless wafer of a 48 µm thickness using the standard architecture of the Al back surface field.

Suppressed Formation of Conductive Phases in One-Pot Electrodeposited CuInSe2 by Tuning Se Concentration in Aqueous Electrolyte.

The single-bath electrochemical deposition of CuInSe2 often leads to short-circuit behavior of the resulting solar cells due to the high shunt conductance. In this study, in an attempt to resolve this problem, the influence of the Se precursor concentration (CSe) on electrodeposited CuInSe2 films and solar cell devices is examined in the CSe range of 4.8 to 12.0 mM in selenite-based aqueous solutions containing Cu and In chlorides along with sulfamic acid (H3NSO3) and potassium hydrogen phthalate (C8H5KO4) additives. As CSe increases, the CuInSe2 layers become porous, and the grain growth of the CuInSe2 phase is restricted, while the parasitic shunting problem was markedly alleviated, as unambiguously demonstrated by measurements of the local current distribution. Due to these ambivalent influences, an optimal value of CSe that achieves the best quality of the films for high-efficiency solar cells is identified. Thus, the device prepared with 5.2 mM Se exhibits a power-conversion efficiency exceeding 10% with greatly improved device parameters, such as the shunt conductance and the reverse saturation current. The rationale of the present approach along with the physicochemical origin of its conspicuous impact on the resulting devices is discussed in conjunction with the electro-crystallization mechanism of the CuInSe2 compound.

Compositional and Interfacial Modification of Cu2 ZnSn(S,Se)4 Thin-Film Solar Cells Prepared by Electrochemical Deposition.

A highly efficient Cu2 ZnSn(S,Se)4 (CZTSSe)-based thin-film solar cell (9.9%) was prepared using an electrochemical deposition method followed by thermal annealing. The Cu-Zn-Sn alloy films was grown on a Mo-coated glass substrate using a one-pot electrochemical deposition process, and the metallic precursor films was annealed under a mixed atmosphere of S and Se to form CZTSSe thin films with bandgap energies ranging from 1.0 to 1.2 eV. The compositional modification of the S/(S+Se) ratio shows a trade-off effect between the photocurrent and photovoltage, resulting in an optimum bandgap of roughly 1.14 eV. In addition, the increased S content near the p-n junction reduces the dark current and interface recombination, resulting in a further enhancement of the open-circuit voltage. As a result of the compositional and interfacial modification, the best CZTSSe-based thin-film solar cell exhibits a conversion efficiency of 9.9%, which is among the highest efficiencies reported so far for electrochemically deposited CZTSSe-based thin-film solar cells.

High-Performance Planar Perovskite Optoelectronic Devices: A Morphological and Interfacial Control by Polar Solvent Treatment.

Highly efficient planar perovskite optoelectronic devices are realized by amine-based solvent treatment on compact TiO2 and by optimizing the morphology of the perovskite layers. Amine-based solvent treatment between the TiO2 and the perovskite layers enhances electron injection and extraction and reduces the recombination of photogenerated charges at the interface.

Tailoring of energy levels in D-π-A organic dyes via fluorination of acceptor units for efficient dye-sensitized solar cells.

A molecular design is presented for tailoring the energy levels in D-π-A organic dyes through fluorination of their acceptor units, which is aimed at achieving efficient dye-sensitized solar cells (DSSCs). This is achieved by exploiting the chemical structure of common D-π-A organic dyes and incorporating one or two fluorine atoms at the ortho-positions of the cyanoacetic acid as additional acceptor units. As the number of incorporated fluorine atoms increases, the LUMO energy level of the organic dye is gradually lowered due to the electron-withdrawing effect of fluorine, which ultimately results in a gradual reduction of the HOMO-LUMO energy gap and an improvement in the spectral response. Systematic investigation of the effects of incorporating fluorine on the photovoltaic properties of DSSCs reveals an upshift in the conduction-band potential of the TiO2 electrode during impedance analysis; however, the incorporation of fluorine also results in an increased electron recombination rate, leading to a decrease in the open-circuit voltage (Voc). Despite this limitation, the conversion efficiency is gradually enhanced as the number of incorporated fluorine atoms is increased, which is attributed to the highly improved spectral response and photocurrent.

