Resonant Infrared Matrix-assisted Pulsed Laser Evaporation Research Articles

Correlation of Emulsion Chemistry, Film Morphology, and Device Performance in Polyfluorene LEDs Deposited by RIR-MAPLE

Thin films of polyfluorene (PFO) were deposited using emulsion-based resonant infrared, matrix-assisted pulsed laser evaporation (RIR-MAPLE). Here, it is shown that properly selected surfactant chemistry in the emulsion can increase crystalline β phase (β-PFO) content and consequently improve the color purity of light emission. To determine the impact of surfactant on the device performance of resulting films, blue light-emitting diodes (LEDs) with PFO as an active region were fabricated and compared. Molecular dynamics (MD) simulations were used to explain the physical and chemical changes in the emulsion properties as a function of the surfactant. The results indicate that the experimental film morphology and device performance are highly correlated to the emulsion droplet micelle structure and interaction energy among PFO, primary solvent, and water obtained from MD simulations. While the champion device performance was lower than other reported devices (luminous flux ∼0.0206 lm, brightness ∼725.58 cd/m2, luminous efficacy ∼0.0548 lm/W, and luminous efficiency ∼0.174 cd/A), deep blue emission with good color purity (CIE chromaticity diagram coordinate of (0.177,0.141)) was achieved for low operating voltages around 3 V. Furthermore, a much higher β-phase content of 21% was achieved in annealed films (without the pinholes typically found in β-PFO deposited by other techniques) by using sodium dodecyl sulfate (SDS) as the surfactant.

Phenomenological mechanisms of hybrid organic–inorganic perovskite thin film deposition by RIR-MAPLE

Resonant infrared, matrix-assisted pulsed laser evaporation (RIR-MAPLE) is a promising technique for the physical vapor deposition of hybrid organic–inorganic perovskites. The approach already has been used to deposit both three-dimensional and two-dimensional hybrid perovskites with material quality comparable to those synthesized by solution processing. However, the phenomenological mechanisms of hybrid perovskite film formation by RIR-MAPLE have not been articulated. Therefore, this work presents a careful investigation of film formation mechanisms of three-dimensional methylammonium lead halide perovskites by considering the temporal evolution of morphology, crystallinity, and optical properties of films deposited by RIR-MAPLE.

Transparent MXene-Polymer Supercapacitive Film Deposited Using RIR-MAPLE

In this work, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE), a novel deposition technique, was used to produce a transparent composite electrode of polyflourene (PFO) and two-dimensional (2D) Ti3C2Tx nanosheets, which are part of the broader MXene family of transition metal carbides and nitrides. This deposition technique offers a facile way to vary film composition in polymer/polymer and polymer/nanoparticle films. Through this method, composite PFO and MXene films were studied across six different compositions, enabling the identification of a film composition that exhibited excellent charge storage (above 10 mF/cm2) and transparency (over 75% transmittance) when used as a supercapacitor electrode material. Thus, RIR-MAPLE shows promise as a controllable and facile deposition technique for organic/inorganic composite films for use in transparent supercapacitors, as well as in other energy storage applications.

Deposition of β-Polyfluorene by Resonant Infrared Matrix-Assisted Pulsed Laser Evaporation

Emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) was used to deposit thin films of polyfluorene (PFO) with semi-crystalline phase domains (β-PFO), which has been performed, previously, only by solution phase processing. Various target emulsion recipes were studied, with emphasis on the primary solvent choice, emulsion mixing time, secondary solvent concentration, or total water concentration. The emulsified particle size for each recipe was compared using dynamic light scattering. Additionally, elevated growth temperature of the substrate was considered for controlling film formation. The surface quality of films was determined by atomic force microscopy, and β-PFO concentration was monitored using photoluminescence or UV–visible absorbance spectroscopy. Importantly, in contrast to solution-based deposition of β-PFO in thin films, emulsion-based RIR-MAPLE demonstrated the ability to increase β-PFO content without degrading, simultaneously, the surface properties of the films. This initial result helps establish the ability of RIR-MAPLE to control and promote semi-crystalline phases in polymer films.

