Element Diffusion Induced Carrier Transport Enhancement in High-Performance CZTSSe Self-Powered Photodetector.

Cu2ZnSn(S,Se)4 (CZTSSe) has attracted great interest in thin-film solar cells due to its excellent photoelectric performance in past decades, and recently is gradually expanding to the field of photodetectors. Here, the CZTSSe self-powered photodetector is prepared by using traditional photovoltaic device structure. Under zero bias, it exhibits the excellent performance with a maximum responsivity of 0.77 A W-1, a high detectivity of 8.78 × 1012 Jones, and a wide linear dynamic range of 103 dB. Very fast response speed with the rise/decay times of 0.576/1.792 µs, and ultra-high switching ratio of 3.54 × 105 are obtained. Comprehensive electrical and microstructure characterizations confirm that element diffusion among ITO, CdS, and CZTSSe layers not only optimizes band alignment of CdS/CZTSSe, but also suppresses the formation of interface defects. Such a suppression of interface defects and spike-like band alignment significantly inhibit carrier nonradiative recombination at interface and promote carrier transport capability. The low trap density in CZTSSe and low back contact barrier of CZTSSe/Mo could be responsible for the very fast response time of photodetector. This work definitely provides guidance for designing a high performance self-powered photodetector with high photoresponse, high switching ratio, fast response speed, and broad linear dynamic range.

Anisotropy and thermal properties in GeTe semiconductor by Raman analysis.

Low-symmetric GeTe semiconductors have attracted wide-ranging attention due to their excellent optical and thermal properties, but only a few research studies are available on their in-plane optical anisotropic nature that is crucial for their applications in optoelectronic and thermoelectric devices. Here, we investigate the optical interactions of anisotropy in GeTe using polarization-resolved Raman spectroscopy and first-principles calculations. After determining both armchair and zigzag directions in GeTe crystals by transmission electron microscopy, we found that the Raman intensity of the two main vibrational modes had a strong in-plane anisotropic nature; the one at ∼88.1 cm-1 can be used to determine the crystal orientation, and the other at ∼124.6 cm-1 can reveal a series of temperature-dependent phase transitions. These results provide a general approach for the investigation of the anisotropy of light-matter interactions in low-symmetric layered materials, benefiting the design and application of optoelectronic, anisotropic thermoelectric, and phase-transition memory devices based on bulk GeTe.

Deep defects limiting the conversion efficiency of Sb2Se3 thin-film solar cells.

Quasi-one-dimensional (Q1D) semiconductor antimony selenide (Sb2Se3) shows great potential in the photovoltaic field, but the photoelectric conversion efficiency (PCE) of Sb2Se3-based solar cells has shown no obvious breakthrough during the past several years, of which the intrinsic reasons are pending experimentally. Here, we prepare high-quality Q1D Sb2Se3 thin films via the vapor transport deposition technique. By investigating the bandedge electronic level structure and carrier relaxation/recombination dynamics, we find that (i) the optimized Se-rich growth conditions can highly improve the crystal quality of the Q1D Sb2Se3 thin films, the carrier lifetime of which is substantially increased up to ∼8.3 µs; (ii) the Se-rich growth conditions have advantages to annihilate the deep selenium vacancies VSei (i = 1 and 3 for non-equivalent Se atomic sites) but is not effective for the deep donor VSe2, which locates at ∼0.3 eV (300 K) below the conduction band and intrinsically limits the PCE value of devices below ∼7.63%. This work suggests that further optimizing the Se-rich conditions to technically eliminate this kind of deep defect is still essential for preparing high-performance Sb2Se3 film solar cells.

Abnormal vibrational anisotropy and thermal properties of a two-dimensional GeAs semiconductor.

Anisotropy in a crystal structure plays a striking role in determining the optical, electrical and thermal properties of the condensed matter. Here, we investigated in-plane vibrational anisotropy in a two-dimensional (2D) van der Waals (vdW)-layered GeAs narrow-gap semiconductor by combining microstructural characterization and polarization Raman spectroscopy. Interestingly, not only the intensities but also the Raman shifts in all modes evolved periodically with different symmetries as the polarization angle changed continuously, which could be well-analyzed using the Raman tensors and further interpreted from the phonon dispersion relations. More importantly, the temperature-dependent Raman intensities of the Raman modes in the range from 83 K to 823 K gave a thermal-related uniform constant, based on which key parameters, including the thermal expansion coefficient, Grüneisen constant and quasi-particle lifetime, could be directly derived, which were in line with the calculated predictions. This investigation provides a comprehensive understanding of structure-dependent optical anisotropy in 2D vdW-layered GeAs and suggests a new idea for exploring the thermal properties of related materials using temperature-dependent Raman spectroscopy.

