Synthesis of <Emphasis Type="Italic">c</Emphasis>-Axis Inclined AlN Films in an Off-Center System for Shear Wave Devices

AlN thin films are of continuing interest for excitation of acoustic waves in surface and bulk acoustic wave devices. We report herein on preparation and characterization of c-axis inclined AlN films by a new method of rotating the substrate holder plate to different angles in an off-center system. The microstructure of the c-axis inclined AlN films was investigated using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The analyses showed that polycrystalline AlN films with c-axis inclination of up to 12° could be obtained using the off-center system. Solidly mounted resonators based on the deposited c-axis inclined and vertical AlN films were successfully realized. The frequency responses showed dual-mode resonance characteristics located at 1.12 GHz and 1.87 GHz, corresponding to shear and longitudinal resonant modes, respectively.     

Preparation of Oriented Aluminum Nitride Thin Films on Polyimide Films and Piezoelectric Response with High Thermal Stability and Flexibility

c‐Axis oriented aluminum nitride (AlN) thin films are successfully prepared on amorphous polyimide films by radiofrequency magnetron reactive sputtering at room temperature. Structural analysis shows that the AlN films have a wurtzite structure and consist of c‐axis oriented columnar grains about 100 nm wide. The full width at half maximum of the X‐ray diffraction rocking curves and piezoelectric coefficient d₃₃ of the AlN films are 8.3° and 0.56 pC N^–1, respectively. The AlN films exhibit a piezoelectric response over a wide temperature range, from –196 to 300 °C, and can measure pressure within a wide range, from pulse waves of hundreds of pascals to 40 MPa. Moreover, the sensitivity of the AlN films increases with the number of times it was folded, suggesting that we can control the sensitivity of the AlN films by changing the geometric form. These results were achieved by a combination of preparing the oriented AlN thin films on polyimide films, and sandwiching the AlN and polymer films between top and bottom electrodes, such as Pt/AlN/polyimide/Pt. They are thin (less than 10 μm), self powered, adaptable to complex contours, and available in a variety of configurations. Although AlN is a piezoelectric ceramic, the AlN films are flexible and excellent in mechanical shock resistance.     

Direct Holographic Patterning of ZnO

Zinc oxide thin films are holographically patterned on submicronic scale by direct photodissolution method. The photodissolution process in solution is highly sensitive in the UV range (355 nm). 1D and 2D nanostructures are successfully obtained by this photoresist‐free process. The kinetic of the reaction is studied by recording the transmitted intensity through the evolution of the ZnO film thickness along the reaction time. Application of an electrical potential strongly increases the dissolution rate (1.5 μm min^?1) and decreases the pattern formation time. As a first demonstration of the potential of all‐in liquid direct ZnO heterostructuring, selective growth of ZnO nanorods is performed by chemical bath deposition using holographically patterned ZnO films as a substrate.     

A Patterned Graphene/ZnO UV Sensor Driven by Integrated Asymmetric Micro‐Supercapacitors on a Liquid Metal Patterned Foldable Paper

A foldable array of patterned graphene/ZnO nanoparticle UV sensor and asymmetric micro‐supercapacitors (AMSCs) integrated on a paper substrate with patterned liquid metal interconnections is reported. The resistor type UV sensor based on graphene/ZnO nanoparticles is patterned to be driven by the stored energy of the integrated AMSCs. The AMSC consists of MnO₂ nanoball deposited multiwalled carbon nanotubes (MWNTs) and V₂O₅ wrapped MWNTs as positive and negative electrodes, respectively. As an electrolyte, propylene carbonate‐poly(methyl methacrylate)‐LiClO₄, an organic solvent‐based gel, is used. The UV sensor and AMSCs can be easily integrated on a liquid metal, Galinstan, patterned, waterproof mineral paper and show a mechanically stable UV sensing, regardless of repetitive folding cycles. This work demonstrates a novel foldable nanomaterial based sensor system driven by integrated energy storage devices, applicable to future wearable and portable electronics.     

