Internal moisture barrier layer for improving high-humidity reliability of miniature light emitting diode die without encapsulation.

Atomic layer deposited Al2O3 films are incorporated into miniature light emitting diodes (mini-LEDs) as an internal moisture barrier layer. The experimental results show that the water vapor transmission rate reaches ≤10-4 g/m2/day when the Al2O3 thickness is ≥40 nm. The mini-LED with a 40 nm-thick Al2O3 layer shows negligible degradation after 1000 h of 85°C/85% relative humidity testing, whereas the device without an Al2O3 layer fails after only 500 h due to delamination occurring at the GaN surface. Current-voltage characteristics of the device without an Al2O3 moisture barrier layer indicate an increase in series resistance and ideality factor. This study provides a simple, light-weighting method to have a satisfactory encapsulation function for miniature LEDs.

Deposition Mechanism and Properties of Plasma-Enhanced Atomic Layer Deposited Gallium Nitride Films with Different Substrate Temperatures.

Gallium nitride (GaN) is a wide bandgap semiconductor with remarkable chemical and thermal stability, making it a competitive candidate for a variety of optoelectronic applications. In this study, GaN films are grown using a plasma-enhanced atomic layer deposition (PEALD) with trimethylgallium (TMG) and NH3 plasma. The effect of substrate temperature on growth mechanism and properties of the PEALD GaN films is systematically studied. The experimental results show that the self-limiting surface chemical reactions occur in the substrate temperature range of 250-350 °C. The substrate temperature strongly affects the crystalline structure, which is nearly amorphous at below 250 °C, with (100) as the major phase at below 400 °C, and (002) dominated at higher temperatures. The X-ray photoelectron spectroscopy spectra reveals the unintentional oxygen incorporation into the films in the forms of Ga2O3 and Ga-OH. The amount of Ga-O component decreases, whereas the Ga-Ga component rapidly increases at 400 and 450 °C, due to the decomposition of TMG. The substrate temperature of 350 °C with the highest amount of Ga-N bonds is, therefore, considered the optimum substrate temperature. This study is helpful for improving the quality of PEALD GaN films.

Crystallinity Effect on Electrical Properties of PEALD-HfO2 Thin Films Prepared by Different Substrate Temperatures.

Hafnium oxide (HfO2) thin film has remarkable physical and chemical properties, which makes it useful for a variety of applications. In this work, HfO2 films were prepared on silicon through plasma enhanced atomic layer deposition (PEALD) at various substrate temperatures. The growth per cycle, structural, morphology and crystalline properties of HfO2 films were measured by spectroscopic ellipsometer, grazing-incidence X-ray diffraction (GIXRD), X-ray reflectivity (XRR), field-emission scanning electron microscopy, atomic force microscopy and x-ray photoelectron spectroscopy. The substrate temperature dependent electrical properties of PEALD-HfO2 films were obtained by capacitance-voltage and current-voltage measurements. GIXRD patterns and XRR investigations show that increasing the substrate temperature improved the crystallinity and density of HfO2 films. The crystallinity of HfO2 films has a major effect on electrical properties of the films. HfO2 thin film deposited at 300 °C possesses the highest dielectric constant and breakdown electric field.

Deposition Mechanism and Characterization of Plasma-Enhanced Atomic Layer-Deposited SnOx Films at Different Substrate Temperatures.

The promising functional tin oxide (SnOx) has attracted tremendous attention due to its transparent and conductive properties. The stoichiometric composition of SnOx can be described as common n-type SnO2 and p-type Sn3O4. In this study, the functional SnOx films were prepared successfully by plasma-enhanced atomic layer deposition (PEALD) at different substrate temperatures from 100 to 400 °C. The experimental results involving optical, structural, chemical, and electrical properties and morphologies are discussed. The SnO2 and oxygen-deficient Sn3O4 phases coexisting in PEALD SnOx films were found. The PEALD SnOx films are composed of intrinsic oxygen vacancies with O-Sn4+ bonds and then transformed into a crystalline SnO2 phase with increased substrate temperature, revealing a direct 3.5−4.0 eV band gap and 1.9−2.1 refractive index. Lower (<150 °C) and higher (>300 °C) substrate temperatures can cause precursor condensation and desorption, respectively, resulting in reduced film qualities. The proper composition ratio of O to Sn in PEALD SnOx films near an estimated 1.74 suggests the highest mobility of 12.89 cm2 V−1 s−1 at 300 °C.

