Effect of Metal-Precursor Stacking Order on Volume-Defect Formation in CZTSSe Thin Film: Formation Mechanism of Blisters and Nanopores.

In this study, we investigated the effect of the stacking order of metal precursors on the formation of volume defects, such as blisters and nanopores, in CZTSSe thin-film solar cells. We fabricated CZTSSe thin films using three types of metal-precursor combinations, namely, Zn/Cu/Sn/Mo, Cu/Zn/Sn/Mo, and Sn/Cu/Zn/Mo, and studied the blister formation. The blister-formation mechanism was based on the delamination model, taking into consideration the compressive stress and adhesion properties. A compressive stress could be induced during the preferential formation of a ZnSSe shell. Under this stress, the adhesion between the ZnSSe film and the Mo substrate could be maintained by the surface tension of a metallic liquid phase with good wettability, or by the functioning of ZnSSe pillars as anchors, depending on the type of metal precursor used. Additionally, the nanopore formation near the back-contact side was found to be induced by the columnar microstructure of the metal precursor with the Cu/Zn/Mo stacking order and its dezincification. Based on the two volume-defect-formation mechanisms proposed herein, further development of volume-defect-formation suppression technology is expected to be made.

Atomic Layer Deposition of Ultrathin ZnO Films for Hybrid Window Layers for Cu(Inx,Ga1-x)Se2 Solar Cells.

The efficiency of thin-film chalcogenide solar cells is dependent on their window layer thickness. However, the application of an ultrathin window layer is difficult because of the limited capability of the deposition process. This paper reports the use of atomic layer deposition (ALD) processes for fabrication of thin window layers for Cu(Inx,Ga1-x)Se2 (CIGS) thin-film solar cells, replacing conventional sputtering techniques. We fabricated a viable ultrathin 12 nm window layer on a CdS buffer layer from the uniform conformal coating provided by ALD. CIGS solar cells with an ALD ZnO window layer exhibited superior photovoltaic performances to those of cells with a sputtered intrinsic ZnO (i-ZnO) window layer. The short-circuit current of the former solar cells improved with the reduction in light loss caused by using a thinner ZnO window layer with a wider band gap. Ultrathin uniform A-ZnO window layers also proved more effective than sputtered i-ZnO layers at improving the open-circuit voltage of the CIGS solar cells, because of the additional buffering effect caused by their semiconducting nature. In addition, because of the precise control of the material structure provided by ALD, CIGS solar cells with A-ZnO window layers exhibited a narrow deviation of photovoltaic properties, advantageous for large-scale mass production purposes.

Design of Grating Al2O3 Passivation Structure Optimized for High-Efficiency Cu(In,Ga)Se2 Solar Cells.

In this paper, we propose an optimized structure of thin Cu(In,Ga)Se2 (CIGS) solar cells with a grating aluminum oxide (Al2O3) passivation layer (GAPL) providing nano-sized contact openings in order to improve power conversion efficiency using optoelectrical simulations. Al2O3 is used as a rear surface passivation material to reduce carrier recombination and improve reflectivity at a rear surface for high efficiency in thin CIGS solar cells. To realize high efficiency for thin CIGS solar cells, the optimized structure was designed by manipulating two structural factors: the contact opening width (COW) and the pitch of the GAPL. Compared with an unpassivated thin CIGS solar cell, the efficiency was improved up to 20.38% when the pitch of the GAPL was 7.5-12.5 µm. Furthermore, the efficiency was improved as the COW of the GAPL was decreased. The maximum efficiency value occurred when the COW was 100 nm because of the effective carrier recombination inhibition and high reflectivity of the Al2O3 insulator passivation with local contacts. These results indicate that the designed structure has optimized structural points for high-efficiency thin CIGS solar cells. Therefore, the photovoltaic (PV) generator and sensor designers can achieve the higher performance of photosensitive thin CIGS solar cells by considering these results.

CZTSSe Formation Mechanism Using a Cu/Zn/SnS Stacked Precursor: Origin of Triple CZTSSe Layer Formation.

