Surface Energy Engineering Research Articles

Surface Energy Engineering of Buried Interface for Highly Stable Perovskite Solar Cells with Efficiency Over 25.

The abundant oxygen-related defects (e.g., O vacancies, O-H) in the TiO2 electron transport layer results in high surface energy, which is detrimental to effective carrier extraction and seriously impairs the photovoltaic performance and stability of perovskite solar cells. Here, novel surface energy engineering (SEE) is developed by applying a surfactant of heptadecafluorooctanesulfonate tetraethylammonium (HFSTA) on the surface of the TiO2 . Theoretical calculations show that the HFSTA-TiO2 is less prone to form O vacancies, leading to lower surface energy, thus improving the carrier-extraction efficiency. The experimental results show that superior perovskite film is obtained due to the reduced heterogeneous nucleation sites and improved crystallization process on the modified TiO2 . Furthermore, the flexible long alkyl chains in HFSTA considerably relieve the compressive stresses at the buried interface. By combining the passivation of TiO2 , crystallization process modulation, and stress relief, a champion PCE up to 25.03% is achieved. The device without encapsulation sustains 92.2% of its initial PCE after more than 2500h storage under air ambient with relative humidity of 25-30%. The SEE of a buried interface paves a new way toward high-efficiency, stable perovskite solar cells.

GaAs to Si Direct Wafer Bonding at T ≤ 220 °C in Ambient Air Via Nano-Bonding™ and Surface Energy Engineering (SEE)

When different semiconductors are integrated into hetero-junctions, native oxides generate interfacial defects and cause electronic recombination. Two state-of-the-art integration methods, hetero-epitaxy and Direct Wafer Bonding (DWB), require temperatures, T > 400 °C to reduce native oxides. However, T > 400 °C leads to defects due to lattice and thermal expansion mismatches. In this work, DWB temperatures are lowered via Nano-Bonding™ (NB) at T ≤ 220 °C and P ≤ 60 kPa (9 psi). NB uses Surface Energy Engineering (SEE) at 300 K to modify surface energies (γT) to far-from-equilibrium states, so cross-bonding occurs with little thermal activation and compression. SEE modifies γT and hydro-affinity (HA) via chemical etching, planarization, and termination that are optimized to yield 2-D Precursor Phases (2D-PP) metastable in ambient air and highly planar at the nano- and micro- scales. Complementary 2D-PPs nano-contact via carrier exchange from donor 2D-PP surfaces to acceptor ones. Here, NB models and SEE are applied to the DWB of GaAs to Si for photovoltaics. SEE modifies (1) the initial γT0 and HA0 measured via Three Liquid Contact Angle Analysis, (2) the oxygen coverage measured via High Resolution Ion Beam Analysis, and (3) the oxidation states measured via X-Ray Photoelectron Spectroscopy. SEE etches hydrophobic GaAs oxides with γT = 33.4 ± 1 mJ/m2, and terminates GaAs (100) with H+, rendering GaAs hydrophilic with γT = 60 ± 2 mJ/m2. Similarly, hydrophilic Si native oxides are etched into hydrophobic SiO4H2. H+- GaAs nano-bonds reproducibly to Si, as measured via Surface Acoustic Wave Microscopy, validating the NB model and SEE design.

Critical Strain-Induced Photoresponse in Folded Graphene Superlattices.

Strain engineering is the most effective method to break the symmetry of the graphene lattice and achieve graphene band gap tunability. However, a critical strain (>20%) is required to open the graphene band gap, and it is very difficult to achieve such a large strain. This limits the development of experimental research and optoelectronic devices based on graphene strain. In this work, we report a method for preparing large-strain graphene superlattices via surface energy engineering. The maximum strain of the curved lattice could reach 50%. In particular, our pioneering work reports the behavior of an ultrafast (as short as 6 ps) photoresponse in a strained folded graphene superlattice. The photocurrent map shows a large increase (up to 102) of the photoresponsivity in the tensile graphene lattice, which is generated by the interaction between the strained and pristine graphene. Through Raman spectroscopy, Kelvin probe force microscopy, and high-resolution transmission electron microscopy, we demonstrate that the ultrathreshold strain in the graphene bends triggers the opening of the graphene band gap and results in a unique photovoltaic effect. This work deepens the understanding of the strain-induced change of the photoelectrical properties of graphene and proves the potential of strained graphene as a platform for the generation of novel high-speed, miniaturized graphene-based photodetectors.

