Low Temperature Thermal Atomic Layer Deposition of Aluminum Nitride Using Hydrazine as the Nitrogen Source.

Aluminum nitride (AlN) thin films were grown using thermal atomic layer deposition in the temperature range of 175-350 °C. The thin films were deposited using trimethyl aluminum (TMA) and hydrazine (N2H4) as a metal precursor and nitrogen source, respectively. Highly reactive N2H4, compared to its conventionally used counterpart, ammonia (NH3), provides a higher growth per cycle (GPC), which is approximately 2.3 times higher at a deposition temperature of 300 °C and, also exhibits a low impurity concentration in as-deposited films. Low temperature AlN films deposited at 225 °C with a capping layer had an Al to N composition ratio of 1:1.1, a close to ideal composition ratio, with a low oxygen content (7.5%) while exhibiting a GPC of 0.16 nm/cycle. We suggest that N2H4 as a replacement for NH3 is a good alternative due to its stringent thermal budget.

A Comprehensive Study on the Effect of TiN Top and Bottom Electrodes on Atomic Layer Deposited Ferroelectric Hf0.5Zr0.5O2 Thin Films.

The discovery of ferroelectricity in HfO2-based materials in 2011 provided new research directions and opportunities. In particular, for atomic layer deposited Hf0.5Zr0.5O2 (HZO) films, it is possible to obtain homogenous thin films with satisfactory ferroelectric properties at a low thermal budget process. Based on experiment demonstrations over the past 10 years, it is well known that HZO films show excellent ferroelectricity when sandwiched between TiN top and bottom electrodes. This work reports a comprehensive study on the effect of TiN top and bottom electrodes on the ferroelectric properties of HZO thin films (10 nm). Investigations showed that during HZO crystallization, the TiN bottom electrode promoted ferroelectric phase formation (by oxygen scavenging) and the TiN top electrode inhibited non-ferroelectric phase formation (by stress-induced crystallization). In addition, it was confirmed that the TiN top and bottom electrodes acted as a barrier layer to hydrogen diffusion into the HZO thin film during annealing in a hydrogen-containing atmosphere. These features make the TiN electrodes a useful strategy for improving and preserving the ferroelectric properties of HZO thin films for next-generation memory applications.

Multifunctional, Room-Temperature Processable, Heterogeneous Organic Passivation Layer for Oxide Semiconductor Thin-Film Transistors.

In recent decades, oxide thin-film transistors (TFTs) have attracted a great deal of attention as a promising technology in terms of next-generation electronics due to their outstanding electrical performance. However, achieving robust electrical characteristics under various environments is a crucial challenge for successful realization of oxide-based electronic applications. To resolve the limitation, we propose a highly flexible and reliable heterogeneous organic passivation layer composed of stacked parylene-C and diketopyrrolopyrrole-polymer films for improving stability of oxide TFTs under various environments and mechanical stress. The presented multifunctional heterogeneous organic (MHO) passivation leads to high-performance oxide TFTs by: (1) improving their electrical characteristics, (2) protecting them from external reactive molecules, and (3) blocking light exposure to the oxide layer. As a result, oxide TFTs with MHO passivation exhibit outstanding stability in ambient air as well as under light illumination: the threshold voltage shift of the device is almost 0 V under severe negative bias illumination stress condition (white light of 5700 lx, gate voltage of -20 V, and drain voltage of 10.1 V for 20 000 s). Furthermore, since the MHO passivation layer exhibits high mechanical stability at a bending radius of ≤5 mm and can be deposited at room temperature, this technique is expected to be useful in the fabrication of flexible/wearable devices.

Realization of Spatially Addressable Library by a Novel Combinatorial Approach on Atomic Layer Deposition: A Case Study of Zinc Oxide.

Though the synthesis of libraries of multicomponent metal oxide systems is prevalent using the combinatorial approach, the combinatorial approach has been rarely realized in studying simple metal oxides, especially applied to the atomic layer deposition (ALD) technique. In this literature, a novel combinatorial approach technique is utilized within an ALD grown simple metal oxide to synthesize a "spatially addressable combinatorial library". The two key factors in gradients were defined during the ALD process: (1) the process temperature and (2) a nonuniform flow of pulsed gases inside a cross-flow reactor. To validate the feasibility of our novel combinatorial approach, a case study of zinc oxide (ZnO), a simple metal oxide whose properties are well-known, is performed. Because of the induced gradient, the ZnO (002) crystallite size was found to gradually vary across a 100 mm wafer (∼10-20 nm) with a corresponding increase in the normalized Raman E2/A1 peak intensity ratio. The findings agree well with the visible grain size observed from scanning electron microscope. The novel combinatorial approach provides a means of systematical interpretation of the combined effect of the two gradients, especially in the analysis of the microstructure of ZnO crystals. Moreover, the combinatorial library reveals that the process temperature, rather than the crystal size, plays the most significant role in determining the electrical conductivity of ZnO.