Enhancement of photo- and electro-luminescence of GaN-based LED structure grown on a nanometer-scaled patterned sapphire substrate

In this study, a 2 in. sized a highly periodic nanometer-scaled patterned sapphire substrate (NPSS) was fabricated using nanoimprint lithography (NIL) and inductively coupled plasma etching to improve the light-extraction efficiency of GaN-based light-emitting diodes (LEDs). A blue LED structure was grown on the nanometer-scale patterned sapphire substrates, and the photoluminescence (PL) and electroluminescence (EL) were measured to confirm the effectiveness of the nanometer-scaled patterns on sapphire. An improvement in luminescence efficiency was observed when NPSS was applied; 2 times stronger PL intensity and 2.8 times stronger EL intensity than the LED structure grown on the unpatterned sapphire wafers were measured. These results show highly periodic nanometer-scaled patterns create multi-photon scattering and effectively enhance the light-extraction efficiency of LEDs.     

Interfacial Strain‐Induced Oxygen Disorder as the Cause of Enhanced Critical Current Density in Superconducting Thin Films

To understand the origin of the increase in critical current density of rare earth barium cuprate superconductor thin films with decreasing thickness, a series of sub‐300‐nm EuBa₂Cu₃O_7?δ thin films deposited on SrTiO₃ substrates are studied by X‐ray diffraction and electrical transport measurements. The out‐of‐plane crystallographic mosaic tilt and the out‐of‐plane microstrain both increase with decreasing film thickness. The calculated density of c‐axis threading dislocations matches the extent of the observed low‐field enhancement in critical current density for fields applied parallel to c. The in‐plane mosaic twist and in‐plane microstrain are both around twice the magnitude of the out‐of‐plane values, and both increase with decreasing film thickness. The results are consistent with the observed stronger field enhancement in critical current density for fields applied parallel to ab. The lattice parameter variation with thickness is not as expected from consideration of the biaxial strain with the substrate, indicative of in‐plane microstrain accommodation by oxygen disorder. Collectively, the results point to an enhancement of critical current by interfacial strain induced oxygen disorder which is greatest closest to the film‐substrate interface. The findings of this study have important implications for other thin functional oxide perovskite films and nanostructures where surface and interfacial strains dominate the properties.     

溅射AlN技术对GaN基LED性能的影响

研究了在图形蓝宝石衬底(PSS)上利用磁控溅射制备AlN薄膜的相关技术,随后通过采用金属有机化学气相沉积(MOCVD)在相关AlN薄膜上生了长GaN基LED.通过一系列对比实验,分析了AlN薄膜的制备条件对GaN外延层晶体质量的影响,研究了AlN薄膜溅射前N2预处理功率和溅射后热处理温度对GaN基LED性能的作用机制.实验结果表明:AlN薄膜厚度的增加,导致GaN缓冲层成核密度逐渐升高和GaN外延膜螺位错密度降低刃位错密度升高;N2处理功率的提升会加剧衬底表面晶格损伤,在GaN外延膜引入更多的螺位错;AlN热处理温度的升高粗化了表面并提高了GaN成核密度,使得GaN外延膜螺位错密度降低刃位错密度升高;而这些GaN外延膜位错密度的变化又进一步影响到LED的光电特性.     

Strongly Anisotropic Thermal Conductivity of Free‐Standing Reduced Graphene Oxide Films Annealed at High Temperature

Thermal conductivity of free‐standing reduced graphene oxide films subjected to a high‐temperature treatment of up to 1000 °C is investigated. It is found that the high‐temperature annealing dramatically increases the in‐plane thermal conductivity, K, of the films from ≈3 to ≈61 W m^?1 K^?1 at room temperature. The cross‐plane thermal conductivity, K_⊥, reveals an interesting opposite trend of decreasing to a very small value of ≈0.09 W m^?1 K^?1 in the reduced graphene oxide films annealed at 1000 °C. The obtained films demonstrate an exceptionally strong anisotropy of the thermal conductivity, K/K_⊥ ≈ 675, which is substantially larger even than in the high‐quality graphite. The electrical resistivity of the annealed films reduces to 1–19 Ω □^?1. The observed modifications of the in‐plane and cross‐plane thermal conductivity components resulting in an unusual K/K_⊥ anisotropy are explained theoretically. The theoretical analysis suggests that K can reach as high as ≈500 W m^?1 K^?1 with the increase in the sp² domain size and further reduction of the oxygen content. The strongly anisotropic heat conduction properties of these films can be useful for applications in thermal management.     