In this study, to control the formation of non-uniformly distributed large voids and Cu-Sn alloy agglomeration, which leads to local compositional misfit and secondary phase formation, a SnS compound precursor was applied instead of metal Sn to avoid compositional non-uniformity. Using a Cu/Zn/SnS stacked precursor, a temperature tracking experiment was conducted to confirm the formation controllability of the void and the secondary phase. According to the results of this temperature-profile tracking experiment, it was confirmed that the large void was successfully controlled; however, an additional ZnSSe secondary phase layer was formed in the middle of the CZTSSe upper layer and small voids were distributed relatively uniformly in the bottom CZTSSe layer. An efficiency of approximately 8% was obtained when the Cu/Zn/SnS stacked precursor was used. The origins of the low short-circuit current and fill factor are posited to be caused by the increase of the energy bandgap of the CZTSSe layer due to the SnS precursor, the thin top CZTSSe layer (around 600 nm) of the triple CZTSSe layer, and the diffusion length extension of the minor carriers caused by bypassing the ZnSSe phase.

Enhanced Power Conversion Efficiency of Dye-Sensitized Solar Cells by Band Edge Shift of TiO2 Photoanode.

By simple soaking titanium dioxide (TiO2) films in an aqueous Na2S solution, we could prepare surface-modified photoanodes for application to dye-sensitized solar cells (DSSCs). An improvement in both the open-circuit voltage (Voc) and the fill factor (FF) was observed in the DSSC with the 5 min-soaked photoanode, compared with those of the control cell without any modification. The UV-visible absorbance spectra, UPS valence band spectra, and dark current measurements revealed that the Na2S modification led to the formation of anions on the TiO2 surface, and thereby shifted the conduction band edge of TiO2 in the negative (upward) direction, inducing an increase of 29 mV in the Voc. It was also found that the increased FF value in the surface-treated device was attributed to an elevation in the shunt resistance.

Flexible Cu2ZnSn(S,Se)4 solar cells with over 10% efficiency and methods of enlarging the cell area.

For kesterite copper zinc tin sulfide/selenide (CZTSSe) solar cells to enter the market, in addition to efficiency improvements, the technological capability to produce flexible and large-area modules with homogeneous properties is necessary. Here, we report a greater than 10% efficiency for a cell area of approximately 0.5 cm2 and a greater than 8% efficiency for a cell area larger than 2 cm2 of certified flexible CZTSSe solar cells. By designing a thin and multi-layered precursor structure, the formation of defects and defect clusters, particularly tin-related donor defects, is controlled, and the open circuit voltage value is enhanced. Using statistical analysis, we verify that the cell-to-cell and within-cell uniformity characteristics are improved. This study reports the highest efficiency so far for flexible CZTSSe solar cells with small and large areas. These results also present methods for improving the efficiency and enlarging the cell area.

Controlled fabrication of mesoporous TiO2 hierarchical structures as scattering layers to enhance the power conversion efficiency of dye-sensitized solar cells.

To meet the nanofabrication requirements, such as control of structure and scalability, we investigated an electrospray-based method to manufacture scattering layers (SLs) for dye-sensitized solar cells (DSSCs). TiO2 spherical and disk-shaped particles with a large surface area, high crystallinity, uniform nanostructure and good light scattering properties were fabricated via a simple electrospray method. We showed how the morphology and structure of the resulting films can be controlled by varying the droplet evaporation rates before impact on the substrate. Thus, by tuning the process conditions, high-quality TiO2 spheres and disks were obtained. Then, these mesoporous TiO2 particles were used as the SLs in photoelectrodes, which resulted in enhanced power conversion efficiency (PCE). Compared with conventional SLs (8.45%), DSSCs based on spherical and disk-shaped particle SLs yield higher PCEs of 9.0% and 9.53%, respectively. This is because the generated TiO2 spheres and disks provide a large surface area and exhibit excellent light scattering capabilities, allowing a low total internal resistance and a long electron lifetime.

Efficient hysteresis-less bilayer type CH3NH3PbI3 perovskite hybrid solar cells.

