Nanomolecularly-induced Effects at Titania/Organo-Diphosphonate Interfaces for Stable Hybrid Multilayers with Emergent Properties.

Nanoscale hybrid inorganic-organic multilayers are attractive for accessing emergent phenomena and properties through superposition of nanomolecularly-induced interface effects for diverse applications. Here, we demonstrate the effects of interfacial molecular nanolayers (MNLs) of organo-diphosphonates on the growth and stability of titania nanolayers during the synthesis of titania/MNL multilayers by sequential atomic layer deposition and single-cycle molecular layer deposition. Interfacial organo-diphosphonate MNLs result in ∼20-40% slower growth of amorphous titania nanolayers and inhibit anatase nanocrystal formation from them when compared to amorphous titania grown without MNLs. Both these effects are more pronounced in multilayers with aliphatic backbone-MNLs and likely related to impurity incorporation and incomplete reduction of the titania precursor indicated by our spectroscopic analyses. In contrast, both MNLs result in two-fold higher titania nanolayer roughness, suggesting that roughening is primarily due to MNL bonding chemistry. Such MNL-induced effects on inorganic nanolayer growth rate, roughening, and stability are germane to realizing high-interface-fraction hybrid nanolaminate multilayers.

Synthesis, Characterization, and Single-Crystal X-ray Structures of Refractory Metal Compounds as Precursors for the Single-Source Chemical Vapor Deposition of Metal Nitrides.

The chemical vapor deposition of refractory metal nitrides requires volatile precursors and has previously been achieved by using metal complexes containing a variety of imide ligands. Recently, the 1,4-di-tert-butyl-1,3-diazabutadiene (DAD) adduct of bis(tert-butylimide)dichloridemolybdenum(VI) was shown to be an excellent precursor for the single-source CVD of Mo2N thin films. Leveraging the success of this work, we prepared chromium and tungsten compounds with the same framework. Additionally, the framework has been modified slightly to allow the isolation of mono(tert-butylimide)trichloride complexes of vanadium, niobium, tantalum, and molybdenum(V) to extend the search for new vapor-phase precursors. These compounds were all fully characterized using the standard methods of multinuclear magnetic resonance spectroscopy, combustion analysis, and single-crystal X-ray diffraction. Their thermal properties were determined by using thermogravimetric analysis and differential scanning colorimetry to assess their utility as vapor-phase precursors. Finally, preliminary deposition studies were carried out to investigate their potential as single-source CVD precursors.

Disturbance of intermolecular forces: eutectics as a new tool for the preparation of vapor-phase deposition precursors.

The volatile bis(tert-butylimido)dichloromolybdenum(VI) compounds, (tBuN)2MoCl2·dad (dad = 1,4-di-tert-butyl-1,3-diazabutadiene) (1) and [(tBuN)2MoCl(µ-Cl)·(tBuNH2)]2 (2), form a eutectic, with a two to one composition (χ2 = 0.33). A decrease of 40 °C in the melting temperature has been observed between the eutectic mixture and the pure compounds. We have isolated a co-crystal of (tBuN)2MoCl2·dme (dme = 1,2-dimethoxyethane) (3) and 2, also in a two to one ratio, which serves as a structural model for such mixtures. The lower melting point of carefully chosen eutectic mixtures can offer more consistent precursor delivery in deposition processes.

Origin of Decomposition in a Family of Molybdenum Precursor Compounds.

