The semiconductor industry faces physical limitations due to its top-down manufacturing processes. High cost of EUV equipment, time loss during tens or hundreds of photolithography steps, overlay, etch process errors, and contamination issues owing to photolithography still exist and may become more serious with the miniaturization of semiconductor devices. Therefore, a bottom-up approach is required to overcome these issues. The key technology that enables bottom-up semiconductor manufacturing is area-selective atomic layer deposition (ASALD). Here, various ASALD processes for elemental metals, such as Co, Cu, Ir, Ni, Pt, and Ru, are reviewed. Surface treatments using chemical species, such as self-assembled monolayers and small-molecule inhibitors, to control the hydrophilicity of the surface have been introduced. Finally, we discuss the future applications of metal ASALD processes.

Thermoelectric materials and devices are energy-harvesting devices that can effectively recycle waste heat into electricity. Thermoelectric power generation is widely used in factories, engines, and even in human bodies as they continuously generate heat. However, thermoelectric elements exhibit poor performance and low energy efficiency; research is being conducted to find new materials or improve the thermoelectric performance of existing materials, that is, by ensuring a high figure-of-merit (zT) value. For increasing zT, higher σ (electrical conductivity) and S (Seebeck coefficient) and a lower к (thermal conductivity) are required. Here, interface engineering by atomic layer deposition (ALD) is used to increase zT of n-type BiTeSe (BTS) thermoelectric powders. ALD of the BTS powders is performed in a rotary-type ALD reactor, and 40 to 100 ALD cycles of ZnO thin films are conducted at 100oC. The physical and chemical properties and thermoelectric performance of the ALD-coated BTS powders and pellets are characterized. It is revealed that electrical conductivity and thermal conductivity are decoupled, and thus, zT of ALD-coated BTS pellets is increased by more than 60% compared to that of the uncoated BTS pellets. This result can be utilized in a novel method for improving the thermoelectric efficiency in materials processing.

Thermoelectric materials can reversely convert heat and electricity into each other; therefore, they can be very useful for energy harvesting from heat waste. Among many thermoelectrical materials, SnSe exhibits outstanding thermoelectric performance along the particular direction of a single crystal. However, single-crystal SnSe has poor mechanical properties and thus it is difficult to apply for mass production. Therefore, polycrystalline SnSe materials may be used to replace single-crystal SnSe by overcoming its inferior thermoelectric performance owing to surface oxidation. Considerable efforts are currently focused on enhancing the thermoelectric performance of polycrystalline SnSe. In this study, we briefly review various enhancement methods for SnSe thermoelectric materials, including doping, texturing, and nano-structuring. Finally, we discuss the future prospects of SnSe thermoelectric powder materials.

The SnSe single crystal shows an outstanding figure of merit (ZT) of 2.6 at 973 K; thus, it is considered to be a promising thermoelectric material. However, the mass production of SnSe single crystals is difficult, and their mechanical properties are poor. Alternatively, we can use polycrystalline SnSe powder, which has better mechanical properties. In this study, surface modification by atomic layer deposition (ALD) is chosen to increase the ZT value of SnSe polycrystalline powder. SnSe powder is ground by a ball mill. An ALD coating process using a rotary-type reactor is adopted. ZnO thin films are grown by 100 ALD cycles using diethylzinc and H2O as precursors at 100oC. ALD is performed at rotation speeds of 30, 40, 50, and 60 rpm to examine the effects of rotation speed on the thin film characteristics. The physical and chemical properties of ALD-coated SnSe powders are characterized by scanning and tunneling electron microscopy combined with energy-dispersive spectroscopy. The results reveal that a smooth oxygenrich ZnO layer is grown on SnSe at a rotation speed of 30 rpm. This result can be applied for the uniform coating of a ZnO layer on various powder materials.

Aluminum nitride (AlN) has versatile and intriguing properties, such as wide direct bandgap, high thermal conductivity, good thermal and chemical stability, and various functionalities. Due to these properties, AlN thin films have been applied in various fields. However, AlN thin films are usually deposited by high temperature processes like chemical vapor deposition. To further enlarge the application of AlN films, atomic layer deposition (ALD) has been studied as a method of AlN thin film deposition at low temperature. In this mini review paper, we summarize the results of recent studies on AlN film grown by thermal and plasma enhanced ALD in terms of processing temperature, precursor type, reactant gas, and plasma source. Thermal ALD can grow AlN thin films at a wafer temperature of 150~550 oC with alkyl/amine or chloride precursors. Due to the low reactivity with NH3 reactant gas, relatively high growth temperature and narrow window are reported. On the other hand, PEALD has an advantage of low temperature process, while crystallinity and defect level in the film are dependent on the plasma source. Lastly, we also introduce examples of application of ALD-grown AlN films in electronics.