Dual‐Tone Patterned Mesoporous Silicate Films Templated From Chemically Amplified Block Copolymers

Directly patterned mesoporous silicate films are prepared using positive‐ and negative‐tone strategies by performing phase selective silica condensation within lithographically exposed poly(styrene‐b‐tert‐butyl acrylate) (PS‐b‐PtbA) templates containing photoacid generators. The use of supercritical fluid as a process medium enables rapid diffusion of the silicate precursor within the prepatterned block copolymer template film without disrupting its morphology. Template exposure through the mask triggers area selective generation of acid, which in turn both deprotects the poly(tert‐butyl acrylate) block to yield a poly(acrylic acid) block and provides a catalyst for silica precursor condensation yielding pattern formation at the device level. Because the acid generated in the UV exposed field preferentially segregates into hydrophilic poly(acrylic acid) domains of the phase segregated, deprotected block copolymer, precursor condensation is simultaneously controlled at nanoscopic length scales via templating by the underlying block copolymer morphology. The ability of PS‐b‐PtbA to undergo chemical transformation in two stages, deprotection followed by crosslinking, enables precise replications of the photomask in positive and negative tones. Detemplating via calcination yields patterned mesoporous silicate films without etching. Template formulations are optimized using infrared spectroscopic studies and the silicate films are characterized using electron microscopy and scanning force microscopy.     

Deposition Characteristics of AlN Thin Film Prepared by the Dual Ion Beam Sputtering System

In this experiment, a radio frequency dual ion beam sputtering (DIBS) system was used to prepare aluminum nitride (AlN) films with a bottom Al electrode on a Si (100) substrate. After systematic testing of the processing variables, a high-quality film with preferred c-axis orientation was grown successfully on the Si (100) substrate with an Al target under 700 eV energy flux, N₂/(N₂ + Ar) ratio of 55%, and 4 × 10⁻⁴ torr in vacuum. The characteristics of the deposited AlN thin films were studied by x-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), secondary ion mass spectrometry (SIMS), and electronic spectroscopy for chemical analysis (ESCA). The surface roughness was also measured. It was found that AlN films prepared by DIBS at room temperature are better than those prepared at 300°C, and those prepared with an Al target are better than those prepared with an AlN target. The inferiority of AlN films prepared with AlN targets is due to the AlN bond being broken down by the ion beam source.     

A Universal Method of Producing Transparent Electrodes Using Wide‐Bandgap Materials

A UV light‐emitting diode (LED) is an eco‐friendly optical source with diverse applications. However, currently, the external quantum efficiency (EQE) of AlGaN‐based UV LEDs, particularly in the UV‐C band (<280 nm), is very low (<11%) mainly due to a large optical absorption via p‐GaN contact layers. A direct Ohmic contact to p‐AlGaN layers should be obtained using UV‐transparent conductive electrodes (TCEs) to solve this problem. A universal method is presented here to make such contact using electrical breakdown, with wide‐bandgap materials, to form conductive filaments (CFs), providing a current path between the TCEs and the p‐(Al)GaN layers. The contact resistance between the TCEs and the p‐GaN layers (or p‐AlGaN) is found to be on the order of 10^?5 Ω cm² (or 10^?3 Ω cm²), while optical transmittance is maintained up to 95% for AlN‐based TCEs at 250 nm. These findings could be a critical turning point delivering a breakthrough in UV LED technologies.     

