Inorganic Thin Films Research Articles

Photothermal Infrared Radiometry and Thermoreflectance—Unique Strategy for Thermal Transport Characterization of Nanolayers

Thermal transport properties for the isotropic and anisotropic characterization of nanolayers have been a significant gap in the research over the last decade. Multiple studies have been close to determining the thermal conductivity, diffusivity, and boundary resistance between the layers. The methods detailed in this work involve non-contact frequency domain pump-probe thermoreflectance (FDTR) and photothermal radiometry (PTR) methods for the ultraprecise determination of in-plane and cross-plane thermal transport properties. The motivation of one of the works is the advantage of the use of amplitude (TR signal) as one of the input parameters along with the phase for the determination of thermal parameters. In this article, we present a unique strategy for measuring the thermal transport parameters of thin films, including cross-plane thermal diffusivity, in-plane thermal conductivity, and thermal boundary resistance as a comprehensively reviewed article. The results obtained for organic and inorganic thin films are presented. Precise ranges for the thermal conductivity can be across confidence intervals for material measurements between 0.5 and 60 W/m-K for multiple nanolayers. The presented strategy is based on frequency-resolved methods, which, in contrast to time-resolved methods, make it possible to measure volumetric-specific heat. It is worth adding that the presented strategy allows for accurate (the signal in both methods depends on cross-plane thermal conductivity and thermal boundary resistance) and precise measurement.

Flame-Resistant Inorganic Films by Self-Assembly of Clay Nanotubes and their Conversion to Geopolymer for CO2 Capture.

Self-assembling of very long natural clay nanotubes represents a powerful strategy to fabricate thermo-stable inorganic thin films suitable for environmental applications. In this work, self-standing films with variable thicknesses (from 60 to 300µm) are prepared by the entanglement of 20-30µm length Patch halloysite clay nanotubes (PT_Hal), which interconnect into fibrosus structures. The thickness of the films is crucial to confer specific properties like transparency, mechanical resistance, and water uptake. Despite its completely inorganic composition, the thickest nanoclay film possesses elasticity comparable with polymeric materials as evidenced by its Young's modulus (ca. 1710MPa). All PT_Hal-based films are fire resistant and stable under high temperature conditions preventing flame propagation. After their direct flame exposure, produced films do not show neither deterioration effects nor macroscopic alterations. PT_Hal films are employed as precursors for the development of functional materials by alkaline activation and thermal treatment, which generate highly porous geopolymers or ceramics with a compact morphology. Due to its high porosity, geopolymer can be promising for CO2 capture. As compared to the corresponding inorganic film, the CO2 adsorption efficiency is doubled for the halloysite geopolymeric materials highlighting their potential use as a sorbent.

Effect of organic spacer cations on the stability of organic–inorganic hybrid perovskite thin film transistors

Effect of organic spacer cations on the stability of organic–inorganic hybrid perovskite thin film transistors

From molecules to materials: SHG-CD microscopy of structured chiral films

The interplay between molecular and structural chirality as a function of local sample morphology determines the nonlinear optical properties of many organic and hybrid organic–inorganic thin films. Here, we used second harmonic generation circular dichroism (SHG-CD) microscopy of thin molecular films of 1,1′-bi-2-naphthol (R-BINOL) as a research model. Our results show that the SHG signal measured at frequencies close to the electronic transition of BINOL molecules is resonantly enhanced by more than an order of magnitude compared to the non-resonant case. The extracted resonant SHG-CD signal is dominated by the chiral response of the molecule. In contrast, structural chirality determines the non-resonant SHG-CD images. We see clear evidence that the interference of the SHG signals caused by the molecular and structural chirality can lead to a decrease in the overall SHG intensity when both SHG signals are out of phase. These findings highlight the intricate relationship between molecular and structural chirality on the one hand and structural morphology on the other hand and pave the way for novel applications by exploiting the chiroptic properties of thin films.

Through thickness anisotropy in all inorganic perovskite thin films via two-step synthesis: implications for voltaic devices.

Cesium-lead-bromide (CsPbBr3) has shown promise in thin film photovoltaics due to its desirable energy band gap, charge mobility and chemical and thermal stability. The low solubility of its single crystal in organic solvents has driven development of the two-step spin-coating technique. In this work, precursor solutions of different PbBr2 and CsBr concentrations were spin-coated and investigated via Photoelectron Spectroscopy. The properties of the CsxPbyBrz film in cross-section demonstrate this method leads to varying stoichiometries, work functions and band gaps through the thickness. This anisotropy of the perovskite thickness has ramifications for design of photovoltaic devices.