Bilayer type CH3NH3PbI3 (MAPbI3) perovskite hybrid solar cells were fabricated via a one-step spin-coating process by using solubility controlled MAPbI3 solutions of MAPbI3-DMSO (dimethyl sulfoxide) and MAPbI3-DMF (N, N-dimethylformamide)-HI. The best DMSO-bilayer device showed 1.07 ± 0.02 V V(oc) (open-circuit voltage), 20.2 ± 0.1 mA cm(-2) J(sc) (short-circuit current density), 68 ± 2% FF (fill factor), and 15.2 ± 0.3% η (overall power conversion efficiency) under the forward scan direction and 1.07 ± 0.02 V V(oc), 20.4 ± 0.1 mA cm(-2) J(sc), 70 ± 3% FF, and 15.9 ± 0.4% η under the reverse scan direction. The best HI-bilayer device had 1.08 ± 0.02 V V(oc), 20.6 ± 0.1 mA cm(-2) J(sc), 75 ± 1% FF, and 17.2 ± 0.2% η under the forward scan direction and 1.08 ± 0.02 V V(oc), 20.6 ± 0.1 mA cm(-2) J(sc), 76 ± 2% FF, and 17.4 ± 0.3% η under the reverse scan direction. The deviation of average device efficiency (η(avg)) of 20 DMSO samples and 20 HI samples was 14.2 ± 0.95% and 16.2 ± 0.85%, respectively. Therefore, the HI-bilayer devices exhibited better device efficiency and smaller J-V (current density-voltage) hysteresis with respect to the scan direction than the DMSO-bilayer devices due to the reduced recombination and traps by the formation of a purer and larger MAPbI3 perovskite crystalline film.

Effects of Ta Addition Through Co-Sputtering on the Electrical Characteristics of Indium Tin Oxide Thin Film Transistors.

We have investigated the effects of adding (Ta) ions to InSnO thin films by co-sputtering on the performance of InSnO thin film transistors (TFTs). TaInSnO TFTs exhibited significantly lower off currents and higher on/off current ratios. Ta ions, owing to their strong affinity to oxygen suppress the formation of free electron carriers in thin films; and hence, play an important role in enhancing the electrical characteristics of the TFTs. The optimized TaInSnO TFTs showed high on/off ratios and low subthreshold swings.

Effect of Sulfurization Temperature on Solution-Processed Cu2ZnSnS4 Thin Films.

Cu2ZnSnS4 (CZTS) solar cells are attracting significant attention as an alternative to CIGS (Culn1-xGa(x)S2) solar cells because of the non-toxic and inexpensive constituent elements of CZTS. Recently, solution-based deposition methods are being developed because they have advantages such as suitability for use in large-area deposition, high-throughput manufacturing, and a very short energy payback time with drastically lower manufacturing costs. In this work, we fabricated solution-based CZTS thin films and investigated them in order to observe the effects of sulfurization temperature on CZTS thin films. We confirmed the grain size, morphology, chemical composition, crystallinity, and electrical properties of CZTS thin films depending on various sulfurization temperatures.

Crystallization Behavior of Solution-Processed CIGSe Thin Film Semiconductor by Stepwise Annealing Process.

CuIn(x)Ga1-xSe2 (CIGS) thin films were prepared by a solution-based CuInGa (CIG) precursor- selenization process. First, we investigated the effect of selenization temperature on the formation of polycrystalline CIGS and grain growth. The CIG precursor films were selenized using a two-step process to investigate the reaction of Se and CIG precursors during the formation of CIGS thin films. Depending on the temperature in the 1st step of the selenization process, the CIG precursor forms a different intermediate phase between the single phase to ternary phase such as Cu, Se, CuSe, InSe, and CuInSe2. In addition, the intermediate phase exerts a significant influence on the final phase obtained after the 2nd step of the selenization process, particularly with regard to characteristics such as polycrystalline structure and grain growth in the CIGS films. The photoelectron conversion efficiency of devices prepared using CIGS thin films was approximately 1.59-2.75%.

Nanostructured p-type CZTS thin films prepared by a facile solution process for 3D p-n junction solar cells.

Nanoporous p-type semiconductor thin films prepared by a simple solution-based process with appropriate thermal treatment and three-dimensional (3D) p-n junction solar cells fabricated by depositing n-type semiconductor layers onto the nanoporous p-type thin films show considerable photovoltaic performance compared with conventional thin film p-n junction solar cells. Spin-coated p-type Cu2ZnSnS4 (CZTS) thin films prepared using metal chlorides and thiourea show unique nanoporous thin film morphology, which is composed of a cluster of CZTS nanograins of 50-500 nm, and the obvious 3D p-n junction structure is fabricated by the deposition of n-type CdS on the nanoporous CZTS thin films by chemical bath deposition. The photovoltaic properties of 3D p-n junction CZTS solar cells are predominantly affected by the scale of CZTS nanograins, which is easily controlled by the sulfurization temperature of CZTS precursor films. The scale of CZTS nanograins determines the minority carrier transportation within the 3D p-n junction between CZTS and CdS, which are closely related with the photocurrent of series resistance of 3D p-n junction solar cells. 3D p-n junction CZTS solar cells with nanograins below 100 nm show power conversion efficiency of 5.02%, which is comparable with conventional CZTS thin film solar cells.

