Aromatic sensitizers in luminescent hybrid films.

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.

Molecular layer deposition of photoactive metal-naphthalene hybrid thin films.

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 known zirconium chloride (ZrCl4) based system. All metal-naphthalene films are amorphous as-deposited and show self-saturating growth as expected for an ideal MLD process with varied growth rates depending on the choice of metal precursor. The growth was studied in situ using quartz crystal microbalance (QCM) and the films were further characterised using spectroscopic ellipsometry (SE), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and UV-Vis and photoluminescence (PL) spectroscopy to obtain information on their physicochemical properties. The hybrid thin films display intense blue photoluminescence, except for the Ti-organic complex in which titanium clusters were found to be an effective PL quencher for the organic linker. We demonstrate how the optical properties of the films depend on the choice of metal component to make a foundation for further studies on these types of organic-inorganic hybrid materials for applications as photoactive agents.

Quinizarin: a large aromatic molecule well suited for atomic layer deposition.

Atomic layer deposition (ALD) is a remarkable synthesis tool due to the vast array of materials that can be deposited and the complexity of structures that can be designed. The low-temperature layer-by-layer approach even allows organic and inorganic components to be combined as hybrid or composite materials. The technique is then called molecular layer deposition (MLD). This opens the door for deposition of advanced optical materials using highly absorbing aromatic molecules. Unfortunately, most large aromatic molecules are difficult to sublime or have insufficient reactivity. This is a major barrier for ALD when designing with the use of organic components for dye-sensitized solar cells, luminescence, visible light photochemistry, chemical sensors and organic electronics. In this work, we introduce a well-known orange dye molecule, quinizarin. This molecule has a large conjugated aromatic system with strong absorption of visible light and shows strong luminescence both in solutions and as a complex together with aluminium ions. Interestingly, quinizarin also shows surprisingly good properties for film deposition due to reactive -OH groups and low sublimation temperature (130 °C). Strongly coloured pink hybrid films were deposited with trimethylaluminium and quinizarin at 175 °C with a growth rate of 0.28 nm per cycle. These films were not luminescent although their optical absorption spectra are similar to those of the corresponding solution. An attempt was made to dilute quinizarin through partial replacement with pentaerythritol as a multilayer structure or simultaneous co-pulsing, although this also did not produce luminescent films. The low sublimation temperature, good reactivity and large conjugated system of quinizarin open the way for exploration of solid-state hybrid and organic films based on this molecule along many different technological pathways.

Single-step approach to sensitized luminescence through bulk-embedded organics in crystalline fluorides.

Luminescent materials enable warm white LEDs, molecular tagging, enhanced optoelectronics and can improve energy harvesting. With the recent development of multi-step processes like down- and upconversion and the difficulty in sensitizing these, it is clear that optimizing all properties simultaneously is not possible within a single material class. In this work, we have utilized the layer-by-layer approach of atomic layer deposition to combine broad absorption from an aromatic molecule with the high emission yields of crystalline multi-layer lanthanide fluorides in a single-step nanocomposite process. This approach results in complete energy transfer from the organic molecule while providing inorganic fluoride-like lanthanide luminescence. Sm3+ is easily quenched by organic sensitizers, but in our case we obtain strong fluoride-like Sm3+ emission sensitized by strong UV absorption of terephthalic acid. This design allows combinations of otherwise incompatible species, both with respect to normally incompatible synthesis requirements and in controlling energy transfer and quenching routes.

Sensors for optical thermometry based on luminescence from layered YVO4: Ln3+ (Ln = Nd, Sm, Eu, Dy, Ho, Er, Tm, Yb) thin films made by atomic layer deposition.

