This article takes an effort to establish the potential of atomic layer deposition (ALD) technique toward the field of supercapacitors by preparing molybdenum disulfide (MoS) as its electrode. While molybdenum hexacarbonyl [Mo(CO)] serves as a novel precursor toward the low-temperature synthesis of ALD-grown MoS, HS plasma helps to deposit its polycrystalline phase at 200 °C. Several ex situ characterizations such as X-ray diffractometry (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and so forth are performed in detail to study the as-grown MoS film on a Si/SiO substrate. While stoichiometric MoS with very negligible amount of C and O impurities was evident from XPS, the XRD and high-resolution transmission electron microscopy analyses confirmed the (002)-oriented polycrystalline h-MoS phase of the as-grown film. A comparative study of ALD-grown MoS as a supercapacitor electrode on 2-dimensional stainless steel and on 3-dimensional (3D) Ni-foam substrates clearly reflects the advantage and the potential of ALD for growing a uniform and conformal electrode material on a 3D-scaffold layer. Cyclic voltammetry measurements showed both double-layer capacitance and capacitance contributed by the faradic reaction at the MoS electrode surface. The optimum number of ALD cycles was also found out for achieving maximum capacitance for such a MoS@3D-Ni-foam electrode. A record high areal capacitance of 3400 mF/cm was achieved for MoS@3D-Ni-foam grown by 400 ALD cycles at a current density of 3 mA/cm. Moreover, the ALD-grown MoS@3D-Ni-foam composite also retains high areal capacitance, even up to a high current density of 50 mA/cm. Finally, this directly grown MoS electrode on 3D-Ni-foam by ALD shows high cyclic stability (>80%) over 4500 charge-discharge cycles which must invoke the research community to further explore the potential of ALD for such applications.

We review the present state-of-the-art within back and front contacts in kesterite thin film solar cells, as well as the current challenges. At the back contact, molybdenum (Mo) is generally used, and thick Mo(S, Se) 2 films of up to several hundred nanometers are seen in record devices, in particular for selenium-rich kesterite. The electrical properties of Mo(S, Se) 2 can vary strongly depending on orientation and indiffusion of elements from the device stack, and there are indications that the back contact properties are less ideal in the sulfide as compared to the selenide case. However, the electronic interface structure of this contact is generally not well-studied and thus poorly understood, and more measurements are needed for a conclusive statement. Transparent back contacts is a relatively new topic attracting attention as crucial component in bifacial and multijunction solar cells. Front illuminated efficiencies of up to 6% have so far been achieved by adding interlayers that are not always fully transparent. For the front contact, a favorable energy level alignment at the kesterite/CdS interface can be confirmed for kesterite absorbers with an intermediate [S]/([S]+[Se]) composition. This agrees with the fact that kesterite absorbers of this composition reach highest efficiencies when CdS buffer layers are employed, while alternative buffer materials with larger band gap, such as Cd 1−x Zn x S or Zn 1−x Sn x O y , result in higher efficiencies than devices with CdS buffers when sulfurrich kesterite absorbers are used. Etching of the kesterite absorber surface, and annealing in air or inert atmosphere before or after buffer layer deposition, has shown strong impact on device performance. Heterojunction annealing to promote interdiffusion was used for the highest performing sulfide kesterite device and air-annealing was reported important for selenium-rich record solar cells. Cu 2 ZnSnS 4 (CZTS) absorbers for solar cell applications was first reported by Ito and Nakazawa [1]. Early results on CZTS device performance were reported by Friedlmeier et al [2], Seol et al [3], and Katagiri et al [4]. Later a group at IBM reached record performances with power conversion efficiencies (PCEs) above 10% for CZTSSe devices in 2010 [5] and the current record PCE of 12.6% in 2013 [6]. In 2018, researchers from DGIST reached the same performance, 12.6%, but for a larger device area [7]. The device structure used for kesterite solar cells was originally copied from that of Cu(In, Ga)Se 2 , (CIGSe) TFSCs, and is formed by sequential deposition, upon a soda lime glass substrate, of a Mo back contact, the absorber, a CdS buffer layer, and a ZnO/ZnO:Al bi-layer window (i.e. transparent top contact). This structure, schematically shown for CZTSSe in figure 1, is not necessarily ideal for kesterite solar cells, and extensive work has been invested into studies of alternative backand front contacts and related deposition processes. In this paper, the state-of-the-art and current open questions related to the back and front c...

This article demonstrates the atomic layer deposition (ALD) of tungsten nitride using tungsten hexacarbonyl [W(CO)6] and ammonia [NH3] and its use as a lithium-ion battery anode. In situ quartz crystal microbalance (QCM), ellipsometry and X-ray reflectivity (XRR) measurements are carried out to confirm the self-limiting behaviour of the deposition. A saturated growth rate of ca. 0.35 Å per ALD cycle is found within a narrow temperature window of 180-195 °C. In situ Fourier transform infrared (FTIR) vibrational spectroscopy is used to determine the reaction pathways of the surface bound species after each ALD half cycle. The elemental presence and chemical composition is determined by XPS. The as-deposited material is found to be amorphous and crystallized to h-W2N upon annealing at an elevated temperature under an ammonia atmosphere. The as-deposited materials are found to be n-type, conducting with an average carrier concentration of ca. 10(20) at room temperature. Electrochemical studies of the as-deposited films open up the possibility of this material to be used as an anode material in Li-ion batteries. The incorporation of MWCNTs as a scaffold layer further enhances the electrochemical storage capacity of the ALD grown tungsten nitride (WNx). Ex situ XRD analysis confirms the conversion based reaction mechanism of the as-grown material with Li under operation.

No abstract

Atomic layer deposition was adopted to deposit VO thin films using vanadyl tri-isopropoxide {VO[O(CH)], VTIP} and water (HO) at 135 °C. The self-limiting and purge-time-dependent growth behaviors were studied by ex situ ellipsometry to determine the saturated growth conditions for atomic-layer-deposited VO. The as-deposited films were found to be amorphous. The structural, chemical, and optical properties of the crystalline thin films with controlled phase formation were investigated after postdeposition annealing at various atmospheres and temperatures. Reducing and oxidizing atmospheres enabled the formation of pure VO and VO phases, respectively. The possible band structures of the crystalline VO and VO thin films were established. Furthermore, an electrochemical response and a voltage-induced insulator-to-metal transition in the vertical metal-vanadium oxide-metal device structure were observed for VO and VO films, respectively.