The electrical and interfacial properties of HfO2/Al2O3 and Al2O3/HfO2 dielectrics on AlN/p-Ge interface prepared by thermal atomic layer deposition are investigated by capacitance–voltage(C–V) and current–voltage(I–V) measurements. In the C–V measurements, humps related to mid-gap states are observed when the ac frequency is below 100 kHz, revealing lower mid-gap states for the HfO2/Al2O3 sample. Higher frequency dispersion in the inversion region is observed for the Al2O3/HfO2 sample, indicating the presence of slow interface states A higher interface trap density calculated from the high-low frequency method is observed for the Al2O3/HfO2 sample. The parallel conductance method, applied to the accumulation region, shows border traps at 0.3~0.32 eV for the Al2O3/HfO2 sample, which are not observed for the Al2O3/HfO2 sample. I–V measurements show a reduction of leakage current of about three orders of magnitude for the HfO2/Al2O3 sample. Using the Fowler-Nordheim emission, the barrier height is calculated and found to be about 1.08 eV for the HfO2/Al2O3 sample. Based on these results, it is suggested that HfO2/Al2O3 is a better dielectric stack than Al2O3/HfO2 on AlN/p-Ge interface.

Atomic layer deposition (ALD) is widely used as a tool for the formation of near-atomically flat and uniform thin films in the semiconductor and display industries because of its excellent uniformity. Nowadays, ALD is being extensively used in diverse fields, such as energy and biology. By controlling the reactivity of the surface, either homogeneous or inhomogeneous coating on the shell of nanostructured powder can be accomplished by the ALD process. However, the ALD process on the powder largely depends on the displacement of powder in the reactor. Therefore, the technology for the fluidization of the powder is very important to redistribute its position during the ALD process. Herein, an overview of the three types of ALD reactors to agitate or fluidize the powder to improve the conformality of coating is presented. The principle of fluidization its advantages, examples, and limitations are addressed.

An Al2O3/AlN bilayer deposited on GaN by atomic layer deposition (ALD) is employed to prepare Al2O3/AlN/GaN metal-insulator-semiconductor (MIS) diodes, and their interfacial properties are investigated using X-ray photoelectron spectroscopy (XPS) with sputter etch treatment and current-voltage (I-V) measurements. XPS analyses reveal that the native oxides on the GaN surface are reduced significantly during the early ALD stage, indicating that AlN deposition effectively clelans up the GaN surface. In addition, the suppression of Al-OH bonds is observed through the ALD process. This result may be related to the improved device performance because Al-OH bonds act as interface defects. Finally, temperature dependent I-V analyses show that the barrier height increases and the ideality factor decreases with an increase in temperature, which is associated with the barrier inhomogeneity. A Modified Richardson plot produces the Richardson constant of A** as 30.45 Acm−2K−2, which is similar to the theoretical value of 26.4 Acm−2K−2 for n-GaN. This indicates that the barrier inhomogeneity appropriately explains the forward current transport across the Au/Al2O3/AlN/GaN interface.

TaNx film is grown by plasma enhanced atomic layer deposition (PEALD) using t-butylimido tris(dimethylamido) tantalum as a metalorganic source with various reactive gas species, such as N2+H2 mixed gas, NH3, and H2. Although the pulse sequence and duration are the same, aspects of the film growth rate, microstructure, crystallinity, and electrical resistivity are quite different according to the reactive gas. Crystallized and relatively conductive film with a higher growth rate is acquired using NH3 as a reactive gas while amorphous and resistive film with a lower growth rate is achieved using N2+H2 mixed gas. To examine the relationship between the chemical properties and resistivity of the film, X-ray photoelectron spectroscopy (XPS) is conducted on the ALD-grown TaNx film with N2+H2 mixed gas, NH3, and H2. For a comparison, reactive sputter-grown TaNx film with N2 is also studied. The results reveal that ALD-grown TaNx films with NH3 and H2 include a metallic Ta-N bond, which results in the film’s higher conductivity. Meanwhile, ALD-grown TaNx film with a N2+H2 mixed gas or sputtergrown TaNx film with N2 gas mainly contains a semiconducting Ta3N5 bond. Such a different portion of Ta-N and Ta3N5 bond determins the resistivity of the film. Reaction mechanisms are considered by means of the chemistry of the Ta precursor and reactive gas species.

Carbon nanofibers (CNF) are widely used as active agents for electrodes in Li-ion secondary battery cells, supercapacitors, and fuel cells. Nanoscale coatings on CNF electrodes can increase the output and lifespan of battery devices. Atomic layer deposition (ALD) can control the coating thickness at the nanoscale regardless of the shape, suitable for coating CNFs. However, because the CNF surface comprises stable C–C bonds, initiating homogeneous nuclear formation is difficult because of the lack of initial nucleation sites. This study introduces uniform nucleation site formation on CNF surfaces to promote a uniform SnO2 layer. We pretreat the CNF surface by introducing H2O or Al2O3 (trimethylaluminum + H2O) before the SnO2 ALD process to form active sites on the CNF surface. Transmission electron microscopy and energy-dispersive spectroscopy both identify the SnO2 layer morphology on the CNF. The Al2O3-pretreated sample shows a uniform SnO2 layer, while island-type SnOx layers grow sparsely on the H2Opretreated or untreated CNF.