Effects of Sodium Dodecyl Sulfate as a Co-Adsorbate on the Performance of Dye-Sensitized Solar Cells.

As a surface modifier, sodium dodecyl sulfate (SDS), was applied to dye-sensitized solar cells (DSSCs), and its effects on the photovoltaic performance of the solar cells were investigated. When the SDS was co-adsorbed with dye (N719) onto TiO2 surface, the DSSCs with SDS showed an increase in short-circuit current (Jsc), open-circuit voltage (Voc) and fill factor, leading to a considerable improvement of over 23% in power conversion efficiency, compared to the reference cell without SDS. Incorporation of SDS on TiO2 surface induced longer lifetime of electrons injected from excited dyes to conduction band of TiO2, leading to an increase in the electron collection efficiency and thus an enhancement in Jsc. The longer lifetime by a suppression of the interfacial charge recombination could also contribute to an increment in Voc.

Fabrication of Double-Layered TiO2 Films with Nanosphere Light Scatterers by One-Step Soaking Method.

Nanostructured TiO2 films with a double-layered structure are prepared by a lacile one-step soaking method. We have investigated the morphology of nanostructured TiO2 films according to the reaction time, concentration of the reactant, and reaction temperature of the soaking reaction, which all have a significant effect on the thickness and layered-structure of the nanostructured TiO2 films. The TiO2 films prepared by this soaking method have a unique double-layered structure, which is composed of a dense TiO2 bottom layer and stacked TiO2 nanospheres on the top layer. The growth of TiO2 nanospheres on the top of the double-layered TiO2 films shows stepwise behavior, which means there are two different growth mechanisms resulting in the dense TiO2 bottom layer and the spherical TiO2 top layer. There is an optimum reactant concentration and reaction temperature for achieving double-layered TiO2 films, which can be explained by the theory of nanoparticle synthesis. The stacked TiO2 nanospheres of double-layered TiO2 films contribute to the light scattering effects of TiO2 films, which could be used for the performance improvement of TiO2 photoelectrodes for sensitized solar cells.

Effect of TiCl4 Post-Treatment on the Embedded-Type TiO2 Nanotubes Dye-Sensitized Solar Cells.

We have studied the effect of TiCl4 post-treatment on the embedded-type TiO2 nanotubes (NT)-dye-sensitized solar cells (DSSCs). The TiO2 nanoparticles layer formed on TiO2 NTs surface by TiCl4 post-treatment showed different morphologies depending on TiCl4 treatment temperature. These different morphologies influenced the cell efficiency of TiO2 NT-DSSCs. The TiO2 NT treated with TiCl4 at 50 °C exhibited a rougher surface than that treated at 70 °C. The rough surface of the TiO2 NT improved the charge exchange between the dye and electrolyte. The TiO2 NT treated with TiCl4 at 50 °C showed better fill factor and cell efficiency than that treated at 70 °C. The TiCl4 post-treatment of TiO2 NT was effective at conditions of low temperature and long times. The TiO2 NT-DSSCs with TiCl4 post-treatment at 50 °C for 1.5 h showed an efficiency of 6.52%.

Improved Photovoltaic Properties of Dye-Sensitized Solar Cells with KNO3-Modified Photoelectrodes.

The surface of a TiO2 photoelectrode was modified through a dip-coating process using an aqueous potassium nitrate (KNO3) solution to increase the power-conversion efficiency of dye-sensitized solar cells (DSSCs). The KNO3-modified TiO2 electrode was applied to the photoanode of the DSSCs. The DSSC with the KNO3-modified TiO2 electrode exhibited a short-circuit current (J(sc)) of 15.26 mA/cm2 and an open-circuit voltage (V(oc)) of 671 mV, compared with a J(sc) of 13.74 mA/cm2 and V(oc) of 654 mV for a reference device with a pristine TiO2 electrode. The results in combination with relevant data from electrochemical impedance spectroscopy, open-circuit voltage decay, and dark current measurements revealed that the modification of the TiO2 surface using the surface modifier (KNO3) led to a longer electron lifetime by the suppression of the charge recombination between injected electrons and I3- ions, resulting in an increase in both J(sc) and V(oc), compared with those of the reference device without surface modification.

