Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications

The surface science of titanium dioxide

The chemistry of heterocyclic carbenes has experienced a rapid development over the last years. In addition to the imidazolin-2-ylidenes, a large number of cyclic diaminocarbenes with different ring sizes have been described. Aside from diaminocarbenes, P-heterocyclic carbenes, and derivatives with only one, or even no heteroatom within the carbene ring are known. New methods for the synthesis of complexes with N-heterocyclic carbene ligands such as the oxidative addition or the metal atom template controlled cyclization of β-functionalized isocyanides have been developed recently. This review summarizes the new developments regarding the synthesis of N-heterocyclic carbenes and their metal complexes.

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

Surfactant-mediated synthesis methods have attracted much interest for the production of inorganic mesoporous materials, which can, on removal of the surfactant template, incorporate polymeric, organic, inorganic and organometallic guests' in their pores 1,2 . These materials-initially made of silica 3-5 , but now also available in the form of other oxides 6-9 , sulphides 10,11 , phosphates 12 and metals 13 -could find application in fields ranging from catalysis, adsorption and sensing technology to nanoelectronics. The extension of surfactant-mediated synthesis to produce inorganic-organic hybrid material (that is, materials that contain organic groups as an integral part of their framework structure) promises access to an even wider range of application possibilities. Such hybrid materials have been produced in the form of amorphous silicates (xerogels) that indeed display unique properties different to those of the individual components 14-20 , but their random networks with broad pore-size distributions severely limit the shape and size selectivity of these materials. Mesoporous hybrid materials with periodic frameworks have been synthesized, but the organic groups are all terminally bonded to the pore surface, rather than incorporated into the pore walls 21-26 . Here we describe a periodic mesoporous organosilica containing bridge-bonded ethene groups directly integrated into the silica framework. We are able to solvent-extract and ion-exchange the surfactant templates to create a stable and periodic mesoporous ethenesilica with high surface area and ethene groups that are readily accessible for chemical reaction. Recent syntheses of similar periodic mesoporous organosilicas 27,28 and the ability to incorporate a variety of bridging organic and organometallic species raise the prospect of being able to fuse organic synthesis and inorganic materials chemistry to generate new materials with interesting chemical, mechanical electronic, optical and magnetic properties.

Periodic mesoporous organosilicas with organic groups inside the channel walls

The ever increasing requirements for electrical performance of on-chip wiring has driven three major technological advances in recent years. First, copper has replaced Aluminum as the new interconnect metal of choice, forcing also the introduction of damascene processing. Second, alternatives for SiO2 with a lower dielectric constant are being developed and introduced in main stream processing. The many new resulting materials needs to be classified in terms of their materials characteristics, evaluated in terms of their properties, and tested for process compatibility. Third, in an attempt to lower the dielectric constant even more, porosity is being introduced into these new materials. The study of processes such as plasma interactions and swelling in liquid media now becomes critical. Furthermore, pore sealing and the deposition of a thin continuous copper diffusion barrier on a porous dielectric are of prime importance. This review is an attempt to give an overview of the classification, the character...

Low dielectric constant materials for microelectronics

This review focuses on some aspects of the chemistry involved in the preparation of oxides by sol–gel methods. This field is opening interesting possibilities for molecular chemistry and among those presented herein are: (1) the use of precursors containing functional groups for the preparation of solids with specific chemical reactivity; (2) the non-hydrolytic gelation (NHG) route, a new general method for the synthesis of oxides that allows the use of oxygen donors (ethers, alcohols, alkoxides) other than water; the mechanism is based on oxygen–carbon bond cleavage; (3) organic–inorganic hybrid solids containing covalent bonds for which the chemical reactivity is used to demonstrate the presence of substructure in the globally amorphous solid; the substructure greatly depends on the geometry of the organic moiety.