Calcination‐ and Etching‐Free Photolithography of Inorganic Phosphor Films Consisting of Rare Earth Ion Doped Nanoparticles on Plastic Sheets

It is demonstrated that patterned inorganic phosphor films consisting of rare earth ion doped nanoparticles (RE‐NPs) can be fabricated on plastic sheets using calcination‐ and etching‐free photolithography. Green up‐conversion luminescence and near‐infrared (NIR) fluorescence appears from the RE‐NPs that are prepared from Y₂O₃ doped with 1 mol% Er³⁺ and 0.85 mol% Yb³⁺. The diameter of the RE‐NPs is estimated to be about 300 nm using dynamic light scattering. Visible transmittance of the RE‐NP film fabricated by dip‐coating is more than 90%. Patterned RE‐NP films are obtained by dip‐coating the RE‐NPs on patterned photoresist films fabricated by UV exposure through a photomask, followed by selective removal of the photoresist. Optical, fluorescence, scanning electron, atomic force, and Kelvin probe force microscopies are used for the characterization of the patterned RE‐NP films. The present methodology enables fabrication of patterned RE‐NP films, not only on inorganic substrates but also on plastic sheets, with low cost and material consumption.     

Pulsed laser deposition and processing of wide band gap semiconductors and related materials

The present work describes the novel, relatively simple, and efficient technique of pulsed laser deposition for rapid prototyping of thin films and multi-layer heterostructures of wide band gap semiconductors and related materials. In this method, a KrF pulsed excimer laser is used for ablation of polycrystalline, stoichiometric targets of wide band gap materials. Upon laser absorption by the target surface, a strong plasm a plume is produced which then condenses onto the substrate, kept at a suitable distance from the target surface. We have optimized the processing parameters such as laser fluence, substrate temperature, background gas pressure, target to substrate distance, and pulse repetition rate for the growth of high quality crstalline thin films and heterostructures. The films have been characterized by x-ray diffraction, Rutherford backscattering and ion channeling spectrometry, high resolution transmission electron microscopy, atomic force microscopy, ultraviolet (UV)-visible spectroscopy, cathodoluminescence, and electrical transport measurements. We show that high quality AlN and GaN thin films can be grown by pulsed laser deposition at relatively lower substrate temperatures (750–800°C) than those employed in metal organic chemical vapor deposition (MOCVD), (1000–1100°C), an alternative growth method. The pulsed laser deposited GaN films (∼0.5 μm thick), grown on AlN buffered sapphire (0001), shows an x-ray diffraction rocking curve full width at half maximum (FWHM) of 5–7 arc-min. The ion channeling minimum yield in the surface region for AlN and GaN is ∼3%, indicating a high degree of crystallinity. The optical band gap for AlN and GaN is found to be 6.2 and 3.4 eV, respectively. These epitaxial films are shiny, and the surface root mean square roughness is ∼5–15 nm. The electrical resistivity of the GaN films is in the range of 10⁻²–10² Θ-cm with a mobility in excess of 80 cm²V⁻¹s⁻¹ and a carrier concentration of 10¹⁷–10¹⁹ cm⁻³, depending upon the buffer layers and growth conditions. We have also demonstrated the application of the pulsed laser deposition technique for integration of technologically important materials with the III–V nitrides. The examples include pulsed laser deposition of ZnO/GaN heterostructures for UV-blue lasers and epitaxial growth of TiN on GaN and SiC for low resistance ohmic contact metallization. Employing the pulsed laser, we also demonstrate a dry etching process for GaN and AlN films.     

Effect of substrate biasing and temperature on AlN thin film deposited by cathodic arc ion

Aluminum nitride (AlN) films have been grown in pure N₂ plasma using cathodic arc ion deposition process. The films were prepared at different substrate bias voltages and temperatures. The aim was to investigate their influence on the Al macro-particles, structural and optical properties of deposited films. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Scanning electron microscope (SEM) and Rutherford backscattering spectrometry (RBS) were employed to characterize AlN thin films. XRD patterns indicated the formation of polycrystalline (hexagonal) films with preferential orientation of (002), which is suppressed at higher substrate bias voltage. FTIR and Raman spectroscopic analysis were used to assess the nature of chemical bonding and vibrational phonon modes of AlN thin films respectively. FTIR spectra depicted a dominant peak around 850 cm^?1 corresponding to the longitudinal optical (LO) mode of vibration. A shift in this LO mode peak towards higher wavenumbers was observed with the increase of substrate bias voltage and temperature, showing the upsurge of nitrogen concentration in the deposited film. Raman spectra illustrated a peak at 650 cm^?1 corresponding to E₂ (high) phonon mode depicting the c-axis oriented (perpendicular to substrate) AlN film. SEM analysis showed the AlN film deposited at higher substrate bias voltage contains fewer amounts of Al macro-particles.     

