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.

Growth of GaN Thin Films Using Plasma Enhanced Atomic Layer Deposition: Effect of Ammonia-Containing Plasma Power on Residual Oxygen Capture.

In recent years, the application of (In, Al, Ga)N materials in photovoltaic devices has attracted much attention. Like InGaN, it is a direct band gap material with high absorption at the band edge, suitable for high efficiency photovoltaic devices. Nonetheless, it is important to deposit high-quality GaN material as a foundation. Plasma-enhanced atomic layer deposition (PEALD) combines the advantages of the ALD process with the use of plasma and is often used to deposit thin films with different needs. However, residual oxygen during growth has always been an unavoidable issue affecting the quality of the resulting film, especially in growing gallium nitride (GaN) films. In this study, the NH3-containing plasma was used to capture the oxygen absorbed on the growing surface to improve the quality of GaN films. By diagnosing the plasma, NH2, NH, and H radicals controlled by the plasma power has a strong influence not only on the oxygen content in growing GaN films but also on the growth rate, crystallinity, and surface roughness. The NH and NH2 radicals contribute to the growth of GaN films while the H radicals selectively dissociate Ga-OH bonds on the film surface and etch the grown films. At high plasma power, the GaN film with the lowest Ga-O bond ratio has a saturated growth rate, a better crystallinity, a rougher surface, and a lower bandgap. In addition, the deposition mechanism of GaN thin films prepared with a trimethylgallium metal source and NH3/Ar plasma PEALD involving oxygen participation or not is also discussed in the study.

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.

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.

Chemical Reaction and Ion Bombardment Effects of Plasma Radicals on Optoelectrical Properties of SnO2 Thin Films via Atomic Layer Deposition.

In this study, the effect of radical intensity on the deposition mechanism, optical, and electrical properties of tin oxide (SnO2) thin films is investigated. The SnO2 thin films are prepared by plasma-enhanced atomic layer deposition with different plasma power from 1000 to 3000 W. The experimental results show that plasma contains different amount of argon radicals (Ar*) and oxygen radicals (O*) with the increased power. The three deposition mechanisms are indicated by the variation of Ar* and O* intensities evidenced by optical emission spectroscopy. The adequate intensities of Ar* and O* are obtained by the power of 1500 W, inducing the highest oxygen vacancies (OV) ratio, the narrowest band gap, and the densest film structure. The refractive index and optical loss increase with the plasma power, possibly owing to the increased film density. According to the Hall effect measurement results, the improved plasma power from 1000 to 1500 W enhances the carrier concentration due to the enlargement of OV ratio, while the plasma powers higher than 1500 W further cause the removal of OV and the significant bombardment from Ar*, leading to the increase of resistivity.

Air Annealing Effect on Oxygen Vacancy Defects in Al-doped ZnO Films Grown by High-Speed Atmospheric Atomic Layer Deposition.

In this study, aluminum-doped zinc oxide (Al:ZnO) thin films were grown by high-speed atmospheric atomic layer deposition (AALD), and the effects of air annealing on film properties are investigated. The experimental results show that the thermal annealing can significantly reduce the amount of oxygen vacancies defects as evidenced by X-ray photoelectron spectroscopy spectra due to the in-diffusion of oxygen from air to the films. As shown by X-ray diffraction, the annealing repairs the crystalline structure and releases the stress. The absorption coefficient of the films increases with the annealing temperature due to the increased density. The annealing temperature reaching 600 °C leads to relatively significant changes in grain size and band gap. From the results of band gap and Hall-effect measurements, the annealing temperature lower than 600 °C reduces the oxygen vacancies defects acting as shallow donors, while it is suspected that the annealing temperature higher than 600 °C can further remove the oxygen defects introduced mid-gap states.

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.

Deposition of Silicon-Based Stacked Layers for Flexible Encapsulation of Organic Light Emitting Diodes.

In this study, inorganic silicon oxide (SiOx)/organic silicon (SiCxHy) stacked layers were deposited by a radio frequency inductively coupled plasma chemical vapor deposition system as a gas diffusion barrier for organic light-emitting diodes (OLEDs). The effects of thicknesses of SiOx and SiCxHy layers on the water vapor transmission rate (WVTR) and residual stress were investigated to evaluate the encapsulation capability. The experimental results showed that the lowest WVTR and residual stress were obtained when the thicknesses of SiOx and SiCxHy were 300 and 30 nm, respectively. Finally, different numbers of stacked pairs of SiOx/SiCxHy were applied to OLED encapsulation. The OLED encapsulated with the six-pair SiOx/SiCxHy exhibited a low turn-on voltage and low series resistance, and device lifetime increased from 7 h to more than 2000 h.

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.

Thin-Film Coated Plastic Wrap for Food Packaging.

In this study, the antimicrobial property and food package capability of polymethylpentene (PMP) substrate with silicon oxdie (SiOx) and organic silicon (SiCxHy) stacked layers deposited by an inductively coupled plasma chemical vapor deposition system were investigated. The experimental results show that the stacked pair number of SiOx/SiCxHy on PMP is limited to three pairs, beyond which the films will crack and cause package failure. The three-pair SiOx/SiCxHy on PMP shows a low water vapor transmission rate of 0.57 g/m²/day and a high water contact angle of 102°. Three-pair thin-film coated PMP demonstrates no microbe adhesion and exhibits antibacterial properties within 24 h. Food shelf life testing performed at 28 °C and 80% humidity reports that the three-pair thin-film coated PMP can enhance the food shelf-life to 120 h. The results indicate that the silicon-based thin film may be a promising material for antibacterial food packaging applications to extend the shelf-life of food products.

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.

Low Cost Local Contact Opening by Using Polystyrene Spheres Spin-Coating Method for PERC Solar Cells.

The passivated emitter and rear cell (PERC) concept is one of the most promising technologies for increasing crystalline silicon solar cell efficiency. Instead of using the traditional laser ablation process, this paper demonstrates spin-coated polystyrene spheres (PS) to create local openings on the rear side of PERCs. Effects of PS concentration and post-annealing temperature on PERC performance are investigated. The experimental results show that the PS are randomly distributed on wafers and no PS are joined together at a spin rate of 2000 rpm. The PS can be removed at a temperature of 350 °C, leaving holes on the passivation layers without damaging the wafer surfaces. As compared to the laser opening technique with the same contact fraction, the PS opening technique can yield a higher minority effective lifetime, a higher implied open-circuit voltage, and a slightly higher short-circuit current. Although the fill factor of the PS opening technique is lower owing to non-optimized distribution of the openings, the conversion efficiency of the devices is comparable to that of devices prepared via the laser opening process.