Understanding gaas Native Oxides By Correlating Three Liquid Contact Angle Analysis (3LCAA) and High Resolution Ion Beam Analysis (HR-IBA) to X-Ray Photoelectron Spectroscopy (XPS) as Function of Surface Processing

ABSTRACTChemical bonding in native oxides of GaAs, before and after etching, is detected by X-Ray Photoelectron Spectroscopy (XPS). It is correlated with surface energy engineering (SEE), measured via Three Liquid Contact Angle Analysis (3LCAA), and oxygen coverage, measured by High Resolution Ion Beam Analysis (HR-IBA).Before etching, GaAs native oxides are found to be hydrophobic with an average surface energy, γT, of 33 ± 1 mJ/m2, as measured by 3LCAA. After dilute NH4OH etching, GaAs becomes highly hydrophilic and its surface energy, γT, increases by a factor 2 to a reproducible value of 66 ± 1 mJ/m2. Using HR-IBA, oxygen coverage on GaAs is found to decrease from 7.2 ± 0.5 monolayers (ML) to 3.6 ± 0.5 ML. The 1.17 ratio of Ga to As, measured by HR-IBA, remains constant after etching.XPS is used to measure oxidation of Ga and As, as well as surface stoichiometry on two locations of several GaAs(100) wafers before and after etching. The relative proportions of Ga and As are unaffected by adventitious carbon contamination. The 1.16 Ga:As ratio, measured by XPS, matches HR-IBA analysis. The proportions of oxidized Ga and As do not change significantly after etching. However, the initial ratio of As2O5 to As2O3, within the oxidized As, significantly decreases after etching from approximately 3:1 to 3:2.Absolute oxygen coverage, as a function of surface processing, is determined within 0.5 ML by HR-IBA. XPS offers insight into these modifications by detecting electronic states and phase composition changes of GaAs oxides. The changes in surface chemistry are correlated to changes in hydro-affinity and surface energies measured by 3LCAA.

Surface energy engineering for LiTaO3 and α-quartz SiO2 for low temperature (<220 °C) wafer bonding

Wafer bonding can be substituted for heteroepitaxy when manufacturing specific heterojunction-based devices. Devices manufactured using wafer bonding include multijunction solar cells, integrated sensors, heterogeneously integrated photonic devices on Si (such as high-performance laser diodes), Mach-Zehnder modulators, photodetectors, optical filters, and surface acoustic wave devices. In these devices, creating heterointerfaces between different semiconductors with heavily mismatched lattice constants and/or significant thermal expansion mismatch presents significant challenges for heteroepitaxial growth. High costs and poor yields in heavily mismatched heteroepitaxy can be addressed by wafer bonding in these optoelectronic devices and sensors, including the LiTaO3/Si and LiTaO3/SiO2 heterostructures. In the present work, heterostructure formation between piezoelectric LiTaO3 (100) and Si (100) and α-quartz SiO2 (100) is investigated via wafer bonding. Direct bonding is selected instead of heteroepitaxy due to a significant thermal expansion mismatch between LiTaO3 and Si-based materials. The coefficient of thermal expansion (CTE) of LiTaO3 is 18.3 × 10−6/K. This is 1 order of magnitude larger than the CTE for Si, 2.6–2.77 × 10−6/K and 25–30 times larger than the CTE for fused SiO2 and quartz (which ranges 0.54–0.76 × 10−6/K). Thus, even at 200 °C, a 4 in. LiTaO3/Si bonded pair would delaminate with LiTaO3 expanding 300 μm in length while Si would expand only by 40 μm. Therefore, direct wafer bonding of LiTaO3/Si and LiTaO3/SiO2 is investigated with low temperature (T < 500 K) Nano-Bonding™, which uses surface energy engineering (SEE). SEE is guided by fast, high statistics surface energy measurements using three liquid contact angle analysis, the van Oss/van Oss–Chaudhury–Good theory, and a new, fast Drop Reflection Operative Program analysis algorithm. Bonding hydrophobic LiTaO3 to hydrophilic Si or SiO2 is found to be more effective than hydrophilic LiTaO3 to hydrophobic Si or SiO2 temperatures for processing LiTaO3 are limited by thermal decomposition LiTaO3 into Ta2O5 at T ≥ 180 °C due to Li out-diffusion as much as by LiTaO3 fractures due to thermal mismatch.