Surface‐Directed Phase Separation of Conjugated Polymer Blends for Efficient Light‐Emitting Diodes

The ability to control organic‐organic interfaces in conjugated polymer blends is critical for further device improvement. Here, we control the phase separation in blends of poly(9,9‐di‐n‐octylfluorene‐alt‐benzothiadiazole) (F8BT) and poly(9,9‐di‐n‐octylfluorene‐alt‐(1,4‐phenylene‐((4‐sec‐butylphenyl)imino)‐1,4‐phenylene) (TFB) via chemical modification of the substrate by microcontact printing of octenyltrichlorosilane molecules. The lateral phase‐separated structures in the blend film closely replicate the underlying micrometer‐scale chemical pattern. We found nanometer‐scale vertical segregation of the polymers within both lateral domains, with regions closer to the substrate being substantially pure phases of either polymer. Such phase separation has important implications for the performance of light‐emitting diodes fabricated using these patterned blend films. In the absence of a continuous TFB wetting layer at the substrate interface, as typically formed in spin‐coated blend films, charge carrier injection is confined in the well‐defined TFB‐rich domains. This confinement leads to high electroluminescence efficiency, whereas the overall reduction in the roughness of the patterned blend film results in slower decay of device efficiency at high voltages. In addition, the amount of surface out‐coupling of light in the forward direction observed in these blend devices is found to be strongly correlated to the distribution of periodicity of the phase‐separated structures in the active layer.     

Direct Threat of a UV‐Ozone Treated Indium‐Tin‐Oxide Substrate to the Stabilities of Common Organic Semiconductors

Ultraviolet‐ozone treated indium‐tin‐oxide (UV‐ITO) glass substrates have been widely and unquestioningly used in the field of organic electronics to improve both device performance and stability. Evidence is presented here for rapid decay of common organic films such as N,N′‐bis(naphthalen‐1‐ yl)‐N,N′‐bis(phenyl)‐benzidine (NPB), tris(8‐hydroxy‐quinolinato)aluminum (Alq₃), and rubrene when they are in contact with an UV‐ITO substrate. While the photoluminescence (PL) of these organic films deposited on an UV‐ITO substrate decay rapidly under illumination; those on quartz substrates are comparatively much more stable. Results from X‐ray and UV photoemission spectroscopies (XPS and UPS) further suggest that degradations of the rubrene films on UV‐ITO substrate are mainly attributed to active oxygen species generated upon UV‐ozone treatment. These reactive oxygen species on the UV‐ITO surface behave as a reservoir of oxygen that interacts with rubrene and shifts its highest occupied molecular orbital (HOMO) level away from the Fermi level. This interaction induces a gap‐state in the energy gap of rubrene, which acts as a charge recombination center. More importantly, enhanced stabilities of rubrene‐based organic photovoltaic (OPV) devices are demonstrated when they are fabricated on gold‐coated or trifluoromethane (CHF₃) plasma‐treated ITO. The presented works shows that the commonly used UV‐ITO substrate is a threat to the stability of addlayer organic semiconducting films.     