Role of Ambient Hydrogen in HiPIMS-ITO Film during Annealing Process in a Large Temperature Range.

Indium tin oxide (ITO) thin films were prepared by high power impulse magnetron sputtering (HiPIMS) and annealed in hydrogen-containing forming gas to reduce the film resistivity. The film resistivity reduces by nearly an order of magnitude from 5.6 × 10-3 Ω·cm for the as-deposited film to the lowest value of 6.7 × 10-4 Ω·cm after annealed at 700 °C for 40 min. The role of hydrogen (H) in changing the film properties was explored and discussed in a large temperature range (300-800 °C). When annealed at a low temperature of 300-500 °C, the incorporated H atoms occupied the oxygen sites (Ho), acting as shallow donors that contribute to the increase of carrier concentration, leading to the decrease of film resistivity. When annealed at an intermediate temperature of 500-700 °C, the Ho defects are thermally unstable and decay upon annealing, leading to the reduction of carrier concentration. However, the film resistivity keeps decreasing due to the increase in carrier mobility. Meanwhile, some locally distributed metallic clusters formed due to the reduction effect of H2. When annealed at a high temperature of 700-800 °C, the metal oxide film is severely reduced and transforms to gaseous metal hydride, leading to the dramatic reduction of film thickness and carrier mobility at 750 °C and vanish of the film at 800 °C.

Compact Ga2O3 Thin Films Deposited by Plasma Enhanced Atomic Layer Deposition at Low Temperature.

Amorphous Gallium oxide (Ga2O3) thin films were grown by plasma-enhanced atomic layer deposition using O2 plasma as reactant and trimethylgallium as a gallium source. The growth rate of the Ga2O3 films was about 0.6 Å/cycle and was acquired at a temperature ranging from 80 to 250 °C. The investigation of transmittance and the adsorption edge of Ga2O3 films prepared on sapphire substrates showed that the band gap energy gradually decreases from 5.04 to 4.76 eV with the increasing temperature. X-ray photoelectron spectroscopy (XPS) analysis indicated that all the Ga2O3 thin films showed a good stoichiometric ratio, and the atomic ratio of Ga/O was close to 0.7. According to XPS analysis, the proportion of Ga3+ and lattice oxygen increases with the increase in temperature resulting in denser films. By analyzing the film density from X-ray reflectivity and by a refractive index curve, it was found that the higher temperature, the denser the film. Atomic force microscopic analysis showed that the surface roughness values increased from 0.091 to 0.187 nm with the increasing substrate temperature. X-ray diffraction and transmission electron microscopy investigation showed that Ga2O3 films grown at temperatures from 80 to 200 °C were amorphous, and the Ga2O3 film grown at 250 °C was slightly crystalline with some nanocrystalline structures.

Tantalum-Doped TiO2 Prepared by Atomic Layer Deposition and Its Application in Perovskite Solar Cells.

