Zinc oxide thin films have been deposited at high growth rates (up to ~1 nm/s) by spatial atomic layer deposition technique at atmospheric pressure. Water has been used as oxidant for diethylzinc (DEZ) at deposition temperatures between 75 and 250 °C. The electrical, structural (crystallinity and morphology), and optical properties of the films have been analyzed by using Hall, four-point probe, X-ray diffraction, scanning electron microscopy, spectrophotometry, and photoluminescence, respectively. All the films have c-axis (100) preferential orientation, good crystalline quality and high transparency (∼ 85%) in the visible range. By varying the DEZ partial pressure, the electrical properties of ZnO can be controlled, ranging from heavily n-type conductive (with 4 mOhm.cm resistivity for 250 nm thickness) to insulating. Combining the high deposition rates with a precise control of functional properties (i.e., conductivity and transparency) of the films, the industrially scalable spatial ALD technique can become a disruptive manufacturing method for the ZnO-based industry.

Atmospheric pressure spatial atomic layer deposition (AP-SALD) has recently emerged as an appealing technique for rapidly producing high quality oxides. Here, we focus on the use of AP-SALD to deposit functional ZnO thin films, particularly on the reactors used, the film properties, and the dopants that have been studied. We highlight how these films are advantageous for the performance of solar cells, organometal halide perovskite light emitting diodes, and thin-film transistors. Future AP-SALD technology will enable the commercial processing of thin films over large areas on a sheet-to-sheet and roll-to-roll basis, with new reactor designs emerging for flexible plastic and paper electronics.

Spatial atomic layer deposition can be used as a high-throughput manufacturing technique in functional thin film deposition for applications such as flexible electronics. This; however, requires low-temperature processing and handling of flexible substrates. The authors investigate the process conditions under which low-temperature spatial atomic layer deposition of alumina from trimethyl aluminum and water is possible. The water partial pressure is the critical parameter in this case. Finally, our approach to roll-to-roll spatial atomic layer deposition is discussed.

The possibility of growing multicomponent oxides by spatial atmospheric atomic layer deposition has been investigated. To this end, Al(x)Zn(1-x)O films have been deposited using diethyl zinc (DEZ), trimethyl aluminum (TMA), and water as Zn, Al, and O precursors, respectively. When the metal precursors (i.e., TMA and DEZ) are coinjected in the deposition region, the Al/(Al + Zn) ratio can be accurately controlled by either varying the TMA flow to the reactor or the exposure time of the substrate to the precursors. A high doping efficiency level (up to 70%) is achieved in Al-doped ZnO, resulting in films with a high carrier density (5 × 10(20) cm(-3)), low resistivity (2 × 10(-3) Ω cm), and good optical transparency (>85%) in the visible range. The morphology of the films changes from polycrystalline, in conductive i-ZnO and Al-doped ZnO, to amorphous, in highly resistive Al-rich films. The unique combination of the fine tuning of the composition, morphology, and electrical properties of the films with high deposition rates (>0.2 nm/s) paves the way for spatial ALD as an emerging disruptive technique for the growth of multicomponent oxides over large areas.

Spatial atomic layer deposition (ALD) is a promising technology for high deposition rate and high-throughput ALD that can be used for roll-to-roll and large-area applications. In an ideal spatial ALD reactor, the design of the injector should be tuned to the deposition kinetics of the ALD reaction, requiring an in-depth knowledge of the dependencies of the growth per cycle (GPC) on the main kinetic parameters. The authors have investigated the deposition kinetics of spatial ALD of alumina from trimethylaluminum and H2O at atmospheric pressure. A kinetic model was developed, which describes the growth per cycle as a function of the main kinetic parameters. The observation of a √t time dependency in the GPC indicates that precursor diffusion to substrate is rate limiting. Next to a fundamental insight into the kinetics of atmospheric pressure spatial ALD, this model can be used for design optimization of new spatial ALD reactors. Furthermore, the model shows that the maximum alumina deposition rates obtainable with spatial ALD are in the order of several nm/s.

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We have investigated the nucleation and growth of InGaZnO thin films by spatial atmospheric atomic layer deposition. Diethyl zinc (DEZ), trimethyl indium (TMIn), triethyl gallium (TEGa), and water were used as Zn, In, Ga and oxygen precursors, respectively. The vaporized metal precursors have been coinjected in the reactor. The metal composition of InGaZnO has been controlled by varying the TMIn or TEGa flow to the reactor, for a given DEZ flow and exposure time. The morphology of the films changes from polycrystalline, for ZnO and In-doped ZnO, to amorphous for In-rich IZO and InGaZnO. The use of these films as the active channel in TFTs has been demonstrated and the influence of In and Ga cations on the electrical characteristics of the TFTs has been studied.

The industrial need for high-throughput and low-cost ZnO deposition processes has triggered the development of atmospheric vapor-phase deposition techniques which can be easily applied to continuous, in-line manufacturing. While atmospheric CVD is a mature technology, new processes for the growth of transparent conductive oxides on thermally sensitive materials or flexible substrates are being developed, such as atmospheric plasma-enhanced (PE)-CVD and atmospheric spatial atomic layer deposition (ALD). In this article, the challenges and recent results on the growth of ZnO under atmospheric pressure by CVD, PE-CVD, and spatial ALD are reviewed and the use of these films as transparent electrodes in thin film solar cells are presented.