Below the Earth's crust, temperatures may reach beyond 600 K, impeding the batteries used to power conventional thermometers. Fluorescence intensity ratio based temperature probes can be used with optical fibers that can withstand these conditions. However, the probes tend to exhibit narrow operating ranges and poor sensitivity above 400 K. In this study, we have investigated single and dual layered YVO4: Ln3+ (Ln = Nd, Sm, Eu, Dy, Ho, Er, Tm, Yb) thin films (100-150 nm) for use in fluorescence intensity ratio based temperature sensors in the 300-850 K range. The type of lanthanide emission can be fine-tuned by adjusting the thickness of each layer, and the layered structure allows for emission from otherwise incompatible lanthanide pairs. This novel multi-layered approach enables high sensitivity over a broad temperature range. The highest relative sensitivity was achieved for a dual layered YVO4: Eu3+/YVO4: Dy3+ sample, exhibiting a maximum sensitivity of 3.6% K-1 at 640 K. The films were successfully deposited on all tested substrates (silicon, iron, aluminum, glass, quartz, and steel), and can be applied homogenously to most surfaces without the use of binders. The films are unaffected by water, enabling non-contact temperature sensing in water, where IR thermometers are not an option.

Luminescent YbVO4 by atomic layer deposition.

UV to visible and near-infrared converting thin films of YbVO4 have been deposited by atomic layer deposition, using the precursor combinations Yb(thd)3 (thd = 2,2,6,6-tetramethyl-3,5-heptanedione) and O3, and VO(thd)2 and O3 at a deposition temperature of 240 °C, followed by post deposition annealing at 400-1000 °C. The UV absorption and the visible and near-infrared emission have been investigated in detail. The structure, thickness and composition of the deposited films have been studied by X-ray diffraction, ellipsometry, and X-ray fluorescence, respectively. The optimal pulse ratio of Yb(thd)3 and VO(thd)2 with respect to near-infrared emission was found to be 1 : 3, which also yielded the most crystalline sample after annealing. Crystallization of the films is accelerated when an excess of V2O5 is present, enabling crystallization at temperatures as low as 500 °C, probably through a flux aided process.

Structural and optical properties of lanthanide oxides grown by atomic layer deposition (Ln = Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb).

Ln2O3 thin films with optically active f-electrons (Ln = Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb) have been grown on Si(100) and soda lime glass substrates by atomic layer deposition (ALD) using Ln(thd)3 (Hthd = 2,2,6,6-tetramethyl-3,5-heptanedione) and ozone as precursors. The temperature range for depositions was 200-400 °C. Growth rates were measured by spectroscopic ellipsometry and a region with a constant growth rate (ALD window) was found for Ln = Ho and Tm. All the compounds are grown as amorphous films at low temperatures, whereas crystalline films (cubic C-Ln2O3) are obtained above a certain temperature ranging from 300 to 250 °C for Nd2O3 to Yb2O3, respectively. AFM studies show that the films were smooth (rms < 1 nm) except for depositions at the highest temperatures. The refractive index was measured by spectroscopic ellipsometry and was found to depend on the deposition temperature. Optical absorption measurements show that the absorption from the f-f transitions depends strongly on the crystallinity of the material. The clear correlation between the degree of crystallinity, optical absorptions and refractive indices is discussed.

Atomic layer deposition of organic-inorganic hybrid materials based on saturated linear carboxylic acids.

Atomic layer deposition (ALD) has successfully provided thin films of organic-inorganic hybrid materials based on saturated linear carboxylic acids and trimethylaluminium (TMA). Films were grown for seven carboxylic acids: oxalic, malonic, succinic, glutaric, pimelic, suberic and sebacic acid, i.e. ranging from 2 to 10 carbon atoms in the molecular structure. These processes show exceptionally high growth rates; up to 4.3 nm/cycle for the pimelic acid-TMA system. Quartz crystal microbalance measurements of the growth dynamics indicate that all systems are of a self limiting ALD-type. Nevertheless, temperature dependent growth was observed in several systems. The width of the ALD windows shows correlations with the length of the carbon chains. Fourier transform infrared spectroscopy clearly proved that the deposited films are of a hybrid character, where the carboxylic acids primarily form bidentate complexes, though bridging complexes may also form. All films are X-ray amorphous as deposited. The films were further analyzed by atomic force microscopy for surface roughness and topography, UV-Vis spectroscopy and ellipsometry for optical properties, and the goniometer method for measuring sessile drops for surface wetting properties. Apart from the oxalic and malonic acid-TMA systems, the films are stable in contact with water. The films are generally smooth, transparent and have a refractive index close to 1.5. The complete coverage and accurate growth control offered by the ALD technique is here proven to provide surface-functionalized hybrid materials resembling metal-organic frameworks (MOF), probably as rather dense structures, yet with substantial potential for applications.