Tantalum (Ta)-doped titanium oxide (TiO2) thin films are grown by plasma enhanced atomic layer deposition (PEALD), and used as both an electron transport layer and hole blocking compact layer of perovskite solar cells. The metal precursors of tantalum ethoxide and titanium isopropoxide are simultaneously injected into the deposition chamber. The Ta content is controlled by the temperature of the metal precursors. The experimental results show that the Ta incorporation introduces oxygen vacancies defects, accompanied by the reduced crystallinity and optical band gap. The PEALD Ta-doped films show a resistivity three orders of magnitude lower than undoped TiO2, even at a low Ta content (0.8-0.95 at.%). The ultraviolet photoelectron spectroscopy spectra reveal that Ta incorporation leads to a down shift of valance band and conduction positions, and this is helpful for the applications involving band alignment engineering. Finally, the perovskite solar cell with Ta-doped TiO2 electron transport layer demonstrates significantly improved fill factor and conversion efficiency as compared to that with the undoped TiO2 layer.

Deposition and Characterization of RP-ALD SiO2 Thin Films with Different Oxygen Plasma Powers.

In this study, silicon oxide (SiO2) films were deposited by remote plasma atomic layer deposition with Bis(diethylamino)silane (BDEAS) and an oxygen/argon mixture as the precursors. Oxygen plasma powers play a key role in the quality of SiO2 films. Post-annealing was performed in the air at different temperatures for 1 h. The effects of oxygen plasma powers from 1000 W to 3000 W on the properties of the SiO2 thin films were investigated. The experimental results demonstrated that the SiO2 thin film growth per cycle was greatly affected by the O2 plasma power. Atomic force microscope (AFM) and conductive AFM tests show that the surface of the SiO2 thin films, with different O2 plasma powers, is relatively smooth and the films all present favorable insulation properties. The water contact angle (WCA) of the SiO2 thin film deposited at the power of 1500 W is higher than that of other WCAs of SiO2 films deposited at other plasma powers, indicating that it is less hydrophilic. This phenomenon is more likely to be associated with a smaller bonding energy, which is consistent with the result obtained by Fourier transformation infrared spectroscopy. In addition, the influence of post-annealing temperature on the quality of the SiO2 thin films was also investigated. As the annealing temperature increases, the SiO2 thin film becomes denser, leading to a higher refractive index and a lower etch rate.

Properties and Mechanism of PEALD-In2O3 Thin Films Prepared by Different Precursor Reaction Energy.

Indium oxide (In2O3) film has excellent optical and electrical properties, which makes it useful for a multitude of applications. The preparation of In2O3 film via atomic layer deposition (ALD) method remains an issue as most of the available In-precursors are inactive and thermally unstable. In this work, In2O3 film was prepared by ALD using a remote O2 plasma as oxidant, which provides highly reactive oxygen radicals, and hence significantly enhancing the film growth. The substrate temperature that determines the adsorption state on the substrate and reaction energy of the precursor was investigated. At low substrate temperature (100-150 °C), the ratio of chemically adsorbed precursors is low, leading to a low growth rate and amorphous structure of the films. An amorphous-to-crystalline transition was observed at 150-200 °C. An ALD window with self-limiting reaction and a reasonable film growth rate was observed in the intermediate temperature range of 225-275 °C. At high substrate temperature (300-350 °C), the film growth rate further increases due to the decomposition of the precursors. The resulting film exhibits a rough surface which consists of coarse grains and obvious grain boundaries. The growth mode and properties of the In2O3 films prepared by plasma-enhanced ALD can be efficiently tuned by varying the substrate temperature.

Suppression of Oxygen Vacancy Defects in sALD-ZnO Films Annealed in Different Conditions.

Zinc oxide (ZnO) has drawn much attention due to its excellent optical and electrical properties. In this study, ZnO film was prepared by a high-deposition-rate spatial atomic layer deposition (ALD) and subjected to a post-annealing process to suppress the intrinsic defects and improve the crystallinity and film properties. The results show that the film thickness increases with annealing temperature owing to the increment of oxide layer caused by the suppression of oxygen vacancy defects as indicated by the X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) spectra. The film transmittance is seldom influenced by annealing. The refractive index increases with annealing temperature at 300-700 °C, possibly due to higher density and crystallinity of the film. The band gap decreases after annealing, which should be ascribed to the decrease in carrier concentration according to Burstein-Moss model. The carrier concentration decreases with increasing annealing temperature at 300-700 °C since the oxygen vacancy defects are suppressed, then it increases at 800 °C possibly due to the out-diffusion of oxygen atoms from the film. Meanwhile, the carrier mobility increases with temperature due to higher crystallinity and larger crystallite size. The film resistivity increases at 300-700 °C then decreases at 800 °C, which should be ascribed primarily to the variation of carrier concentration.