Completely transparent conducting oxide-free and flexible dye-sensitized solar cells fabricated on plastic substrates.

To achieve commercialization and widespread application of next-generation photovoltaics, it is important to develop flexible and cost-effective devices. Given this, the elimination of expensive transparent conducting oxides (TCO) and replacement of conventional glass substrates with flexible plastic substrates presents a viable strategy to realize extremely low-cost photovoltaics with a potentially wide applicability. To this end, we report a completely TCO-free and flexible dye-sensitized solar cell (DSSC) fabricated on a plastic substrate using a unique transfer method and back-contact architecture. By adopting unique transfer techniques, the working and counter electrodes were fabricated by transferring high-temperature-annealed TiO2 and Pt/carbon films, respectively, onto flexible plastic substrates without any exfoliation. The fabricated working electrode with the conventional counter electrode exhibited a record efficiency for flexible DSSCs of 8.10%, despite its TCO-free structure. In addition, the completely TCO-free and flexible DSSC exhibited a remarkable efficiency of 7.27%. Furthermore, by using an organic hole-transporting material (spiro-MeOTAD) with the same transfer method, solid-state flexible TCO-free DSSCs were also successfully fabricated, yielding a promising efficiency of 3.36%.

Monolithic DSSC/CIGS tandem solar cell fabricated by a solution process.

Tandem architecture between organic (dye-sensitized solar cell, DSSC) and inorganic (CuInGaSe2 thin film solar cell, CIGS) single-junction solar cells was constructed particularly based on a solution process. Arc-plasma deposition was employed for the Pt interfacial layer to minimize the damage to the layers of the CIGS bottom cell. Solar cell efficiency of 13% was achieved, which is significant progress from individual single-junction solar cells (e.g., 7.25 and 6.2% for DSSC and CIGS, respectively).

Printable, wide band-gap chalcopyrite thin films for power generating window applications.

Printable, wide band-gap chalcopyrite compound films (CuInGaS2, CIGS) were synthesized on transparent conducting oxide substrates. The wide band-gap and defective nature of the films reveal semi-transparent and bifacial properties that are beneficial for power generating window applications. Importantly, solar cell devices with these films demonstrate a synergistic effect for bifacial illumination resulting in a 5.4-16.3% increase of the apparent power conversion efficiency compared to the simple sum of the efficiencies of the front and rear side illumination only. We also confirmed that this extra output power acquisition due to bifacial irradiation is apparently not influenced by the light intensity of the rear side illumination, which implies that weak light (e.g., indoor light) can be efficiently utilized to improve the overall solar cell efficiency of bifacial devices.

Colloidal solution-processed CuInSe2 solar cells with significantly improved efficiency up to 9% by morphological improvement.

We demonstrate here that an improvement in the green density leads to a great enhancement in the photovoltaic performance of CuInSe2 (CISe) solar cells fabricated with Cu-In nanoparticle precursor films via colloidal solution deposition. Cold-isostatic pressing (CIP) increases the precursor film density by ca. 20%, which results in an appreciable improvement in the microstructural features of the sintered CISe film in terms of a lower porosity, a more uniform surface morphology, and a thinner MoSe2 layer. The low-band-gap (1.0 eV) CISe solar cells with the CIP-treated films exhibit greatly enhanced open-circuit voltage (V(OC), typically from 0.265 to 0.413 V) and fill factor (FF, typically from 0.34 to 0.55), compared to the control devices. As a consequence, an almost 3-fold increase in the average efficiency, from 3.0 to 8.2% (with the highest value of 9.02%), is realized. Diode analysis reveals that the enhanced V(OC) and FF are essentially attributed to the reduced reverse saturation current density and diode ideality factor. This is associated with suppressed recombination, likely due to the reduction in recombination sites at grain/air surfaces, intergranular interfaces, and defective CISe/CdS junctions. From the temperature dependences of V(OC), it is revealed that CIP-treated devices suffer less from interface recombination.