MAPbI3 Solar Cells with Absorber Deposited by Resonant Infrared Matrix-Assisted Pulsed Laser Evaporation

Resonant infrared, matrix-assisted pulsed laser evaporation (RIR-MAPLE) is a gentle thin-film deposition technique that combines the facile chemical control of solution processing with the growth control of vapor-phase deposition, yet one that has not been widely applied to crystalline organic–inorganic hybrid materials. In this work, we investigate the optoelectronic quality of RIR-MAPLE-deposited CH3NH3PbI3 (MAPbI3) perovskite films and report on the fabrication of perovskite solar cells in which the absorber is deposited by RIR-MAPLE. We find the composition, morphology, and optical properties of these perovskite films to be comparable to those produced by more conventional methods, such as spin coating. The champion device reaches a stabilized power conversion efficiency of over 12%, a high value for perovskite solar cells deposited by a laser ablation process, highlighting the ability of this new technique to produce device-quality films.

Deposition of Methylammonium Lead Triiodide by Resonant Infrared Matrix-Assisted Pulsed Laser Evaporation

Resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) was used to deposit the metal-halide perovskite (MHP) CH3NH3PbI3 (methylammonium lead triiodide, or MAPbI), creating phase-pure films. Given the moisture sensitivity of these crystalline, multi-component organic–inorganic hybrid materials, deposition of MAPbI by RIR-MAPLE required a departure from the use of water-based emulsions as deposition targets. Different chemistries were explored to create targets that properly dissolved MAPbI components, were stable under vacuum conditions, and enabled resonant laser energy absorption. Secondary phases and solvent contamination in the resulting films were studied through Fourier transform infrared (FTIR) absorbance and x-ray diffraction (XRD) measurements, suggesting that lingering excess methylammonium iodide (MAI) and low-vapor pressure solvents can distort the microstructure, creating crystalline and amorphous non-perovskite phases. Thermal annealing of films deposited by RIR-MAPLE allowed for excess solvent to be evaporated from films without degrading the MAPbI structure. Further, it was demonstrated that RIR-MAPLE does not require excess MAI to create stoichiometric films with optoelectronic properties, crystal structure, and film morphology comparable to films created using more established spin-coating methods for processing MHPs. This work marks the first time a MAPLE-related technique was used to deposit MHPs.

RIR-MAPLE deposition of plasmonic silver nanoparticles

Nanoparticles are being explored in many different applications due to the unique properties offered by quantum effects. To broaden the scope of these applications, the deposition of nanoparticles onto substrates in a simple and controlled way is highly desired. In this study, we use resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) for the deposition of metallic, silver nanoparticles for plasmonic applications. We find that RIR-MAPLE, a simple and versatile approach, is able to deposit silver nanoparticles as large as 80 nm onto different substrates with good adhesion, regardless of substrate properties. In addition, the nanoparticle surface coverage of the substrates, which result from the random distribution of nanoparticles across the substrate per laser pulse, can be simply and precisely controlled by RIR-MAPLE. Polymer films of poly(3-hexylthiophene-2,5-diyl) (P3HT) are also deposited by RIR-MAPLE on top of the deposited silver nanoparticles in order to demonstrate enhanced absorption due to the localized surface plasmon resonance effect. The reported features of RIR-MAPLE nanoparticle deposition indicate that this tool can enable efficient processing of nanoparticle thin films for applications that require specific substrates or configurations that are not easily achieved using solution-based approaches.

Emulsion-Based RIR-MAPLE Deposition of Conjugated Polymers: Primary Solvent Effect and Its Implications on Organic Solar Cell Performance.

Emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) has been demonstrated as an alternative technique to deposit conjugated polymer films for photovoltaic applications; yet, a fundamental understanding of how the emulsion target characteristics translate into film properties and solar cell performance is unclear. Such understanding is crucial to enable the rational improvement of organic solar cell (OSC) efficiency and to realize the expected advantages of emulsion-based RIR-MAPLE for OSC fabrication. In this paper, the effect of the primary solvent used in the emulsion target is studied, both experimentally and theoretically, and it is found to determine the conjugated polymer cluster size in the emulsion as well as surface roughness and internal morphology of resulting polymer films. By using a primary solvent with low solubility-in-water and low vapor pressure, the surface roughness of deposited P3HT and PCPDTBT polymer films was reduced to 10 nm, and the efficiency of P3HT:PC61BM OSCs was increased to 3.2% (∼100 times higher compared to the first MAPLE OSC demonstration [ Caricato , A. P. ; Appl. Phys. Lett. 2012 , 100 , 073306 ]). This work unveils the mechanism of polymer film formation using emulsion-based RIR-MAPLE and provides insight and direction to determine the best ways to take advantage of the emulsion target approach to control film properties for different applications.