The bis(tert-butylimido)-molybdenum(VI) framework has been used successfully in the design of vapor-phase precursors for molybdenum-containing thin films, so understanding its thermal behavior is important for such applications. Here, we report the thermal decomposition mechanism for a series of volatile bis(alkylimido)-dichloromolybdenum(VI) adducts with neutral N,N'-chelating ligands, to probe the stability and decomposition pathways for these molecules. The alkyl groups explored were tert-butyl, tert-pentyl, 1-adamantyl, and a cyclic imido (from 2,5-dimethylhexane-2,5-diamine). We also report the synthesis of the new tert-octyl imido adducts, (tOctN)2MoCl2·L (L = N,N,N',N'-tetramethylethylenediamine or 2,2'-bipyridine), which have been fully characterized by spectroscopic techniques as well as single-crystal X-ray diffraction and thermal analysis. We found that the decomposition of all compounds follows the same general pathway, proceeding first by the dissociation of the chelating ligand to give the coordinatively unsaturated species (RN)2MoCl2. Subsequent dimerization results in either an imido bridged adduct, [(RN)Mo(µ-NR)Cl2]2, or a chloride bridged adduct, [(RN)2Mo(µ-Cl)Cl]2, depending on the size of the R group. The dimeric species then likely undergoes an intramolecular γ-hydrogen transfer to yield a nitrido-amido adduct, (RHN)MoNCl2, and an alkene. Ultimately, the resulting molybdenum species appears to decompose into free tert-alkylamine and Mo2N or Mo2C. The thermolysis reactions have been monitored using 1H NMR spectroscopy, and the volatile decomposition products were analyzed using gas chromatography-mass spectrometry. A key intermediate has also been detected using electron ionization high-resolution mass spectrometry. Finally, a detailed computational investigation supports the mechanism outlined above and helps explain the relative stabilities of different N,N'-chelated bis(alkylimido)-dichloromolybdenum(VI) adducts.

Atomic layer deposition of PbCl2, PbBr2 and mixed lead halide (Cl, Br, I) PbXnY2-n thin films.

Atomic layer deposition offers outstanding film uniformity and conformality on substrates with high aspect ratio features. These qualities are essential for mixed-halide perovskite films applied in tandem solar cells, transistors and light-emitting diodes. The optical and electronic properties of mixed-halide perovskites can be adjusted by adjusting the ratios of different halides. So far ALD is only capable of depositing iodine-based halide perovskites whereas other halide processes are lacking. We describe six new low temperature (≤100 °C) ALD processes for PbCl2 and PbBr2 that are crucial steps for the deposition of mixed-halide perovskites with ALD. Lead bis[bis(trimethylsilyl)amide]-GaCl3 and -TiBr4 processes yield the purest, crystalline, uniform and conformal films of PbCl2 and PbBr2 respectively. We show that these two processes in combination with a PbI2 process from the literature deposit mixed lead halide films. The four less optimal processes revealed that reaction by-products in lead halide deposition processes may cause film etching or incorporate themselves into the film.

Thermal Stability and Decomposition Pathways in Volatile Molybdenum(VI) Bis-imides.

The vapor deposition of many molybdenum-containing films relies on the delivery of volatile compounds with the general bis(tert-butylimido)molybdenum(VI) framework, both in atomic layer deposition and chemical vapor deposition. We have prepared a series of (tBuN)2MoCl2 adducts using neutral N,N'-chelates and investigated their volatility, thermal stability, and decomposition pathways. Volatility has been determined by thermogravimetric analysis, with the 1,4-di-tert-butyl-1,3-diazabutadiene adduct (5) found to be the most volatile (1 Torr of vapor pressure at 135 °C). Thermal stability was measured primarily using differential scanning calorimetry, and the 1,10-phenanthroline adduct (4) was found to be the most stable with an onset of decomposition of 303 °C. We have also investigated molybdenum compounds with other alkyl-substituted imido groups: these compounds all follow a similar decomposition pathway, γ-H activation, with varying reaction barriers. The tert-pentyl, 1-adamantyl, and a cyclic imido (from 2,5-dimethylhexane-2,5-diamine) were systematically studied to probe the kinetics of this pathway. All of these compounds have been fully characterized, including via single-crystal X-ray diffraction, and a total of 19 new structures are reported.

Synthesis, Characterization, and Thermal Study of Divalent Germanium, Tin, and Lead Triazenides as Potential Vapor Deposition Precursors.

Only a few M-N bonded divalent group 14 precursors are available for vapor deposition, in particular for Ge and Pb. A majority of the reported precursors are dicoordinated with the Sn(II) amidinates, the only tetracoordinated examples. No Ge(II) and Pb(II) amidinates suitable for vapor deposition have been demonstrated. Herein, we present tetracoordinated Ge(II), Sn(II), and Pb(II) complexes bearing two sets of chelating 1,3-di-tert-butyltriazenide ligands. These compounds are thermally stable, sublime quantitatively between 60 and 75 °C (at 0.5 mbar), and show ideal single-step volatilization by thermogravimetric analysis.