Influence of Substrate Temperature on Structural Properties and Deposition Rate of AlN Thin Film Deposited by Reactive Magnetron Sputtering

Aluminum nitride (AlN) thin films with c-axis preferred orientation have been prepared by reactive direct-current (DC) magnetron sputtering. The degree of preferred crystal orientation, the cross-sectional structure, and the surface morphology of AlN thin films grown on Si (100) substrates at various substrate temperatures from 60°C to 520°C have been investigated by x-ray diffraction, scanning electron microscopy, and atomic force microscopy. Results show that the substrate temperature has a significant effect on the structural properties, such as the degree of c-axis preferred orientation, the full-width at half-maximum (FWHM) of the rocking curve, the surface morphology, and the cross-sectional structure as well as the deposition rate of the AlN thin films. The optimal substrate temperature is 430°C, with corresponding root-mean-square surface roughness (R _rms) of 1.97?nm, FWHM of AlN (002) diffraction of 2.259°, and deposition rate of 20.86?nm/min. The mechanisms behind these phenomena are discussed. Finally, film bulk acoustic resonators based on AlN films were fabricated; the corresponding typical electromechanical coupling coefficient (k _t ² ) is 5.1% with series and parallel frequencies of 2.37?GHz and 2.42?GHz, respectively.     

Autonomously Controlled Homogenous Growth of Wafer‐Sized High‐Quality Graphene via a Smart Janus Substrate

The work reports a new method for large‐area growth of graphene films, which have been predicted to have novel and broad applications in the future. While chemical vapor deposition (CVD) is currently the preferred method, it suffers from a rather narrow processing window, and there is also much to be desired in the electrical properties of the CVD films. A new method for large‐area growth of graphene films is reported to overcome the narrow processing window of the CVD method. A composite substrate made of a C‐dissolving top (Ni) layer and a C‐rejecting bottom (Cu) layer is designed, which evolves into a C‐rejecting mixture, to autonomously regulate the C content at an elevated yet stable level at and near the surface over an extended duration. This “smart” substrate promotes graphene formation over a wide temperature‐gas composition window, leading to reliable growth of wafer‐sized graphene films of defined layer‐thickness and superior electrical–optical properties. This “smart”‐substrate strategy can also be implemented on Si and SiO₂ supports, paving the way toward the direct fabrication of large area, graphene‐enabled electronic and photonic devices.     

Improved Heat Spreading Performance of Functionalized Graphene in Microelectronic Device Application

It is demonstrated that a graphene‐based film (GBF) functionalized with silane molecules strongly enhances thermal performance. The resistance temperature detector results show that the inclusion of silane molecules doubles the heat spreading ability. Furthermore, molecular dynamics simulations show that the thermal conductivity (κ) of the GBF increased by 15%–56% with respect to the number density of molecules compared to that with the nonfunctionalized graphene substrate. This increase in κ is attributed to the enhanced in‐plane heat conduction of the GBF, resulting from the simultaneous increase of the thermal resistance between the GBF and the functionalized substrate limiting cross‐plane phonon scattering. Enhancement of the thermal performance by inserting silane‐functionalized molecules is important for the development of next‐generation electronic devices and proposed application of GBFs for thermal management.     

Single‐Crystal Hybrid Perovskite Platelets on Graphene: A Mixed‐Dimensional Van Der Waals Heterostructure with Strong Interface Coupling

Van der Waals (vdW) heterostructures open up excellent prospects in electronic and optoelectronic applications. In this work, mixed‐dimensional metal‐halide perovskite/graphene heterostructures are prepared through selective growth of CH₃NH₃PbBr₃ platelets on patterned single‐layer graphene using chemical vapor deposition. Preferred growth of single‐crystal CH₃NH₃PbBr₃ platelets on graphene surfaces is achieved, which is accompanied by significant photoluminescence quenching. Raman spectra reveal that perovskite platelets cause p‐type doping in the graphene layer. A significant Fermi level decrease of 272 meV in graphene is estimated, which corresponds to a high doping density of 7.5 × 10¹² cm^?2. Surface potentials measured by Kelvin probe force microscopy indicate a negatively charged perovskite surface under illumination, which is consistent with the upward band bending deduced from conducting atomic force microscopy measurements. Moreover, a field‐effect phototransistor is fabricated using the perovskite/graphene heterostructure channel, and the increased Dirac voltage under illumination confirms an enhanced p‐type character in graphene. These findings enrich the understanding of strong interface coupling in such mixed‐dimensional vdW heterostructures and pave the way toward novel perovskite‐based optoelectronic devices.