Modulation of Ferroelectric and Optical Properties of La/Co-Doped KNbO3 Ceramics.

The phase transition, microscopic morphology and optical and ferroelectric properties are studied in a series of La- and Co-doped KNbO3-based ceramics. The results show that the doping induces the transformation from the orthorhombic to the cubic phase of KNbO3, significantly reduces the optical bandgap and simultaneously evidently improves the leakage, with a slight weakening of ferroelectric polarization. Further analysis reveals that (i) the Co doping is responsible for the obvious reduction of the bandgap, whereas it is reversed for the La doping; (ii) the slight deterioration of ferroelectricity is due to the doping-induced remarkable extrinsic defect levels and intrinsic oxygen vacancies; and (iii) the La doping can optimize the defect levels and inhibit the leakage. This investigation should both provide novel insight for exploring the bandgap engineering and ferroelectric properties of KNbO3, and suggest its potential applications, e.g., photovoltaic and multifunctional materials.

Modification of Back Contact in Cu2ZnSnS4 Solar Cell by Inserting Al-Doped ZnO Intermediate Layer.

The optimization of back contact interface is crucial to improve the performance of Cu2ZnSnS4 (CZTS) thin film solar cells. In this paper, we first employ Al-doped ZnO (AZO) as the intermediate layer into the Mo/CZTS interface to improve the quality of back contact region. This AZO intermediate layer, obtained from the sputtering method prior to the CZTS precursor deposition, initially blocks the direct contact of CZTS with the Mo layer and thus indeed suppresses the decomposition reaction between Mo and CZTS. Consequently, the generation of voids at the back contact region is obviously avoided. Besides, the AZO intermediate layer can inhibit the reaction between sulfur (S) and Mo during sulfurization process, and thus significantly reduce the thickness of MoS2. Meanwhile, the AZO intermediate layer with suitable thickness does not affect the crystal quality of CZTS absorber layer. Moreover, the effects of different thicknesses of predeposited AZO on the film morphology, composition, and corresponding device performance were systematically studied. After optimizing the thickness of the AZO layer, the efficiency of the resultant device has increased from 7.1% to 8.4% (the active area efficiency is 9.2%).

A sputtered CdS buffer layer for co-electrodeposited Cu2ZnSnS4 solar cells with 6.6% efficiency.

Cu2ZnSnS4 thin films with thicknesses ranging from 0.35 to 1.85 µm and micron-sized grains (0.5-1.5 µm) were synthesized using co-electrodeposited Cu-Zn-Sn-S precursors with different deposition times. Here we have introduced a sputtered CdS buffer layer for the development of CZTS solar cells for the first time, which enables breakthrough efficiencies up to 6.6%.

Co-electroplated Kesterite Bifacial Thin-Film Solar Cells: A Study of Sulfurization Temperature.

Earth-abundant material, kesterite Cu2ZnSnS4 (CZTS), demonstrates the tremendous potential to serve as the absorber layer for the bifacial thin-film solar cell. The exploration of appropriate sulfurization conditions including annealing temperature is significant to gain insight into the growth mechanism based on the substrates using transparent conductive oxides (TCO) and improve device performance. The kesterite solar absorbers were fabricated on ITO substrates by sulfurizing co-electroplated Cu-Zn-Sn-S precursors in argon diluted H2S atmosphere at different temperatures (475-550 °C) for 30 min. Experimental proof, including cross-section scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, UV-vis-NIR transmission spectrum, and Raman and far-infrared spectroscopy, is presented for the crystallization of CZTS on an ITO substrate and the interfacial reaction between the ITO back contact and CZTS absorber. The complete conversion of precursor into CZTS requires at least 500 °C sulfurization temperature. The aggressive interfacial reaction leading to the out-diffusion of In into CZTS to a considerable extent, formation of tin sulfides, and electrically conductive degradation of ITO back contact occurs at the sulfurization temperatures higher than 500 °C. The bifacial devices obtained by 520 °C sulfurization exhibit the best conversion efficiencies and open circuit voltages. However, the presence of non-ohmic back contact (secondary diode), the short minority lifetime, and the high interfacial recombination rates negatively limit the open circuit voltage, fill factor, and efficiency, evidenced by illumination/temperature-dependent J-V, frequency-dependent capacitance-voltage (C-V-f), time-resolved PL (TRPL), and bias-dependent external quantum efficiency (EQE) measurements.