We performed temperature dependent current-voltage (I-V) measurements to characterize the electrical properties of Au/Al2O3/n-Ge metal-insulator-semiconductor (MIS) diodes prepared with and without H2O prepulse treatment by atomic layer deposition (ALD). By considering the thickness of the Al2O3 interlayer, the barrier height for the treated sample was found to be 0.61 eV, similar to those of Au/n-Ge Schottky diodes. The thermionic emission (TE) model with barrier inhomogeneity explained the final state of the treated sample well. Compared to the untreated sample, the treated sample was found to have improved diode characteristics for both forward and reverse bias conditions. These results were associated with the reduction of charge trapping and interface states near the Ge/Al2O3 interface.

Insulating TaNx films were grown by plasma enhanced atomic layer deposition using butylimido tris dimethylamido tantalum and N2+H2 mixed gas as metalorganic source and reactance gas, respectively. Crossbar devices having a Pt/TaNx/Pt stack were fabricated and their electrical properties were examined. The crossbar devices exhibited temperature-dependent nonlinear I (current) - V (voltage) characteristics in the temperature range of 90-300 K. Various electrical conduction mechanisms were adopted to understand the governing electrical conduction mechanism in the device. Among them, the Poole- Frenkel emission model, which uses a bulk-limited conduction mechanism, may successfully fit with the I - V characteristics of the devices with 5- and 18-nm-thick TaNx films. Values of ~0.4 eV of trap energy and ~20 of dielectric constant were extracted from the fitting. These results can be well explained by the amorphous micro-structure and point defects, such as oxygen substitution (ON) and interstitial nitrogen (Ni) in the TaNx films, which were revealed by transmission electron microscopy and UV-Visible spectroscopy. The nonlinear conduction characteristics of TaNx film can make this film useful as a selector device for a crossbar array of a resistive switching random access memory or a synaptic device.

Lithium-ion batteries (LIBs) are rapidly improving in capacity and life cycle characteristics to meet the requirements of a wide range of applications, such as portable electronics, electric vehicles, and micro- or nanoelectromechanical systems. Recently, atomic layer deposition (ALD), one of the vapor deposition methods, has been explored to expand the capability of LIBs by producing near-atomically flat and uniform coatings on the shell of nanostructured electrodes and membranes for conventional LIBs. In this paper, we introduce various ALD coatings on the anode, cathode, and separator materials to protect them and improve their electrochemical and thermomechanical stability. In addition, we discuss the effects of ALD coatings on the three-dimensional structuring and conduction layer through activation of electrochemical reactions and facilitation of fluent charge collection.

The triboelectric property of a material is important to improve an efficiency of triboelectric generator(TEG) in energy harvesting from an ambient energy. In this study, we have studied the TEG property of a semicon-ducting SnO2 which has yet to be explored so far. As a counter triboelectric material, PET and glass are used. Verticalcontact mode is utilized to evaluate the TEG efficiency. SnO2 thin film is deposited by atomic layer deposition on bareSi wafer for various thicknesses from 5.2 nm to 34.6 nm, where the TEG output is increased from 13.9V to 73.5V. Tri-boelectric series are determined by comparing the polarity of output voltage of 2 samples among SnO2, PET, and glass.In conclusion, SnO2, as an intrinsic n-type material, has the most strong tendency to be positive side to lose the electronand PET has the most strong tendency to be negative side to get the electron, and glass to be between them. Therefore,the SnO2-PET combination shows the highest TEG efficiency.

Resistance switching memory cells were fabricated using atomically dispersed Pt-SiO2 thin film prepared via RF co-sputtering. The memory cell can switch between a low-resistance-state and a high-resistance-state reversibly and reproducibly through applying alternate voltage polarities. Percolated conducting paths are the origin of the low-resistance-state, while trapping electrons in the negative U-center in the Pt-SiO2 interface cause the high-resistance-state. Intermediate resistance-states are obtained through controlling the compliance current, which can be applied to multi-level operation for high memory density. It is found that the resistance value is related to the capacitance of the memory cell: a 265-fold increase in resistance induces a 2.68-fold increase in capacitance. The exponential growth model of the conducting paths can explain the quantitative relationship of resistance-capacitance. The model states that the conducting path generated in the early stage requires a larger area than that generated in the last stage, which results in a larger decrease in the capacitance.