Five Volts Lithium Batteries with Advanced Carbonate-Based Electrolytes: A Rational Design via a Trio-Functional Addon Materials.

Lithium metal batteries paired with high-voltage LiNi0.5Mn1.5O4 (LNMO) cathodes are a promising energy storage source for achieving enhanced high energy density. Forming durable and robust solid-electrolyte interphase (SEI) and cathode-electrolyte interface (CEI) and the ability to withstand oxidation at high potentials are essential for long-lasting performance. Herein, advanced electrolytes are designed via trio-functional additives to carbonate-based electrolytes for 5V Li||LNMO and graphite||LNMO cells achieving 88.3% capacity retention after 500 charge-discharge cycles. Theoretical calculations reveal that adding adiponitrile facilitates the presence of more hierarchical DFOB- and PF6 - dual anion structure in the solvation sheath, leading to a faster de-solvation of the Li cation. By combining both fluorine and nitrile additives, an efficient synergistic effect is obtained, generating robust thin inorganic SEI and CEI films, respectively. These films enhance microstructural stability; Li dendrite growth on the Li electrode is being suppressed at the anode side and transition-metals dissolution from the cathode is being mitigated, as evidenced by cryo-transmission electron microscopy and synchrotron studies.

Layer‐Engineered Functional Multilayer Thin‐Film Structures and Interfaces through Atomic and Molecular Layer Deposition

AbstractAtomic layer deposition (ALD) technology is one of the cornerstones of the modern microelectronics industry, where it is exploited in the fabrication of high‐quality inorganic thin films with excellent precision for film thickness and conformality. Molecular layer deposition (MLD) is a counterpart of ALD for purely organic thin films. Both ALD and MLD rely on self‐limiting gas‐surface reactions of vaporized and sequentially pulsed precursors and are thus modular, meaning that different precursor pulsing cycles can be combined in an arbitrary manner for the growth of elaborated superstructures. This allows the fusion of different building blocks — either inorganic or organic — even with contradicting properties into a single thin‐film material, to realize unforeseen material functions which can ultimately lead to novel application areas. Most importantly, many of these precisely layer‐engineered materials with attractive interfacial properties are inaccessible to other synthesis/fabrication routes. In this review, the intention is to present the current state of research in the field by i) summarizing the ALD and MLD processes so far developed for the multilayer thin films, ii) highlighting the most intriguing material properties and potential application areas of these unique layer‐engineered materials, and iii) outlining the future perspectives for this approach.

Strain hardening and toughening in metal/molecular nanolayer/metal nanosandwiches

Introducing molecular nanolayers (MNLs) is attractive for enhancing the stability of, and inducing unusual properties at, inorganic thin film interfaces. Although organic molecules anchored to inorganic surfaces have been studied extensively, property enhancement mechanisms underpinned by molecular assemblies at inorganic thin film interfaces are yet to be revealed and understood. Here, ab initio molecular dynamics simulations of tensile strain of Au/MNL/Au thin film nanosandwich models provide insights into molecularly induced strain hardening and toughening. Au/MNL/Au nanosandwiches support up to ≈30% higher stresses and exhibit up to ≈140% higher toughness than pure Au slab models. Both hardening and toughening are governed by molecular length and terminal chemistry in the MNL. Strong Au/MNL interface bonding and greater molecular length promote defect creation in Au, which results in strain hardening. Accommodation of increasing post-hardening strains in the MNL mitigates the stress increase in the Au slabs, delays interface fracture, and contributes to toughening. Remarkably, toughening correlates with equilibrium interface strain, which could be used as a proxy for efficiently identifying promising inorganic/MNL combinations that provide toughening. Our findings are important for the discovery and design of inorganic–organic interfaces, nanomaterials, and composites.

12‐4: Inorganic Halide Perovskite Thin Films Realized by Pulsed Laser Deposition over Large Area for MicroLEDs Color Conversion Layers

This paper reports the deposition of inorganic halide perovskite thin films, using pulsed laser deposition, as a way to fabricate green and red color conversion layers for microLEDs. The photoluminescence of the thin film reveal pure colors and uniform emission on 200 mm wafers. The unencapsulated thin films are stable under ambient air.