Hybrid nanocomposite thin films deposited by emulsion-based resonant infrared matrix-assisted pulsed laser evaporation for photovoltaic applications

Emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) was used to deposit CdSe nanoparticle films and hybrid nanocomposite films comprising colloidal CdSe nanoparticles embedded in a low band gap polymer, poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT). We show that, in contrast to traditional MAPLE deposition, the CdSe nanoparticle film deposited by emulsion based RIR-MAPLE is contiguous and uniform, and it maintains the optical properties of the nanoparticle solution. Moreover, we show that the RIR-MAPLE deposited PCPDTBT/CdSe hybrid nanocomposite film exhibits a relatively random and uniform distribution of CdSe nanoparticles without the significant phase segregation that is observed in hybrid nanocomposite films deposited by spin-casting. Finally, hybrid organic solar cells based on nanocomposite films deposited by the RIR-MAPLE technique were fabricated and characterized, showing 0.4% power conversion efficiency. This is the first demonstration of a polymer–nanoparticle hybrid organic solar cell fabricated by a MAPLE-related technique.

Antimicrobial and bacteria-releasing multifunctional surfaces: Oligo (p-phenylene-ethynylene)/poly (N-isopropylacrylamide) films deposited by RIR-MAPLE

Antimicrobial oligo (p-phenylene-ethynylene) (OPE) films have previously been demonstrated to show effective ultraviolet A (UVA) light-induced biocidal activity; however, a serious problem arises from the accumulation of dead bacteria and debris on the films that limits their effectiveness and application. In this work, we address this challenge by incorporating thermally-responsive poly (N-isopropylacrylamide) (PNIPAAm), which provides on-demand bacteria-releasing functionality. Multifunctional surfaces comprising blended films of OPE and PNIPAAm were deposited on substrates by resonant infrared, matrix-assisted pulsed laser evaporation (RIR-MAPLE) using a sequential co-deposition mode. In this way, RIR-MAPLE enabled the deposition of multifunctional films with surface properties and film functionality that can be tailored, precisely and systematically, by controlling the chemical composition of the deposited film. The surface properties of these films were characterized by UV–visible (UV–vis) absorbance spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and water contact angle measurements. The interactions between bacteria and the deposited films were tested using two model bacteria: Escherichia coli K12 (Gram-negative) and Staphylococcus epidermidis (Gram-positive). The antimicrobial and bacteria-release properties of the blended films were controlled by varying the OPE/PNIPAAm ratio in the RIR-MAPLE emulsion target, providing an easy way to optimize the multifunctional surface. The OPE/PNIPAAm blended films with optimized composition killed a majority of attached E. coli bacteria at 37°C and under UVA exposure, and the dead bacteria were then removed from the films simply by rinsing with water at 25°C.

Bulk heterojunction PCPDTBT:PC71BM organic solar cells deposited by emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation

Organic solar cells based on poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) were fabricated by emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE). Two different deposition modes, namely simultaneous deposition and sequential deposition, were investigated for fabricating bulk-heterojunction organic solar cells. This work demonstrates that the RIR-MAPLE sequential deposition mode provides precise ratio control for the fabrication of bulk-heterojunction organic solar cells.

Antimicrobial oligo(p-phenylene-ethynylene) film deposited by resonant infrared matrix-assisted pulsed laser evaporation

The antimicrobial oligomer, oligo(p-phenylene-ethynylene) (OPE), was deposited as thin films by resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) on solid substrates and exhibited light-induced biocidal activity. The biocidal activity of OPE thin films deposited by spin-coating and drop-casting was also investigated for comparison. Enhanced bacterial attachment and biocidal efficiency of the film deposited by RIR-MAPLE were observed and attributed to nanoscale surface topography of the thin film.

Organic Semiconductor Thin Films Deposited by Resonant Infrared Matrix-Assisted Pulsed Laser Evaporation: A Fundamental Study of the Emulsion Target

ABSTRACTPoly (3-hexylthiophene) (P3HT) thin films were deposited using emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) from emulsions containing different solvents and different alcohols, to investigate the impact of emulsion on film morphology. The atomic force microscopy (AFM) and grazing-incidence, wide angle x-ray scattering (GIWAXS) results show that surface morphology of RIR-MAPLE as-deposited films can be varied from rough to smooth and the microcrystalline domain orientations with respect to the substrate can be tuned from randomly oriented to preferentially oriented in the vertical direction. The demonstrated ability to tune the structural characteristics of polymer thin films by controlling the target emulsion is important for the application of organic optoelectronic devices deposited by RIR-MAPLE.

RIR-MAPLE deposition of multifunctional films combining biocidal and fouling release properties.