Stress-Induced Crystallization of Thin Hf1- XZr XO2 Films: The Origin of Enhanced Energy Density with Minimized Energy Loss for Lead-Free Electrostatic Energy Storage Applications.

Increasing interest in the development of alternative energy storage technologies has led to efforts being taken to improve the energy density of dielectric capacitors with high power density. However, dielectric polymer materials still have low energy densities because of their low dielectric constant, whereas Pb-based materials are limited by environmental issues and regulations. Here, the energy storage behaviors of atomic layer-deposited Hf1- XZr XO2 ( X = 0-1) thin films (10 nm) and the phase transformation mechanism associated with an enhancement of their energy density are reported using unipolar pulse measurements. Based on electrical and material characterization, the energy density and energy efficiency are dependent on the Zr content, and stress-induced crystallization by the encapsulating Hf1- XZr XO2 films with TiN top electrodes prior to annealing can enhance the energy density (up to 47 J/cm3 at a small voltage value of 3.5 MV/cm) while minimizing energy loss even at low process temperatures (400 °C). This work will facilitate the realization of Hf1- XZr XO2-based capacitors for lead-free electrostatic energy storage applications.

Investigation of the Physical Properties of Plasma Enhanced Atomic Layer Deposited Silicon Nitride as Etch Stopper.

Correlations between physical properties linking film quality with wet etch rate (WER), one of the leading figures of merit, in plasma-enhanced atomic layer deposition (PEALD) grown silicon nitride (SiN x) films remain largely unresearched. Achieving a low WER of a SiN x film is especially significant in its use as an etch stopper for technology beyond 7 nm node semiconductor processing. Herein, we explore the correlation between the hydrogen concentration, hydrogen bonding states, bulk film density, residual impurity concentration, and the WERs of PEALD SiN x using Fourier transform infrared spectrometry, X-ray reflectivity, and spectroscopic ellipsometry, etc. PEALD SiN x films for this study were deposited using hexachlorodisilane and hollow cathode plasma source under a range of process temperatures (270-360 °C) and plasma gas compositions (N2/NH3 or Ar/NH3) to understand the influence of hydrogen concentration, hydrogen bonding states, bulk film density, and residual impurity concentration on the WER. Varying hydrogen concentration and differences in the hydrogen bonding states resulted in different bulk film densities and, accordingly, a variation in WER. We observe a linear relationship between hydrogen bonding concentration and WER as well as a reciprocal relationship between bulk film density and WER. Analogous to the PECVD SiN x processes, a reduction in hydrogen bonding concentration arises from either (1) thermal activation or (2) plasma excited species. However, unlike the case with silane (SiH4)-based PECVD SiN x, PEALD SiN x WERs are affected by residual impurities of Si precursors (i.e., chlorine impurity). Thus, possible wet etching mechanisms in HF in which the WER is affected by hydrogen bonding states or residual impurities are proposed. The shifts of amine basicity in SiN x due to different hydrogen bonding states and the changes in Si electrophilicity due to Cl impurity content are suggested as the main mechanisms that influence WER in the PEALD processes.

Boosting Visible Light Absorption of Metal-Oxide-Based Phototransistors via Heterogeneous In-Ga-Zn-O and CH3NH3PbI3 Films.

To broaden the availability and application of metal-oxide (M-O)-based optoelectronic devices, we suggest heterogeneous phototransistors composed of In-Ga-Zn-O (IGZO) and methylammonium lead iodide (CH3NH3PbI3) layers, which act as the amplifier layer (channel layer) and absorption layer, respectively. These heterogeneous phototransistors showed low persistence photocurrent compared with IGZO-only phototransistors and exhibited high photoresponsivity of 61 A/W, photosensitivity of 3.48 × 106, detectivity of 9.42 × 1010 Jones, external quantum efficiency of 154% in an optimized structure, and high photoresponsivity under water exposure via the deposition of silicon dioxide as a passivation layer. On the basis of these electrical results and various analyses, we determined that CH3NH3PbI3 could be activated as a light absorption layer, current barrier, and plasma damage blocking layer, which would serve to widen the range of applications of M-O-based optoelectronic devices with high photoresponsivity and reliability under visible light illumination.

Solution-processed indium oxide electron transporting layers for high-performance and photo-stable perovskite and organic solar cells.