Effect of Annealing Temperature on Spatial Atomic Layer Deposited Titanium Oxide and Its Application in Perovskite Solar Cells.

In this study, spatial atomic layer deposition (sALD) is employed to prepare titanium dioxide (TiO2) thin films by using titanium tetraisopropoxide and water as metal and water precursors, respectively. The post-annealing temperature is varied to investigate its effect on the properties of the TiO2 films. The experimental results show that the sALD TiO2 has a similar deposition rate per cycle to other ALD processes using oxygen plasma or ozone oxidant, implying that the growth is limited by titanium tetraisopropoxide steric hindrance. The structure of the as-deposited sALD TiO2 films is amorphous and changes to polycrystalline anatase at the annealing temperature of 450 °C. All the sALD TiO2 films have a low absorption coefficient at the level of 10-3 cm-1 at wavelengths greater than 500 nm. The annealing temperatures of 550 °C are expected to have a high compactness, evaluated by the refractive index and x-ray photoelectron spectrometer measurements. Finally, the 550 °C-annealed sALD TiO2 film with a thickness of ~8 nm is applied to perovskite solar cells as a compact electron transport layer. The significantly enhanced open-circuit voltage and conversion efficiency demonstrate the great potential of the sALD TiO2 compact layer in perovskite solar cell applications.

Zinc Oxide Films with High Transparency and Crystallinity Prepared by a Low Temperature Spatial Atomic Layer Deposition Process.

Zinc oxide (ZnO) attracts much attention owing to its remarkable electrical and optical properties for applications in optoelectronics. In this study, ZnO thin films were prepared by spatial atomic layer deposition with diethylzinc and water as precursors. The substrate temperature was varied from 55 to 135 °C to investigate the effects on the optical, electrical, and structural properties of the films. All ZnO samples exhibit an average transmittance in visible and near-infrared light range exceeding 80% and a resistivity in the range of (3.2-9.0) × 10-3 Ω·cm when deposited on a borosilicate glass with a refractive index of ≈1.52. The transmittance, band gap, refractive index, and extinction coefficient are rarely affected, while the resistivity only slightly decreases with increasing temperature. This technique provides a wide process window for depositing ZnO thin films. The results revealed that the films deposited at a substrate of 55 °C were highly crystalline with a preferential (1 0 0) orientation. In addition, the grains grow larger as the substrate temperature increases. The electrical properties and reliability of ZnO/PET samples are also studied in this paper.

Low Reflection and Low Surface Recombination Rate Nano-Needle Texture Formed by Two-Step Etching for Solar Cells.

In this study, needle-like and pyramidal hybrid black silicon structures were prepared by performing metal-assisted chemical etching (MACE) on alkaline-etched silicon wafers. Effects of the MACE time on properties of the black silicon wafers were investigated. The experimental results showed that a minimal reflectance of 4.6% can be achieved at the MACE time of 9 min. The height of the nanostructures is below 500 nm, unlike the height of micrometers needed to reach the same level of reflectance for the black silicon on planar wafers. A stacked layer of silicon nitride (SiNx) grown by inductively-coupled plasma chemical vapor deposition (ICPCVD) and aluminum oxide (Al2O3) by spatial atomic layer deposition was deposited on the black silicon wafers for passivation and antireflection. The 3 min MACE etched black silicon wafer with a nanostructure height of less than 300 nm passivated by the SiNx/Al2O3 layer showed a low surface recombination rate of 43.6 cm/s. Further optimizing the thickness of ICPCVD-SiNx layer led to a reflectance of 1.4%. The hybrid black silicon with a small nanostructure size, low reflectance, and low surface recombination rate demonstrates great potential for applications in optoelectronic devices.