Multifunctional films with both antimicrobial activity and fouling-release ability based on a biocidal quaternary ammonium salt (QAS) and thermo-responsive poly(N-isopropylacrylamide) (PNIPAAm) were deposited on substrates using resonant infrared, matrix-assisted pulsed laser evaporation (RIR-MAPLE). The surface properties of these films were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), and water contact angle measurements. The biocidal and release properties of the films were tested against Escherichia coli K12 and Staphylococcus epidermidis. At 37 °C, the deposited film facilitated bacterial attachment and killed a majority of attached bacteria. Decrease of the temperature to 25 °C promoted the hydration and at least partial dissolution of PNIPAAm, leading to bacterial detachment from the film. To enhance the retention of PNIPAAm on the substrate, a small amount of (3-aminopropyl)triethoxysilane (APTES) was incorporated as a stabilizer, resulting in a ternary film with biocidal activity and bacterial-release ability after several attach-kill-release cycles. The simplicity and universality of RIR-MAPLE to form films on a wide range of substrata make it a promising technique to deposit multifunctional films to actively mitigate bacterial biofouling.

Tuning the Refractive Index of Homopolymer Blends by Controlling Nanoscale Domain Size via RIR‐MAPLE Deposition

Anti‐reflection (AR) coatings designed for glass and other rigid, inorganic substrates are commercially available; however, these inorganic AR coatings tend to crack or delaminate on flexible substrates. A polymeric film with a gradient refractive index (GRIN) profile would make an ideal AR coating for flexible substrates, but such coatings are challenging to fabricate using traditional, solution‐based techniques. Emulsion‐based resonant infrared, matrix‐assisted pulsed laser evaporation (RIR‐MAPLE) offers a straightforward approach to enabling the desired GRIN profile in polymeric materials. Two homopolymers (polystyrene (PS) and poly(methyl methacrylate) (PMMA)) are deposited as a blend and one component (PMMA) is dissolved, leaving behind a porous PS film. The porosity and refractive index (RI) are controlled by the volume ratio of the two homopolymers in the film. Structural and optical characterizations, as well as comparison to modeled optical properties, confirm that porous films fabricated from polymer blends deposited by RIR‐MAPLE behave as effective media over most of the visible spectrum. While evidence for the partial collapse of the porous polymer networks is observed, the RI of the porous films is reduced from that of the bulk material. Importantly, these studies demonstrate that RIR‐MAPLE should enable broadband, omnidirectional, polymeric AR coatings appropriate for flexible substrates. image

Resonant infrared matrix-assisted pulsed laser evaporation of TiO2 nanoparticle films

The successful development of flexible, high performance thin films that are competitive with silicon-based technology will likely require fabricating films of hybrid materials that incorporate nanomaterials, glasses, ceramics, polymers, and thin films. Resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) is an ideal method for depositing organic materials and nanoparticles with minimal photochemical or photothermal damage to the deposited material. Furthermore, there are many nonhazardous solvents containing chemical functional groups with infrared absorption bands that are accessible using IR lasers. We report here results of recent work in which RIR-MAPLE has been employed successfully to deposit thin films of TiO2 nanoparticles on Si substrates. Using an Er:YAG laser (λ=2.94 μm), we investigated a variety of MAPLE matrices containing –OH moieties, including water and all four isomers of butyl alcohol. The alcohol isomers are shown to provide effective and relatively nontoxic solvents for use in the RIR-MAPLE process. In addition, we examine the effects of varying concentration and laser fluence on film roughness and surface coverage.

Effects of Emulsion-Based Resonant Infrared Matrix Assisted Pulsed Laser Evaporation (RIR-MAPLE) on the Molecular Weight of Polymers

The molecular weight of a polymer determines key optoelectronic device characteristics, such as internal morphology and charge transport. Therefore, it is important to ensure that polymer deposition techniques do not significantly alter the native polymer molecular weight. This work addresses polymers deposited by resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE). By using a novel emulsion-based target technique, the deposition of smooth, contiguous films with no evidence of chemical degradation have been enabled. However, structural degradation via a reduction in molecular weight remains an open question. The common polymer standard, PMMA, and the optoelectronic polymers, P3HT and MEH-PPV, have been characterized before and after emulsion-based RIR-MAPLE deposition via gel permeation chromatography to determine if RIR-MAPLE affects the deposited polymer molecular weight. Proton nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy measurements have also been conducted to verify the absence of chemical degradation. These measurements verify that there is no chemical degradation of the polymers, and that PMMA and P3HT show no structural degradation, but MEH-PPV exhibits a halving of the weight-averaged molecular weight after RIR-MAPLE deposition. Compared with competing laser deposition techniques, RIR-MAPLE is shown to have the least effect on the molecular weight of the resulting thin films.

Resonant infrared laser deposition of polymer-nanocomposite materials for optoelectronic applications

Polymers find a number of potentially useful applications in optoelectronic devices. These include both active layers, such as light-emitting polymers and hole-transport layers, and passive layers, such as polymer barrier coatings and light-management films. This paper reports the experimental results for polymer films deposited by resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) and resonant infrared pulsed laser deposition (RIR-PLD) for commercial optoelectronic device applications. In particular, light-management films, such as anti-reflection coatings, require refractive-index engineering of a material. However, refractive indices of polymers fall within a relatively narrow range, leading to major efforts to develop both low- and high-refractive-index polymers. Polymer nanocomposites can expand the range of refractive indices by incorporating low- or high-refractive-index nanoscale materials. RIR-MAPLE is an excellent technique for depositing polymer-nanocomposite films in multilayer structures, which are essential to light-management coatings. In this paper, we report our efforts to engineer the refractive index of a barrier polymer by combining RIR-MAPLE of nanomaterials (for example, high refractive-index TiO2 nanoparticles) and RIR-PLD of host polymer. In addition, we report on the properties of organic and polymer films deposited by RIR-MAPLE and/or RIR-PLD, such as Alq3 [tris(8-hydroxyquinoline) aluminum] and PEDOT:PSS [poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate)]. Finally, the challenges and potential for commercializing RIR-MAPLE/PLD, such as industrial scale-up issues, are discussed.

RIR-MAPLE deposition of conjugated polymers for application to optoelectronic devices

Resonant-infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) is a promising deposition technology for the fabrication of conjugated polymer-based optoelectronic devices for two primary reasons: (i) the ability to control film morphology, and (ii) the ability to deposit multi-layered heterostructures. This article reviews a variation of RIR-MAPLE that uses emulsified targets of organic solvents and water such that the incident laser wavelength (Er:YAG at 2.9 μm) is resonant with hydroxyl (O–H) bonds in the host matrix, which are absent from the guest material. The novelty of the approach lies in the fact that while most polymers of interest and many compatible solvents do not resonantly absorb the laser energy at 2.9 μm, the emulsion with water enables high-quality, thin-film deposition with minimal photochemical and structural degradation for almost any polymer of interest. In addition, the advantages of emulsion-based RIR-MAPLE for conjugated polymer-based optoelectronic devices are demonstrated by two important studies. First, conjugated polymer films deposited by RIR-MAPLE are shown to have higher hole drift mobilities than films deposited using traditional drop-casting and spin-casting techniques. Second, the unique capability of RIR-MAPLE to enable conjugated polymer-based optical heterostructures is demonstrated by the fabrication and characterization of a multi-layer, polymer distributed Bragg reflector.

Mechanisms of Resonant Infrared Matrix-Assisted Pulsed Laser Evaporation

For the last decade, a variant of pulsed laser ablation, Resonant-Infrared Matrix-Assisted Pulsed Laser Evaporation (RIR-MAPLE), has been studied as a deposition technique for organic and polymeric materials. RIR-MAPLE minimizes photochemical damage from direct interaction with the intense laser beam by encapsulating the polymer in a high infrared-absorption solvent matrix. This review critically examines the thermally-induced ablation mechanisms resulting from irradiation of cryogenic solvent matrices by a tunable free electron laser (FEL). A semi-empirical model is used to calculate temperatures as a function of time in the focal volume and determine heating rates for different resonant modes in two model solvents, based on the thermodynamics and kinetics of the phase transitions induced in the solvent matrices. Three principal ablation mechanisms are discussed, namely normal vaporization at the surface, normal boiling, and phase explosion. Normal vaporization is a highly inefficient polymer deposition mechanism as it relies on collective collisions with evaporating solvent molecules. Diffusion length calculations for heterogeneously nucleated vapor bubbles show that normal boiling is kinetically limited. During high-power pulsed-FEL irradiation, phase explosion is shown to be the most significant contribution to polymer deposition in RIR-MAPLE. Phase explosion occurs when the target is rapidly heated (108 to 1010 K/s) and the solvent matrix approaches its critical temperature. Spontaneous density stratification (spinodal decay) within the condensed metastable phase leads to rapid homogeneous nucleation of vapor bubbles. As these vapor bubbles interconnect, large pressures build up within the condensed phase, leading to target explosions and recoil-induced ejections of polymer to a near substrate. Phase explosion is a temperature (fluence) threshold-limited process, while surface evaporation can occur even at very low fluences.