Recent developments of molecular chemistry for sol-gel processes

The reaction of manganese(III) acetate meso-tetraphenylporphyrin with phenylphosphinic acid provides the one-dimensional compound of formula [Mn(TPP)O2PHPh] x H2O, which crystallizes in the monoclinic C2/c space group. The chain structure is generated by a glide plane resulting in Jahn-Teller elongation axes of the MnIII octahedra that alternate along the chain. The phenylphosphinate anion transmits a sizable antiferromagnetic exchange interaction that, combined with the easy axis magnetic anisotropy of the MnIII sites, gives rise to a canted antiferromagnetic arrangement of the spins. The static single-crystal magnetic properties have been analyzed with a classical Monte Carlo approach, and the best fit parameters for the exchange and single ion anisotropy are J = -0.68(4) K and D = -4.7(2) K, respectively (using the -2JS(i)S(j) formalism for the exchange). Below 5 K the single-crystal dynamics susceptibility reveals a frequency-dependent out-of-phase signal typical of single-chain magnets. The extracted relaxation time follows the Arrhenius law with delta = 36.8 K. The dynamic behavior has been rationalized and correlated to geometrical parameters of the structure. The contribution of the correlation length to the energy barrier has been investigated, and it has been found that the characteristic length that dominates the dynamics strongly exceeds the correlation length estimated from magnetic susceptibility.

The canted antiferromagnetic approach to single-chain magnets.

SiO2–ZrO2 and SiO2–TiO2 mixed oxides with various metal contents have been prepared by a non-hydrolytic sol–gel route involving the condensation between chloride and isopropoxide functions at 110 °C. Well condensed, monolithic gels were obtained in one step, without the use of additives. The Si/M ratio of the oxide may be controlled easily by the composition of the starting mixture. The Si/Zr oxides remained amorphous after calcination for 5 h at 600 °C; IR and 29Si NMR spectroscopy showed a large amount of Si–O–Zr bonds, indicating a homogeneous distribution of the components on the atomic scale. The crystallization of tetragonal zirconia took place at higher temperature; the transformation of tetragonal to monoclinic zirconia was strongly retarded and did not take place after 2 h at 1300 °C. The crystallization of zircon (for a sample containing 50 mol% Zr) started at 1500°C and was completed after 20 h at 1500°C. IR spectroscopy indicated the presence of a limited number of Si–O–Ti bonds in all the Si/Ti oxides after calcination for 5 h at 500 °C. The sample within the stable glass region (5 mol% Ti) appeared perfectly homogeneous: it crystallized at 900 °C as single-phase cristobalite oxide, with Ti4+ ions substituting Si4+ ions at random. On the other hand, the precipitation of anatase was observed for the Si/Ti oxides with a high Ti content (20–50 mol% Ti), which are outside the stable glass region. The transformation of anatase to rutile was not observed even after 2 h at 1300 °C.

Mixed oxides SiO2–ZrO2 and SiO2–TiO2 by a non-hydrolytic sol–gel route

The etherolysis/condensation of TiCl4 by diisopropyl ether (iPr2O) as well as the direct condensation between TiCl4 and Ti(OiPr)4 are efficient nonhydrolytic sol−gel routes to titania. A comparison of the solution chemistry of the two routes was performed by means of NMR spectroscopy. In both cases the condensation is slow at room temperature; the true precursors are titanium chloroisopropoxides in equilibrium through fast ligand-exchange reactions. The condensation takes place at 100 °C after an induction period which drastically depends upon the OiPr/Ti ratio in the reaction mixture. This behavior is related to the composition of the starting chloroisopropoxides mixture. The key species in the induction process appears to be Ti(OiPr)Cl3, which catalyzes the first condensation reactions.

A Solution Chemistry Study of Nonhydrolytic Sol−Gel Routes to Titania

Titania samples prepared by different non-hydrolytic sol–gel methods, mainly based on the etherolysis and alcoholysis of titanium tetrachloride, have been found to differ in both structure and texture. Thus, the reaction of diethyl ether with TiCl4 at 110 °C affords anatase, which begins to convert into rutile only around 1000 °C. The reaction of TiCl4 with ethanol leads to rutile as early as 110 °C, whereas the reaction of tert-butyl alcohol at 110 °C leads to the singular formation of brookite.

Dominique Leclercq

Papers

Recent developments of molecular chemistry for sol-gel processes

The canted antiferromagnetic approach to single-chain magnets.

Mixed oxides SiO2–ZrO2 and SiO2–TiO2 by a non-hydrolytic sol–gel route

A Solution Chemistry Study of Nonhydrolytic Sol−Gel Routes to Titania

Preparation of anatase, brookite and rutile at low temperature by non-hydrolytic sol–gel methods