Topological Exciton Polaritons in Compact Perovskite Junction Metasurfaces

AbstractExciton polaritons are hybrid light‐matter quasi‐particles that hold exceptional opportunities for future optoelectronic devices. Taking the synergic advantages of room‐temperature perovskite excitons and topological photonic structures, topological exciton‐polaritons are experimentally demonstrated in organic–inorganic hybrid perovskite thin films. Topological junction structures based on perovskite gratings are realized using a momentum‐space analog of the 1D Dirac system. Desired enhancement phenomena are observed including narrow‐beam polariton emission from a tightly localized junction region, polaritonic nonlinearity boost, and enhanced luminescence. These remarkable features are obtained from highly compact devices with footprint widths on the order of a few micrometers and are efficiently tailorable with simple unit‐cell geometry control. Therefore, the proposed approach can be a powerful platform for room‐temperature topological exciton‐polaritons and concomitant device applications.

Reaction mechanisms of α,ω-bifunctional molecules toward atomic layer deposition versus molecular layer deposition

Atomic layer deposition (ALD) and molecular layer deposition (MLD) are key techniques used to fabricate high-quality thin films. Organic α,ω-bifunctional precursors often exhibit different growth behaviors depending on the functional groups as well as the chain length of the molecular backbone, so that some organic precursors produce thin films of organic-inorganic hybrid materials, while others may deposit purely inorganic thin films without incorporation of the hydrocarbon moiety. In this study, we investigated the surface reaction mechanisms of α,ω-bifunctional molecules (X(CH2)nX, n = 2, 3, 4, 5, 6, and X = OH, SH, NH2) with diethylzinc toward MLD and ALD using density functional theory (DFT) calculations. It was found that the length of the aliphatic alkyl chain and the terminal functional groups of bifunctional organic precursors significantly influences their reactivity, resulting in the possibility toward removal or incorporation of the organic moiety in the product. Bifunctional reactants with longer alkyl backbones (n > 4) showed higher reactivity for removal of the hydrocarbon chain, facilitated by a ω-2 hydrogen transfer reaction. Furthermore, a reactivity trend of SH > OH > NH2 for removal of the hydrocarbon chains was observed. Our study provides in-depth theoretical insights into the adsorption reaction mechanisms occurring when bifunctional molecules are employed as organic reactants in ALD and MLD processes.

In situ temperature synthesis and characterization of ferroelectric PZN-4.5PT nanoparticles’ thin films using synchrotron light source

ABSTRACT Despite the excellent properties of Pb(Zn1/3Nb2/3)O3-4.5PbTiO3 (PZN-4.5PT) single crystals, the greatest difficulty for their application on electronic devices is to make them to thin layers related to the difficulty to make them as ceramic materials. In this paper, we use the combined USAXS/SAXS/WAXS instrument at 9ID beamline at APS-ANL for in situ characterization of PZN-4.5PT inorganic perovskite nanoparticles thin films deposited on nanotextured silicon to understand the phase transitions and determine the observed microcrystals' structure. The sample was annealed from ambient to 1000°C. The results revealed structure changes in the nanoparticles' thin films which could be explained by the new phase that can be assigned to the Pb3(PO4)2-based component. The peak at 31° indicates the presence of the rhombohedral phase perovskites assigned to the nanoparticles. WAXS characterization permitted to identification of many transitions during thermal annealing like dehydration or dihydroxylation of phosphorus gel –OH bonds and internal water.

Photocurrent Enhancement by Copper Incorporation in Chemical-Solution-Synthesized Inorganic Lead Perovskite Thin Films.

Perovskite thin films are at the forefront of highly promising photovoltaic technologies due to their remarkable optoelectronic properties. Herein, we explore a low-cost, reproducible, and industry-scalable methodology to synthesize an all-inorganic CsPbI1.5Br1.5 perovskite thin film with additional incorporation of copper and chloride ions into the lattice structure. The synthesis process involves chemical bath deposition of PbS, followed by a gas-solid iodination reaction to yield PbI2. Subsequently, dip-coating incorporates Cs+, Cu2+, Br-, and Cl- ions into PbI2, and annealing at 270 °C produces perovskite thin films. The results show a large coverage area and a uniform thickness of each perovskite thin film. Comprehensive characterization, including X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and photoluminescence, provides the structural, chemical, and optical properties of the synthesized thin films. To evaluate the practical implications of our methodology, we fabricated photodetectors employing CsPbI1.5Br1.5 and (Cs0.95:Cu0.01)PbI1.5Br1.3Cl0.1 perovskite films. A comparative analysis unequivocally demonstrates a significant increase in photodetector performance when utilizing (Cs0.95:Cu0.01)PbI1.5Br1.3Cl0.1 perovskite films. While our findings quantitatively assess the tangible enhancement in photocurrent, we acknowledge the potential for improvement in device fabrication to enhance the overall performance. This study not only affirms the successful low-cost synthesis of perovskite thin films but also emphasizes the pivotal role of Cu2+ and Cl- ions in enhancing the performance of perovskite-based optoelectronic devices.

Ultrahigh thermoelectric properties of p‐type BixSb2−xTe3 thin films with exceptional flexibility for wearable energy harvesting

AbstractUse of a flexible thermoelectric source is a feasible approach to realizing self‐powered wearable electronics and the Internet of Things. Inorganic thin films are promising candidates for fabricating flexible power supply, but obtaining high‐thermoelectric‐performance thin films remains a big challenge. In the present work, a p‐type BixSb2−xTe3 thin film is designed with a high figure of merit of 1.11 at 393 K and exceptional flexibility (less than 5% increase in resistance after 1000 cycles of bending at a radius of ∼5 mm). The favorable comprehensive performance of the BixSb2−xTe3 flexible thin film is due to its excellent crystallinity, optimized carrier concentration, and low elastic modulus, which have been verified by experiments and theoretical calculations. Further, a flexible device is fabricated using the prepared p‐type BixSb2−xTe3 and n‐type Ag2Se thin films. Consequently, an outstanding power density of ∼1028 μW cm−2 is achieved at a temperature difference of 25 K. This work extends a novel concept to the fabrication of high‐performance flexible thin films and devices for wearable energy harvesting.

Ultrathin, Transferred Layers of Silicon Oxynitrides as Tunable Biofluid Barriers for Bioresorbable Electronic Systems.

Bio/ecoresorbable electronic systems create unique opportunities in implantable medical devices that serve a need over a finite time period and then disappear naturally to eliminate the need for extraction surgeries. A critical challenge in the development of this type of technology is in materials that can serve as thin, stable barriers to surrounding ground water or biofluids, yet ultimately dissolve completely to benign end products. This paper describes a class of inorganic material (silicon oxynitride, SiON) that can be formed in thin films by plasma-enhanced chemical vapor deposition for this purpose. In vitro studies suggest that SiON and its dissolution products are biocompatible, indicating the potential for its use in implantable devices. A facile process to fabricate flexible, wafer-scale multilayer films bypasses limitations associated with the mechanical fragility of inorganic thin films. Systematic computational, analytical, and experimental studies highlight the essential materials aspects. Demonstrations in wireless light-emitting diodes both in vitro and in vivo illustrate the practical use of these materials strategies. The ability to select degradation rates and water permeability through fine tuning of chemical compositions and thicknesses provides the opportunity to obtain a range of functional lifetimes to meet different application requirements.

Pulse irradiation synthesis of metal chalcogenides on flexible substrates for enhanced photothermoelectric performance

High synthesis temperatures and specific growth substrates are typically required to obtain crystalline or oriented inorganic functional thin films, posing a significant challenge for their utilization in large-scale, low-cost (opto-)electronic applications on conventional flexible substrates. Here, we explore a pulse irradiation synthesis (PIS) to prepare thermoelectric metal chalcogenide (e.g., Bi2Se3, SnSe2, and Bi2Te3) films on multiple polymeric substrates. The self-propagating combustion process enables PIS to achieve a synthesis temperature as low as 150 °C, with an ultrafast reaction completed within one second. Beyond the photothermoelectric (PTE) property, the thermal coupling between polymeric substrates and bismuth selenide films is also examined to enhance the PTE performance, resulting in a responsivity of 71.9 V/W and a response time of less than 50 ms at 1550 nm, surpassing most of its counterparts. This PIS platform offers a promising route for realizing flexible PTE or thermoelectric devices in an energy-, time-, and cost-efficient manner.

Ultrastable and high-performance amplified spontaneous emission in centimeter-scale inorganic CsPbBr3 single-crystal thin films

In this work, high-quality and centimeter-scale CsPbBr3 perovskite single-crystal thin films were grown using the metal-organic chemical vapor deposition method. Extremely flat surfaces without distinct grain boundaries were observed throughout the thin films. A high polarized degree of approximately 0.52 was measured from the single-crystal thin films by analyzing the polarization of the photoluminescence emission spectra. Low threshold amplified spontaneous emissions with an optical gain coefficient of 1215 cm−1 under the excitation energy of 301 μJ/cm2 and the highest value of 2857 cm−1 under the excitation energy of 1.08 mJ/cm2 were investigated under the excitation of a nanosecond laser at 266 nm. The CsPbBr3 single-crystal thin films showed excellent stability where the optical gain coefficient could be maintained over 1800 cm−1 after exposure to air for ten months. The results of this study not only provide high-quality single-crystal films for laser applications but also put forward a feasible scheme to improve the stability of the materials.

Intense pulsed light annealing of solution-based indium–gallium–zinc–oxide semiconductors with printed Ag source and drain electrodes for bottom gate thin film transistors

In this study, an intense pulsed light (IPL) annealing process for a printed multi-layered indium–gallium–zinc–oxide (IGZO) and silver (Ag) electrode structure was developed for a high performance all-printed inorganic thin film transistor (TFT). Through a solution process using IGZO precursor and Ag ink, the bottom gate structure TFT was fabricated. The spin coating method was used to form the IGZO semiconductor layer on a heavily-doped silicon wafer covered with thermally grown silicon dioxide. The annealing process of the IGZO layer utilized an optimized IPL irradiation process. The Ag inks were printed on the IGZO layer by screen printing to form the source and drain (S/D) pattern. This S/D pattern was dried by near infrared radiation (NIR) and the dried S/D pattern was sintered with intense pulsed light by varying the irradiation energy. The performances of the all-printed TFT such as the field effect mobility and on–off ratio electrical transfer properties were measured by a parameter analyzer. The interfacial analysis including the contact resistance and cross-sectional microstructure analysis is essential because diffusion phenomenon can occur during the annealing and sintering process. Consequently, this TFT device showed noteworthy performance (field effect mobility: 7.96 cm2/V s, on/off ratio: 107). This is similar performance compared to a conventional TFT, which is expected to open a new path in the printed metal oxide-based TFT field.

A facile in-situ reaction method for preparing flexible Sb2Te3 thermoelectric thin films

Inorganic p-type Sb2Te3 flexible thin films (f-TFs) with eco-friendly and high thermoelectric performance have attracted wide research interest and potential for commercial applications. This study employs a facile in-situ reaction method to prepare flexible Sb2Te3 thin films by rationally adjusting the synthesized temperature. The prepared thin films show good crystallinity, which enhances the electrical conductivity of ~1,440 S·cm-1 due to the weakened carrier scattering. Simultaneously, the optimized carrier concentration, through adjusting the synthesis temperature, causes the intermediate Seebeck coefficient. Consequently, a high-power factor (16.0 μW·cm-1·K-2 at 300 K) is achieved for Sb2Te3 f-TFs prepared at 623 K. Besides, the f-TFs also exhibit good flexibility due to the slight change in resistance after bending. This study specifies that the in-situ reaction method is an effective route to prepare Sb2Te3 f-TFs with high thermoelectric performance.

Recent Advances and Prospects of Solution‐Processed Efficient Sb2S3 Solar Cells

AbstractSolar cells comprising earth‐abundant and non‐toxic elements with applicable bandgaps and high absorption coefficients have attracted considerable interest over the past several decades and are important devices for addressing the future demand for clean and renewable energy. Antimony sulfide (Sb2S3) crystal material effectively meets these requirements owing to its suitable bandgap, high absorption coefficient, high electron and hole mobilities, earth abundance, and excellent stability. Solution‐processed Sb2S3 films are essential to facilitate the fabrication of low‐cost, large‐scale, and high‐efficiency photovoltaic devices, but suffer from several shortcomings of large intrinsic defects, high interfacial barrier, and atomic mismatch, uncontrollable film thickness, and crystal orientation. In this review, a systematic overview of the fundamental properties of solution‐processed Sb2S3 materials is presented, and then interface engineering, defect passivation and control strategies, crystal orientation and modulation methods, device structure, and the performance of Sb2S3 solar cells are focused, highlighting the primary advancements and major challenges based on this technology. Finally, several creative perspectives and constructive innovation strategies for future research on Sb2S3 photovoltaic devices are provided, indicating a roadmap for the practical application of other inorganic semiconductor heterojunction thin film solar cells.