Interface engineering is considered the key to improving the device performance and stability of solar cells. In particular, TiO2 nanostructures, when used as electron transporting layers (ETLs) in metal halide perovskite solar cells (PSCs), led to excellent power conversion efficiencies (PCEs) of over 20%. They effectively transferred charge carriers from the perovskite and suppressed charge recombination at the interfaces. However, the photocatalytic effect of TiO2 on the perovskite can significantly degrade the device performance under ultraviolet illumination. Therefore, other classes of n-type metal oxides with a wide band gap should be developed to improve their photo-stability. Herein, we demonstrate the development of In2O3 thin films by a solution process and their application as ETLs in PSCs and organic solar cells (OSCs). Pin hole-free In2O3 ETLs obtained by the thermal decomposition of an In precursor thin film exhibit high conductivity (2.49 × 10-4 S cm-1) and low surface roughness (7.33 nm). This leads to impressive PCEs of 14.63% and 3.03% for the PSC and the inverted OSC, respectively. Furthermore, the In2O3-PSC shows better photo-stability than the TiO2-PSC by virtue of the wider band gap of In2O3, which leads to a PCE retention of 74% and 46%, relative to the initial PCE values of the PSC and the inverted OSC, respectively.

A solution-processed quaternary oxide system obtained at low-temperature using a vertical diffusion technique.

We report a method for fabricating solution-processed quaternary In-Ga-Zn-O (IGZO) thin-film transistors (TFTs) at low annealing temperatures using a vertical diffusion technique (VDT). The VDT is a deposition process for spin-coating binary and ternary oxide layers consecutively and annealing at once. With the VDT, uniform and dense quaternary oxide layers were fabricated at lower temperatures (280 °C). Compared to conventional IGZO and ternary In-Zn-O (IZO) thin films, VDT IGZO thin film had higher density of the metal-oxide bonds and lower density of the oxygen vacancies. The field-effect mobility of VDT IGZO TFT increased three times with an improved stability under positive bias stress than IZO TFT due to the reduction in oxygen vacancies. Therefore, the VDT process is a simple method that reduces the processing temperature without any additional treatment for quaternary oxide semiconductors with uniform layers.

Activation of sputter-processed indium-gallium-zinc oxide films by simultaneous ultraviolet and thermal treatments.

Indium-gallium-zinc oxide (IGZO) films, deposited by sputtering at room temperature, still require activation to achieve satisfactory semiconductor characteristics. Thermal treatment is typically carried out at temperatures above 300 °C. Here, we propose activating sputter- processed IGZO films using simultaneous ultraviolet and thermal (SUT) treatments to decrease the required temperature and enhance their electrical characteristics and stability. SUT treatment effectively decreased the amount of carbon residues and the number of defect sites related to oxygen vacancies and increased the number of metal oxide (M-O) bonds through the decomposition-rearrangement of M-O bonds and oxygen radicals. Activation of IGZO TFTs using the SUT treatment reduced the processing temperature to 150 °C and improved various electrical performance metrics including mobility, on-off ratio, and threshold voltage shift (positive bias stress for 10,000 s) from 3.23 to 15.81 cm(2)/Vs, 3.96 × 10(7) to 1.03 × 10(8), and 11.2 to 7.2 V, respectively.

Fabrication of high performance thin-film transistors via pressure-induced nucleation.

We report a method to improve the performance of polycrystalline Si (poly-Si) thin-film transistors (TFTs) via pressure-induced nucleation (PIN). During the PIN process, spatial variation in the local solidification temperature occurs because of a non-uniform pressure distribution during laser irradiation of the amorphous Si layer, which is capped with an SiO2 layer. This leads to a four-fold increase in the grain size of the poly-Si thin-films formed using the PIN process, compared with those formed using conventional excimer laser annealing. We find that thin films with optimal electrical properties can be achieved with a reduction in the number of laser irradiations from 20 to 6, as well as the preservation of the interface between the poly-Si and the SiO2 gate insulator. This interface preservation becomes possible to remove the cleaning process prior to gate insulator deposition, and we report devices with a field-effect mobility greater than 160 cm(2)/Vs.

Approaches to label-free flexible DNA biosensors using low-temperature solution-processed InZnO thin-film transistors.

Low-temperature solution-processed In-Zn-O (IZO) thin-film transistors (TFTs) exhibiting a favorable microenvironment for electron transfer by adsorbed artificial deoxyribonucleic acid (DNA) have extraordinary potential for emerging flexible biosensor applications. Superb sensing ability to differentiate even 0.5 µL of 50 nM DNA target solution was achieved through using IZO TFTs fabricated at 280 °C. Our IZO TFT had a turn-on voltage (V(on)) of -0.8 V, on/off ratio of 6.94 × 10(5), and on-current (I(on)) value of 2.32 × 10(-6)A in pristine condition. A dry-wet method was applied to immobilize two dimensional double crossover tile based DNA nanostructures on the IZO surface, after which we observed a negative shift of the transfer curve accompanied by a significant increase in the Ion and degradation of the Von and on/off ratio. As the concentration of DNA target solution increased, variances in these parameters became increasingly apparent. The sensing mechanism based on the current evolution was attributed to the oxidation of DNA, in which the guanine nucleobase plays a key role. The sensing behavior obtained from flexible biosensors on a polymeric substrate fabricated under the identical conditions was exactly analogous. These results compare favorably with the conventional field-effect transistor based DNA sensors by demonstrating remarkable sensitivity and feasibility of flexible devices that arose from a different sensing mechanism and a low-temperature process, respectively.