A Stress‐Free and Textured GaP Template on Silicon for Solar Water Splitting

AbstractThis work shows that a large‐scale textured GaP template monolithically integrated on Si can be developed by using surface energy engineering, for water‐splitting applications. The stability of (114)A facets is first shown, based on scanning tunneling microscopy images, transmission electron microscopy, and atomic force microscopy. These observations are then discussed in terms of thermodynamics through density functional theory calculations. A stress‐free nanopatterned surface is obtained by molecular beam epitaxy, composed of a regular array of GaP (114)A facets over a 2 in. vicinal Si substrate. The advantages of such textured (114)A GaP/Si template in terms of surface gain, band lineups, and ohmic contacts for water‐splitting applications are finally discussed.

Self-Patterning of Silica/Epoxy Nanocomposite Underfill by Tailored Hydrophilic-Superhydrophobic Surfaces for 3D Integrated Circuit (IC) Stacking

As microelectronics are trending toward smaller packages and integrated circuit (IC) stacks nowadays, underfill, the polymer composite filled in between the IC chip and the substrate, becomes increasingly important for interconnection reliability. However, traditional underfills cannot meet the requirements for low-profile and fine pitch in high density IC stacking packages. Post-applied underfills have difficulties in flowing into the small gaps between the chip and the substrate, while pre-applied underfills face filler entrapment at bond pads. In this report, we present a self-patterning underfilling technology that uses selective wetting of underfill on Cu bond pads and Si3N4 passivation via surface energy engineering. This novel process, fully compatible with the conventional underfilling process, eliminates the issue of filler entrapment in typical pre-applied underfilling process, enabling high density and fine pitch IC die bonding.

Interface Engineering for Extremely Large Grains in Explosively Crystallized TiO2 Films Grown by Low-Temperature Atomic Layer Deposition

Functionality in thin films is closely linked with both the microstructure of the film as well as the innate nature of the thin film material. The engineering of microstructure, especially the grain size and its distribution in oxide thin films, is critical to designing functionalities targeting specific applications. However, the scope for manipulation of the microstructure of an oxide thin film is generally quite limited because of the lack of mobility of atoms at processing temperatures that are usually employed for the growth of these films. This work reports the observation of very large grains (∼100 times larger than the film thickness) in TiO2 films grown by atomic layer deposition at low temperature (<250 °C). Large grain sizes were observed in the as-grown films even in the absence of postdeposition annealing, wherein substrates with high surface energies were used. It is concluded that the surface energy engineering of substrate offers an efficient method to control the grain size of TiO2 films ...

Tunable wettability of Si through surface energy engineering by nanopatterning

Schematic diagram of a water droplet on an isotropic (flat) and anisotropic (rippled) surfaces.

Tunable Polarity in a III-V Nanowire by Droplet Wetting and Surface Energy Engineering.

Controllable axial switching of polarity in GaAs nanowires with minimal tapering and perfect twin-free ZB structure based on the fundamental understanding of nanowire growth and kinking mechanism is presented. The polarity of the bottom segment is confirmed to be (111)A by atomically resolved scanning transmission electron microscopy.

Control of zinc oxide nanowire array properties with electron-beam lithography templating for photovoltaic applications

Hydrothermally synthesized zinc oxide nanowire arrays have been used as nanostructured acceptors in emerging photovoltaic (PV) devices. The nanoscale dimensions of such arrays allow for enhanced charge extraction from PV active layers, but the device performance critically depends on the nanowire array pitch and alignment. In this study, we templated hydrothermally-grown ZnO nanowire arrays via high-resolution electron-beam-lithography defined masks, achieving the dual requirements of high-resolution patterning at a pitch of several hundred nanometers, while maintaining hole sizes small enough to control nanowire array morphology. We investigated several process conditions, including the effect of annealing sputtered and spincoated ZnO seed layers on nanowire growth, to optimize array property metrics—branching from individual template holes and off-normal alignment. We found that decreasing template hole size decreased branching prevalence but also reduced alignment. Annealing seed layers typically improved alignment, and sputtered seed layers yielded nanowire arrays superior to spincoated seed layers. We show that these effects arose from variation in the size of the template holes relative to the ZnO grain size in the seed layer. The quantitative control of branching and alignment of the nanowire array that is achieved in this study will open new paths toward engineering more efficient electrodes to increase photocurrent in nanostructured PVs. This control is also applicable to inorganic nanowire growth in general, nanomechanical generators, nanowire transistors, and surface-energy engineering.