Resolving Impurities in Atomic Layer Deposited Aluminum Nitride through Low Cost, High Efficiency Precursor Design.

A heteroleptic amidoalane precursor is presented as a more suitably designed candidate to replace trimethylaluminum (TMA) for atomic layer deposition of aluminum nitride (AlN). The lack of C-Al bonds and the strongly reducing hydride ligands in [AlH2(NMe2)]3 (1) were specifically chosen to limit impurities in target aluminum nitride (AlN) films. Compound 1 is made in a high yield, scalable synthesis involving lithium aluminum hydride and dimethylammonium chloride. It has a vapor pressure of 1 Torr at 40 °C and evaporates with negligible residual mass in thermogravimetric experiments. Ammonia (NH3) plasma and 1 in an atomic layer deposition (ALD) process produced crystalline AlN films above 200 °C with an Al:N ratio of 1.04. Carbon and oxygen impurities in resultant AlN films were reduced to <1% and <2%, respectively. By using a precursor with a rational and advantageous design, we can improve the material quality of AlN films compared to those deposited using the industrial standard trimethylaluminum and could reduce material cost by up to 2 orders of magnitude.

A Rare Low-Spin CoIV Bis(ß-silyldiamide) with High Thermal Stability: Steric Enforcement of a Doublet Configuration.

Attempted preparation of a chelated CoII ß-silylamide resulted in the unprecedented disproportionation to Co0 and a spirocyclic cobalt(IV) bis(ß-silyldiamide): [Co[(Nt Bu)2 SiMe2 ]2 ] (1). Compound 1 exhibited a room-temperature magnetic moment of 1.8 B.M. and a solid-state axial EPR spectrum diagnostic of a rare S= 1 / 2 configuration for tetrahedral CoIV . Ab initio semicanonical coupled-cluster calculations (DLPNO-CCSD(T)) revealed the doublet state was clearly preferred (-27 kcal mol-1 ) over higher spin configurations only for the bulky tert-butyl-substituted analogue. Unlike other CoIV complexes, 1 had remarkable thermal stability, and was demonstrated to form a stable self-limiting monolayer in preliminary atomic layer deposition (ALD) surface saturation experiments. The ease of synthesis and high stability make 1 an attractive starting point to investigate otherwise inaccessible CoIV intermediates and for synthesizing new materials.

Reaction mechanism of the Me3AuPMe3-H2 plasma-enhanced ALD process.

The reaction mechanism of the recently reported Me3AuPMe3-H2 plasma gold ALD process was investigated using in situ characterization techniques in a pump-type ALD system. In situ RAIRS and in vacuo XPS measurements confirm that the CH3 and PMe3 ligands remain on the gold surface after chemisorption of the precursor, causing self-limiting adsorption. Remaining surface groups are removed by the H2 plasma in the form of CH4 and likely as PHxMey groups, allowing chemisorption of new precursor molecules during the next exposure. The decomposition behaviour of the Me3AuPMe3 precursor on a Au surface is also presented and linked to the stability of the precursor ligands that govern the self-limiting growth during ALD. Desorption of the CH3 ligands occurs at all substrate temperatures during evacuation to high vacuum, occurring faster at higher temperatures. The PMe3 ligand is found to be less stable on a gold surface at higher substrate temperatures and is accompanied by an increase in precusor decomposition on a gold surface, indicating that the temperature dependent stability of the precursor ligands is an important factor to ensure self-limiting precursor adsorption during ALD. Remarkably, precursor decomposition does not occur on a SiO2 surface, in situ transmission absorption infrared experiments indicate that nucleation on a SiO2 surface occurs on Si-OH groups. Finally, we comment on the use of different co-reactants during PE-ALD of Au and we report on different PE-ALD growth with the reported O2 plasma and H2O process in pump-type versus flow-type ALD systems.

Thermal atomic layer deposition of gold nanoparticles: controlled growth and size selection for photocatalysis.

Gold nanoparticles have been extensively studied for their applications in catalysis. For Au nanoparticles to be catalytically active, controlling the particle size is crucial. