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Possible structures of metal-naphthalene hybrids deposited in this work.
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We here report on photoactive organic-inorganic hybrid thin films prepared by the molecular layer deposition (MLD) method. The new series of hybrid films deposited using 2,6-naphthalenedicarboxylic acid (2,6-NDC) and either hafnium chloride (HfCl4), yttrium tetramethylheptanedionate (Y(thd)3) or titanium chloride (TiCl4) were compared with the know...
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... this work, we created four possible hybrid complexes Ti-NDC, Zr-NDC, Hf-NDC and Y-NDC (Fig. 1). The growth dynamics of all systems were initially investigated using in situ QCM. The standard pulsing sequences and reaction temperatures used throughout the QCM experiments for all systems were chosen after some preliminary experiments and are presented in Table 1. Note that for the Zr-NDC process we used the deposition parameters ...
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... the standard pulsing sequence. The growth rate as a function of inorganic and organic precursor pulse length is shown in Fig. 2a and b. All investigated systems show self-limiting growth for both precursors. The relatively low density of the films measured by XRR was determined to 2.1 g cm −3 for Hf-NDC and ∼1.7 g cm −3 for Ti-, Zr-, and Y-NDC ( Fig. S1 ...
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... all our MLD processes yielded relatively smooth and amorphous thin films ( Fig. S9 and S10 †). Although the Atomic Force Microscopy (AFM) images of the samples based on the chlorine precursors show very small and regular islands on the otherwise almost flat surface, these islands do not produce any diffraction pattern when measured by XRD. The root-mean-square (RMS) surface roughness in islands-free regions estimated by AFM (as ...
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... variations of around 6 nm for Hf-NDC, 8 nm for Zr-NDC and 12 nm for Ti-NDC. Additionally, all films exhibit rather good stability when exposed to DI water, except the Y-NDC sample, which completely dissolved after 24 hours of water treatment (Table S1 †). The wettability of the surfaces was thus investigated by contact angle measurements, see Fig. S12, † showing that Y-NDC has a more hydrophilic nature than the other deposited systems (Ti-NDC = 80°, Zr-NDC/Hf-NDC = 78° and Y-NDC = 68°). Furthermore, sample-tip adhesion measured with AFM was significantly higher for Y-NDC (95.1 ± 4.1 nN) than for Hf-NDC (2.3 ± 0.1 nN) (Fig. S11 †). Such high adhesion measured in air at ambient ...
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... surfaces was thus investigated by contact angle measurements, see Fig. S12, † showing that Y-NDC has a more hydrophilic nature than the other deposited systems (Ti-NDC = 80°, Zr-NDC/Hf-NDC = 78° and Y-NDC = 68°). Furthermore, sample-tip adhesion measured with AFM was significantly higher for Y-NDC (95.1 ± 4.1 nN) than for Hf-NDC (2.3 ± 0.1 nN) (Fig. S11 †). Such high adhesion measured in air at ambient humidity conditions results from capillary condensation and formation of water bridges between an AFM tip and the sample, and points to more hydrophilic surface properties of Y-NDC films in comparison with Hf-NDC. ...
Citations
... [66] -ZrO 2 membrane showed stable separation performance for 120 days with a high selectivity towards water. [77][78][79][80][81][82][83][84][85][86] Tubular MF -ZrO 2 200 9.5 (soya sauce) -Raw soya sauce filtration [82] -Comparison between ZrO 2 (0.2 μm) and Al 2 Table 4 presents a compilation of remarkable works published concerning the fabrication of UF and NF zirconia membranes. ...
... They reported a confirmed linear growth at 145 • C with a growth rate of 0.8 Å per MLD cycle. In 2021, Rogowska et al. [200] reported that photoactive organic molecules could be combined with biocompatible metals like Zr or Ti to create antimicrobial ...
Zirconia (ZrO2) membranes experienced rapid progress in applications demanding high-stability membranes own to their higher chemical resistance and hydrophilicity compared to silica and alumina. Moreover, ZrO2 membranes have increased fouling resistance, high permeability, and a long lifetime making them broadly applied in drinking water production, wastewater treatment, petrochemical, food, and beverages industries. However, fabricating ZrO2 membranes for Nanofiltration and Gas Separation is still challenging. This paper reviews the progress in fabricating ZrO2 membranes, focusing on strategies for achieving smaller pores without losing their high permeability and selectivity. The current state of the art in commercial ZrO2 membranes and the recent innovations in academia are critically reviewed. A comprehensive revision of sol-gel technique's critical synthesis and process parameters is presented along with the most recent molecular layer deposition method. This work aims to provide a guide for both starting and established researchers, thus filling a gap in the present literature.
... In previous works, we have investigated the growth and material chemistry of optically active hybrid materials. 5,6,12,14 Here, we focus on the hybrid materials optical properties, absorption and luminescence colour. ...
Atomic layer deposition offers a unique set of design possibilities due to the vast range of metal and organic precursors that can be used and combined. In this work, we have combined lanthanides with aromatic aids as strongly absorbing sensitizers to form highly luminescent thin films. Terephthalic acid is used as a base sensitizer, absorbing shorter wavelengths than 300 nm. The absorption range is extended towards the near-UV and blue range by increasing the aromatic system and adding functional groups that have strong red-shifting effects. While terbium and europium provide green and red emission, yttrium allows emission from the sensitizer itself spanning the whole color range from purple, blue and green to red. Many organic dye molecules show very high luminescence quantum yields and several of the molecules and materials investigated in this work show bright luminescence.
... We recently reported how the type of transition metal affects the optical properties of MLD hybrid materials based on 2,6naphthalenedicarboxylic acid as the linker. 12 For instance, the presence of d 0 -metals such as Ti, Zr or Hf shis the light absorption towards the visible part of the spectrum and increases the potential application of such hybrid materials as photoactive agents. Moreover, the light absorption properties can be further tuned by increasing the size of the aromatic backbone or by adding various functional groups. ...
... The Zr-2A-BDC and Zr-26-NDC lms were deposited as described in detail in our previous work. 11,12,20 Specically, the standard pulsing sequence for Zr-2A-BDC was 4-3-5-3 s and for Zr-26-NDC was 3-2-20-2 s. In both cases, the deposition temperature was set to 260 C. ...
... 21 Given this information, the D ¼ 120 cm À1 for Zr-25D-BDC lm indicates a bidentate type of coordination, and a possible structure of this Zr-hybrid is shown in the inset of Fig. 4. A similar coordination mode was previously observed for the Zr-2A-BDC and Zr-26-NDC lms. 12,20 The absence of a sharp intense peak at around 1650 cm À1 from the C]O stretching vibrations of free COOH groups in the lm proves that it coordinates to the zirconium atom during formation of the hybrid structure. 10 Similarly, from the spectrum of as-deposited lms, the absence of the broad absorption between 2400 and 3500 cm À1 with the maximum at around 3080 cm À1 arising from stretching vibrations of OH groups from COOH indicates that the oxygen is deprotonated and bonded to the metal. ...
The principle of antimicrobial photodynamic therapy (PDT) is appealing because it can be controlled by an external light source and possibly the use of durable materials. However, to utilise such surfaces requires a process for their production that allows for coating on even complex geometries. We have therefore explored the ability of the emerging molecular layer deposition (MLD) technique to produce and tune PDT active materials. This study demonstrates how the type of aromatic ligand influences the optical and antimicrobial properties of photoactive Zr-organic hybrid thin films made by MLD. The three aromatic dicarboxylic acids: 2,5-dihydroxy-1,4-benzenedicarboxylic acid, 2-amino-1,4-benzenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid have been combined with ZrCl 4 to produce hybrid coatings. The first system has not been previously described by MLD and is therefore more thoroughly investigated using in situ quartz crystal microbalance (QCM), Fourier transform infrared (FTIR) and UV-Vis spectroscopy. The antibacterial phototoxic effects of Zr-organic hybrids have been explored in the Staphylococcus aureus bacteria model using a UVA/blue light source. Films based on the 2,6-naphthalenedicarboxylic acid linker significantly reduced the number of viable bacteria by 99.9%, while no apparent activity was observed for the two other photoactive systems. Our work thus provides evidence that the MLD technique is a suitable tool to produce high-quality novel materials for possible applications in antimicrobial PDT, however it requires a careful selection of aromatic ligands used to construct photoactive materials.
We demonstrate multiple roles for the organic linker in luminescent lanthanide-organic thin films grown with the strongly emerging atomic/molecular layer deposition technique. Besides rendering the hybrid thin film mechanically flexible and keeping the lanthanide nodes at a distance adequate to avoid concentration quenching, the organic moieties can act as efficient sensitizers for the lanthanide luminescence. We investigate six different aromatic organic precursors in combination with Eu3+ ions to reveal that by introducing different nitrogen species within the aromatic ring, it is possible to extend the excitation wavelength area from the UV range to the visible range. This opens new horizons for the application space of these efficiently photoluminescent thin-film materials.
