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.

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.

Self-Alignment of Bottom CZTSSe by Patterning of an Al2O3 Intermediate Layer.

When CZTSSe is synthesized using a metal precursor, large voids of nonuniform size form at Mo back contact side. Herein, we demonstrate that the voids and CZTSSe in the lower part of the CZTSSe double layer can be controlled by using an Al2O3-patterned Mo substrate. The CZTSSe in the lower part self-aligns on the Mo-exposed area, while the voids self-align on the Al2O3-coated area. The origin of the self-alignment is expected to be the difference in bonding characteristics between liquid Sn and the metal or oxide surface, e.g., Al2O3. Good wettability generally forms between nonreactive liquid metals and metal surfaces due to the strong metallic bonding. By contrast, poor wettability generally forms between nonreactive liquid metals and oxide surfaces due to the weak van der Waals bonding between the liquid metal and the oxide layer. When the patterning was added, the device efficiency tended to decrease from 8.6% to 10.5%.

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.

Secondary Phase Formation Mechanism in the Mo-Back Contact Region during Sulfo-Selenization Using a Metal Precursor: Effect of Wettability between a Liquid Metal and Substrate on Secondary Phase Formation.

Recently, highly efficient CZTS solar cells using pure metal precursors have been reported, and our group created a cell with 12.6% efficiency, which is equivalent to the long-lasting world record of IBM. In this study, we report a new secondary phase formation mechanism in the back contact interface. Previously, CZTSSe decomposition with Mo has been proposed to explain the secondary phase and void formation in the Mo-back contact region. In our sulfo-selenization system, the formation of voids and secondary phases is well explained by the unique wetting properties of Mo and the liquid metal above the peritectic reaction (η-Cu6Sn5 → ε-Cu3Sn + liquid Sn) temperature. Good wetting between the liquid Sn and the Mo substrate was observed because of strong metallic bonding between the liquid metal and Mo layer. Thus, some ε-Cu3Sn and liquid Sn likely remained on the Mo layer during the sulfo-selenization process, and Cu-SSe and Cu-Sn-SSe phases formed on the Mo side. When bare soda lime glass (SLG) was used as a substrate, nonwetting adhesion was observed because of weak van der Walls interactions between the liquid metal and substrate. The Cu-Sn alloy did not remain on the SLG surface, and Cu-SSe and Cu-Sn-SSe phases were not observed after the final sulfo-selenization process. Additionally, Mo/SLG substrates coated with a thin Al2O3 layer (1-5 nm) were used to control secondary phase formation by changing the wetting properties between Mo and the liquid metal. A 1 nm Al2O3 layer was enough to control secondary phase formation at the CZTSSe/Mo and void/Mo interfaces, and a 2 nm Al2O3 layer was enough to perfectly control secondary phase formation at the Mo interface and Mo-SSe formation.

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.

The electro-optical behavior of liquid crystal molecules on the surface of SiO2 inorganic thin films.

Inorganic thin films are well known for the liquid crystal alignment layers for LCoS application due to the higher thermal and photochemical stability of inorganic materials. The switching time of liquid crystals is the important factor for the projection application and the faster switching time is required for the high quality display. The switching behavior of liquid crystal molecules on inorganic thin films might be closely related with the surface properties of the inorganic thin films. Therefore the understanding of surface properties of the inorganic thin films is required for the enhancement of the switching time of liquid crystals of LCoS devices. In this work, we prepared the SiO2 inorganic thin films and the electro-optical behavior of liquid crystal molecules on SiO2 thin film was investigated. The sputtering condition of SiO2 thin film was closely related with the thickness and the surface morphology of SiO2 thin film. The switching time of liquid crystals with negative dielectric constant on SiO2 inorganic thin films was dominantly affected by the size of protrusion on the surface of SiO2 thin film and the surface roughness of SiO2 thin film was also related with the switching time of liquid crystals. From these results, it is possible to prepare the SiO2 inorganic thin film suitable for the liquid crystal alignment layer for VAN LC mode.