Surface energy engineering for tunable wettability through controlled synthesis of MoS2.

MoS2 is an important member of the transition metal dichalcogenides that is emerging as a potential 2D atomically thin layered material for low power electronic and optoelectronic applications. However, for MoS2 a critical fundamental question of significant importance is how the surface energy and hence the wettability is altered at the nanoscale in particular, the role of crystallinity and orientation. This work reports on the synthesis of large area MoS2 thin films on insulating substrates (SiO2/Si and Al2O3) with different surface morphology via vapor phase deposition by varying the growth temperatures. The samples were examined using transmission electron microscopy and Raman spectroscopy. From contact angle measurements, it is possible to correlate the wettability with crystallinity at the nanoscale. The specific surface energy for few layers MoS2 is estimated to be about 46.5 mJ/m(2). Moreover a layer thickness-dependent wettability study suggests that the lower the thickness is, the higher the contact angle will be. Our results shed light on the MoS2-water interaction that is important for the development of devices based on MoS2 coated surfaces for microfluidic applications.

Surface Energy Engineering in the Solvothermal Deoxidation of Graphene Oxide

A route to achieving high yields of monodisperse, deeply deoxidized graphene oxide (GO) in solution is presented. It overcomes many of the problems of dispersibility and inefficient reduction of GO in solvothermal deoxidation that are usually observed, despite the previous use of strong reducing agents (e.g. Fe2+, S or hydrazine). It is shown that the incomplete deoxidation is most likely due to agglomeration/self‐assembly of partially reduced GO, which also creates poor dispersibility. GO deoxidation is found to be highly sensitive to the solvent surface energy and, through experiments and empirical calculations, tuning the solvent surface energy to around 85.6 mJ/m2 (at 100 °C) leads to fully deoxidized GO. These calculations also allow appropriate solvent surface energies to be calculated for other temperatures for deep deoxidation of GO. This approach makes solvothermal deoxidation of GO a potential route to large scale, economic production of highly disperse monolayered graphene.

Properties of graphene inks stabilized by different functional groups

Different graphene inks have been synthesized by chemical methods. These uniform dispersionswere stabilized by various functional groups such as room temperature ionic liquid,polyaniline, polyelectrolyte (poly[2,5-bis(3-sulfonatopropoxy)-1,4-ethynylphenylene-alt-1,4-ethynylphenylene] sodium salt) and poly(styrenesulfonate) (PSS). The dispersions can beeasily cast into high-quality, free-standing films but with very different physiochemicalproperties such as surface tension and adhesion. SEM and AFM methods havebeen applied to have a detailed study of the properties of the inks. It is foundthat graphenes modified by p-type polyaniline show the highest surface tension.Diverse surface adhesive properties to the substrate are also found with variousfunctional groups. The different viscoelasticities of graphene inks were related tothe microscopic structure of their coating layer and subsequently related to theconfiguration, chemistry and molecular dimensions of the modifying molecules toestablish the property–structure relationship. Modifications of graphene inks madefrom chemical reduction cannot only enable cost-effective processing for printableelectronics but also extend the applications into, for example, self-assembly ofgraphene via bottom-up nano-architecture and surface energy engineering of thegraphenes. To fabricate useful devices, understanding the surface properties ofgraphene inks is very important. It is the first paper of this kind to study thesurface tension and adhesion of graphene influenced by different functional groups.

Solution processable micron- to nanoscale conducting polymer patterning utilizing selective surface energy engineering

We developed a new conducting polymer microscale and nanoscale patterning method; a bottom-up approach for applying a conducting polymer solution on a substrate with locally varied surface energies. Selective surface energy engineering was achieved by combining conventional photolithography and local hydrophobic treatments with a self-assembled monolayer (SAM) at the exposed surface. The regions under the photoresist patterns remained hydrophilic after the photoresist removal. Here, a poly(3,4-ethylene-dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) conducting polymer solution was dispensed with a razor blade on the substrate, wetting only the hydrophilic regions. Next, conducting source/drain polymer electrodes were fabricated (channel length: 5 μm) and utilized for poly(3-hexylthiophene) (P3HT) organic field-effect transistors. For nanoscale conducting polymer line patterns, a photoresist template with nanoscale features was fabricated using holographic lithography. Finally, multi-step spin coating method reliably produced polymer lines having a linewidth of 292 nm at 1 μm spacing.