As patterning technology for manufacturing highly integrated devices develops in the current semiconductor market, sophisticated technology nodes of 5 nm or smaller are required. Area selective deposition (ASD) is a promising technology alternative to traditional top-down methods by reducing-edge placement error (EPE) and creating self-alignment. A new strategy for applying the qualified molecular layer deposition (MLD) process of highly conformal deposition to ASD as an inhibition material is being studied. In the case of metalcones manufactured using an aromatic ring as an organic precursor, graphitic carbonization proceeds through high-temperature annealing, and the inhibition property can be activated by removing surface functional groups. The characteristics of feasible patterning can be noted as metal elements in the thin film are removed during the annealing process, especially in the case of graphitic carbon. In this review, we introduce the potential application of MLD materials in the development of inhibitors for advanced ASD
The combined atomic/molecular layer deposition (ALD/MLD) technique is emerging as a state-of-the-art synthesis route for new metal-organic thin-film materials with a multitude of properties by combining those of the inorganic and the organic material. A major part of the studies so far reported have focused on aluminum or zinc alkyls, so-called alucone and zincone films, typically grown from trimethyl aluminum (TMA) or diethyl zinc (DEZ) as the metal-bearing precursor, and a simple aliphatic bi-functional alcohol molecule such as ethylene glycol (EG) as the organic precursor. However, these common precursors possess certain disadvantages: both TMA and DEZ are pyrophoric, DEZ being additionally thermally unstable, while EG has a strong tendency for various unideal reaction modes. Here we report novel ALD/MLD processes for alucone and zincone films based on non-pyrophoric bis-diisopropylamido-[3-(N,N-dimethylamino)propyl] aluminum(III) [Al(NiPr2)2(DMP)] and bis-3-(N,N-dimethylamino)propyl zinc(II) [Zn(DMP)2] precursors in combination with hydroquinone (HQ) as the organic precursor. We demonstrate that the [Al(NiPr2)2(DMP)] + HQ and [Zn(DMP)2] + HQ ALD/MLD processes work even at record low deposition temperatures (140 °C and 60 °C, respectively) yielding high-quality and relatively stable Al-HQ and Zn-HQ thin films with appreciably high growth rates (2.8 Å / cycle and 3.2 Å / cycle, respectively). Moreover, these ALD/MLD processes are compatible with the corresponding ALD processes, i.e. [Al(NiPr2)2(DMP)] + H2O and [Zn(DMP)2] + H2O, for the Al2O3 and ZnO films, thus opening up new horizons for the fabrication of novel metal-oxide : organic superlattice structures for e.g. flexible gas-barrier coatings or wearable thermoelectrics.
Atomic layer deposition (ALD) for high‐quality conformal inorganic thin films is one of the cornerstones of modern microelectronics, while molecular layer deposition (MLD) is its less‐exploited counterpart for purely organic thin films. Currently, the hybrid of these two techniques, i.e., ALD/MLD, is strongly emerging as a state‐of‐the‐art gas‐phase route for designer's metal–organic thin films, e.g., for the next‐generation energy technologies. The ALD/MLD literature comprises nearly 300 original journal papers covering most of the alkali and alkaline earth metals, 3d transition metals, and lanthanides as the metal component and a variety of aliphatic, aromatic, and natural organic components. Some of these ALD/MLD processes yield in situ crystalline coordination‐polymer‐ or metal–organic‐framework‐like structures. Another attractive aspect is that many of the metal–organics realized through ALD/MLD are fundamentally new materials, and even unaccessible through conventional synthesis. Here, the current state of research in the field is presented, by i) providing a comprehensive account of the ALD/MLD processes so far developed, ii) addressing the constraints/possibilities for growing in situ crystalline metal–organic films, iii) highlighting some intriguing ALD/MLD materials and their application potential, and iv) making a brief outlook to the future perspectives and challenges in the field. Atomic/molecular layer deposition allows the fusion of inorganic and organic components into designer's hybrid materials in a scientifically elegant yet industry feasible way. It can yield unforeseen crystalline metal–organic thin films and elaborated inorganic‐organic heterostructures towards next‐generation advanced applications. This comprehensive review summarizes the research conducted in the field during its decade‐plus history.