Incorporation of Potassium Water Glass on Photoelectrodes and Its Effects on the Performance of Dye-Sensitized Solar Cells.

We applied potassium water glass (PWG) for a modification of photoelectrodes and investigated the effects of this modification on the photovoltaic properties of dye-sensitized solar cells (DSSCs). The PWG-modified TiO2 electrodes were prepared by soaking the TiO2 films in an aqueous PWG solution, and the resulting electrodes were applied to the photoanodes of DSSCs. Compared with a reference device with pristine TiO2 electrode, the power conversion efficiency of a DSSC with a PWG-modified TiO2 electrode was improved by about 26% because of the enhanced short-circuit photocurrent (J(sc)) and open-circuit voltage (V(oc)). Open-circuit voltage decay, electrochemical impedance spectroscopy, and dark current measurements revealed that the incorporation of PWG on the TiO2 surface led to a longer electron lifetime because of the suppression of charge recombination between injected electrons and I3(-) ions, which, compared with a reference device without surface modification, resulted in an increase in both J(sc) and V(oc).

Highly reproducible planar Sb2S3-sensitized solar cells based on atomic layer deposition.

A high-quality Sb2S3 thin-absorber with controllable thickness was reproducibly formed by atomic layer deposition (ALD) technique. Compared with conventional chemical bath deposition (CBD), the Sb2S3 absorber deposited by ALD did not contain oxide or oxygen impurities and showed a very uniform thickness of Sb2S3 absorbers formed on a rough surface of dense blocking TiO2/F-doped SnOv (bl-TiO2/FTO) substrate. The planar ALD-Sb2S3 solar cells comprised of Au/Poly-3-hexylthiophene/ALD-Sb2S3/bl-TiO2/FTO showed significantly improved power conversion efficiency of 5.77% at 1 sun condition and narrow efficiency deviation, whereas the planar CBD-Sb2S3 solar cells exhibited 2.17% power conversion efficiency. The high efficiency and good reproducibility of ALD-Sb2S3 solar cell devices is attributed to reduced backward recombination because of the inhibition of oxide defects within ALD-Sb2S3 absorber and the conformal deposition of very uniform Sb2S3 absorbers on the blocking TiO2 surface by ALD process.

Effect of Ta addition of co-sputtered amorphous tantalum indium zinc oxide thin film transistors with bias stability.

In this work, we have fabricated thin film transistors (TFTs) using amorphous tantalum indium zinc oxide (a-TaInZnO) channels by the co-sputtering process. The effects of incorporating tantalum on the InZnO material were investigated using Hall-effect measurement results, and electrical characteristics. We also found that the carrier densities of thin films and the transistor on-off currents were greatly influenced by the composition of tantalum addition. Ta ions have strong affinity to oxygen and so suppress the formation of free electron carriers inthin films; they play an important role in enhancing the electrical characteristic due to their high oxygen bonding ability. The electrical characteristics of the optimized TFTs shows a field effect mobility of 3.67 cm2 V(-1) s(-1), a threshold voltage of 1.28 V, an on/off ratio of 1.1 x 10(8), and a subthreshold swing of 480 mV/dec. Under gate bias stress conditions, the TaInZnO TFTs showed lower shift in threshold voltage shifts.

Enhanced performance of polymer solar cells with a fluorocyanophenyl compound as an additive.

The efficiency of polymer solar cells (PSCs) with P3HT [poly(3-hexyl thiophene)]:PC61BM [[6,6]-phenyl C61-butyric acid methyl ester] blend film was improved by the incorporation of a fluorocyanophenyl compound, 3,4,5,6-tetrafluorophthalonitrile (TFP), as an additive. When the amount of TFTadditive was 5 wt% based on the total amount of P3HT and PC61BM, the highest efficiency was achieved. The annealed PSC with 5 wt% TFP had a power conversion efficiency of 4.45% compared with that (3.57%) of the reference cell without the additive, which corresponds to an increase of about 18.7% in the efficiency due to an enhancement in the short circuit current (J(sc)). A seriese of measurements such as UV-visible absorption spectroscopy, X-ray measurements, atomic force microscopic images and incident photon to current conversion efficiency (IPCE) spectra revealed that the increased J(sc) in the PSC with P3HT:PC61BM:TFP blend film was due to an improvement in both exciton generation and charge transport efficiency, resulting from higher absorbance, larger crystal size and more effective phase separation.