Enhanced Si Passivation and PERC Solar Cell Efficiency by Atomic Layer Deposited Aluminum Oxide with Two-step Post Annealing.

In this study, aluminum oxide (Al2O3) films were prepared by a spatial atomic layer deposition using deionized water and trimethylaluminum, followed by oxygen (O2), forming gas (FG), or two-step annealing. Minority carrier lifetime of the samples was measured by Sinton WCT-120. Field-effect passivation and chemical passivation were evaluated by fixed oxide charge (Qf) and interface defect density (Dit), respectively, using capacitance-voltage measurement. The results show that O2 annealing gives a high Qf of - 3.9 × 1012 cm-2, whereas FG annealing leads to excellent Si interface hydrogenation with a low Dit of 3.7 × 1011 eV-1 cm-2. Based on the consideration of the best field-effect passivation brought by oxygen annealing and the best chemical passivation brought by forming gas, the two-step annealing process was optimized. It is verified that the Al2O3 film annealed sequentially in oxygen and then in forming gas exhibits a high Qf (2.4 × 1012 cm-2) and a low Dit (3.1 × 1011 eV-1 cm-2), yielding the best minority carrier lifetime of 1097 µs. The SiNx/Al2O3 passivation stack with two-step annealing has a lifetime of 2072 µs, close to the intrinsic lifetime limit. Finally, the passivated emitter and rear cell conversion efficiency was improved from 21.61% by using an industry annealing process to 21.97% by using the two-step annealing process.

Temperature-Dependent HfO2/Si Interface Structural Evolution and its Mechanism.

In this work, hafnium oxide (HfO2) thin films are deposited on p-type Si substrates by remote plasma atomic layer deposition on p-type Si at 250 °C, followed by a rapid thermal annealing in nitrogen. Effect of post-annealing temperature on the crystallization of HfO2 films and HfO2/Si interfaces is investigated. The crystallization of the HfO2 films and HfO2/Si interface is studied by field emission transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and atomic force microscopy. The experimental results show that during annealing, the oxygen diffuse from HfO2 to Si interface. For annealing temperature below 400 °C, the HfO2 film and interfacial layer are amorphous, and the latter consists of HfO2 and silicon dioxide (SiO2). At annealing temperature of 450-550 °C, the HfO2 film become multiphase polycrystalline, and a crystalline SiO2 is found at the interface. Finally, at annealing temperature beyond 550 °C, the HfO2 film is dominated by single-phase polycrystalline, and the interfacial layer is completely transformed to crystalline SiO2.

Surface Passivation of Silicon Using HfO2 Thin Films Deposited by Remote Plasma Atomic Layer Deposition System.

Hafnium oxide (HfO2) thin films have attracted much attention owing to their usefulness in equivalent oxide thickness scaling in microelectronics, which arises from their high dielectric constant and thermodynamic stability with silicon. However, the surface passivation properties of such films, particularly on crystalline silicon (c-Si), have rarely been reported upon. In this study, the HfO2 thin films were deposited on c-Si substrates with and without oxygen plasma pretreatments, using a remote plasma atomic layer deposition system. Post-annealing was performed using a rapid thermal processing system at different temperatures in N2 ambient for 10 min. The effects of oxygen plasma pretreatment and post-annealing on the properties of the HfO2 thin films were investigated. They indicate that the in situ remote plasma pretreatment of Si substrate can result in the formation of better SiO2, resulting in a better chemical passivation. The deposited HfO2 thin films with oxygen plasma pretreatment and post-annealing at 500 °C for 10 min were effective in improving the lifetime of c-Si (original lifetime of 1 µs) to up to 67 µs.