Low-cost label-free electrical detection of artificial DNA nanostructures using solution-processed oxide thin-film transistors.

A high-sensitivity, label-free method for detecting deoxyribonucleic acid (DNA) using solution-processed oxide thin-film transistors (TFTs) was developed. Double-crossover (DX) DNA nanostructures with different concentrations of divalent Cu ion (Cu(2+)) were immobilized on an In-Ga-Zn-O (IGZO) back-channel surface, which changed the electrical performance of the IGZO TFTs. The detection mechanism of the IGZO TFT-based DNA biosensor is attributed to electron trapping and electrostatic interactions caused by negatively charged phosphate groups on the DNA backbone. Furthermore, Cu(2+) in DX DNA nanostructures generates a current path when a gate bias is applied. The direct effect on the electrical response implies that solution-processed IGZO TFTs could be used to realize low-cost and high-sensitivity DNA biosensors.

Formation of silicon nanoparticles by a pressure induced nucleation mechanism.

Formation of silicon nanoparticles (SiNPs) was achieved using excimer laser crystallization of an amorphous Si (a-Si) thin film using a SiO2 capping layer (C/L) with improved thin-film transistor (TFT) performance due to the enlarged grain size of polycrystalline Si (poly-Si). After laser irradiation of an a-Si thin film covered with C/L, fluctuation in the surface morphology of the C/L was observed above the critical laser energy density (Ecr) with the formation of SiNPs. The grain size of the poly-Si layer after crystallization increased abruptly at the same time. A non-uniform pressure distribution beneath the SiO2 C/L was proposed for the initiation of nucleation, which is named pressure induced nucleation (PIN) mechanism. Following nucleation, the release of latent heat made it difficult for the remnant liquid Si to solidify and the volume increased due to the density difference between the liquid and solid Si. Consequently, the pressure on the liquid Si caused SiNPs to sprout through the SiO2 C/L as grains grew from the low temperature to high temperature point. This study offers not only a simple method to fabricate SiNPs with controllable size/density but also larger grain size with lower laser energy density, which leads to higher TFT performance.

Electrical responses of artificial DNA nanostructures on solution-processed In-Ga-Zn-O thin-film transistors with multistacked active layers.

We propose solution-processed In-Ga-Zn-O (IGZO) thin-film transistors (TFTs) with multistacked active layers for detecting artificial deoxyribonucleic acid (DNA). Enhanced sensing ability and stable electrical performance of TFTs were achieved through use of multistacked active layers. Our IGZO TFT had a turn-on voltage (V(on)) of -0.8 V and a subthreshold swing (SS) value of 0.48 V/decade. A dry-wet method was adopted to immobilize double-crossover DNA on the IGZO surface, after which an anomalous hump effect accompanying a significant decrease in V(on) (-13.6 V) and degradation of SS (1.29 V/decade) was observed. This sensing behavior was attributed to the middle interfaces of the multistacked active layers and the negatively charged phosphate groups on the DNA backbone, which generated a parasitic path in the TFT device. These results compared favorably with those reported for conventional field-effect transistor-based DNA sensors with remarkable sensitivity and stability.

Hole transport enhancing effects of polar solvents on poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) for organic solar cells.

This study analyzed the properties of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) thin-films prepared by spin-coating solutions made with the polar solvents methanol, acetone, or N,N-dimethylformamide (DMF). A characteristic analysis was carried out for poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C(61)-butyric acid methyl ester (PCBM)-based organic solar cells (OSCs) having these modified PEDOT:PSS thin-films as the hole transport layer. The resistivity of the PEDOT:PSS thin-film obtained from the DMF solution was 4.89 × 10(-3) Ω·cm with a roughness of 3.23 × 10° nm, compared to 3.51 × 10(-1) Ω·cm and 7.72 × 10(-1) nm for a pristine PEDOT:PSS thin-film. The dipole moment increase of the solvent led to the decreased resistivity and the increased roughness and transparency of PEDOT:PSS thin-films on the structural arrangement of the polymers. Highly efficient OSCs with a power conversion efficiency of 3.47% were obtained when DMF-treated PEDOT:PSS thin-film was used as the hole transport layer.