Characteristics of in-substituted CZTS thin film and bifacial solar cell.

Implementing bifacial photovoltaic devices based on transparent conducting oxides (TCO) as the front and back contacts is highly appealing to improve the efficiency of kesterite solar cells. The p-type In substituted Cu2ZnSnS4 (CZTIS) thin-film solar cell absorber has been fabricated on ITO glass by sulfurizing coelectroplated Cu-Zn-Sn-S precursors in H2S (5 vol %) atmosphere at 520 °C for 30 min. Experimental proof, including X-ray diffraction, Raman spectroscopy, UV-vis-NIR transmission/reflection spectra, PL spectra, and electron microscopies, is presented for the interfacial reaction between the ITO back contact and CZTS absorber. This aggressive reaction due to thermal processing contributes to substitutional diffusion of In into CZTS, formation of secondary phases and electrically conductive degradation of ITO back contact. The structural, lattice vibrational, optical absorption, and defective properties of the CZTIS alloy absorber layer have been analyzed and discussed. The new dopant In is desirably capable of improving the open circuit voltage deficit of kesterite device. However, the nonohmic back contact in the bifacial device negatively limits the open circuit voltage and fill factor, evidencing by illumination-/temperature-dependent J-V and frequency-dependent capacitance-voltage (C-V-f) measurements. A 3.4% efficient solar cell is demonstrated under simultaneously bifacial illumination from both sides of TCO front and back contacts.

Influence of transition metal doping on the structural, optical, and magnetic properties of TiO2 films deposited on Si substrates by a sol-gel process.

Transition metal (TM)-doped TiO2 films (TM = Co, Ni, and Fe) were deposited on Si(100) substrates by a sol-gel method. With the same dopant content, Co dopants catalyze the anatase-to-rutile transformation (ART) more obviously than Ni and Fe doping. This is attributed to the different strain energy induced by the different dopants. The optical properties of TM-doped TiO2 films were studied with spectroscopic ellipsometry data. With increasing dopant content, the optical band gap (EOBG) shifts to lower energy. With the same dopant content, the EOBG of Co-doped TiO2 film is the smallest and that of Fe-doped TiO2 film is the largest. The results are related to electric disorder due to the ART. Ferromagnetic behaviors were clearly observed for TM-doped TiO2 films except the undoped TiO2 film which is weakly magnetic. Additionally, it is found that the magnetizations of the TM-doped TiO2 films decrease with increasing dopant content.

A first-principles study on the intrinsic asymmetric ferroelectricity of the SrTiO3-BaTiO3-CaTiO3 tricolor superlattice at the nanoscale.

We report a systematic theoretical study on the ferroelectric behavior of ultrathin three-component ferroelectric films, e.g., CaTiO3-BaTiO3-SrTiO3, sandwiched between electrodes. Using first-principles calculations we demonstrate that such structures have intrinsic asymmetric ferroelectricity which is robust even at the nanoscale. In addition, there exists a certain relationship between the polarization directions and geometric stacking sequences of the superlattices. Specifically, the lowest energy states always have polarizations pointing from CaTiO3 via BaTiO3 to SrTiO3, while the sequence in the metastable states is SrTiO3-BaTiO3-CaTiO3. Therefore we were able to distinguish one ferroelectric state from its opposite state by means of their geometric stackings along the polarization directions. Besides this, band alignment analysis reveals that such structures are well behaved at the metal/ferroelectric interface, confirming the credibility and reliability of our first-principles calculation. Our finding may suggest a controllable and unambiguous way to build ferroelectric and multiferroic tunnel junctions.

Nonenzymatic glucose sensor based on over-oxidized polypyrrole modified Pd/Si microchannel plate electrode.

A silicon microchannel plate (MCP) array electrode modified with over-oxidized polypyrrole (OPPy) has been fabricated to detect glucose. The morphology and structure of the electrode are characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The OPPy modified silicon MCP array electrode exhibits high electrocatalytic activity as well as excellent selectivity to the electrochemical oxidation of glucose. At a potential of +0.08 V, good sensitivity of 0.37 mA mM(-1) cm(-2) and detection limit of 2.06 µM are attained. The linear range is up to 24 mM with a linear correlation coefficient of 0.997. Furthermore, the electrode is highly resistant to interfering substances because the effects of common coexisting substances can be effectively eliminated by the OPPy film and the response in the current to interferences on the electrode surface is almost negligible. This novel electrode has high potential in nonenzymatic detection of glucose.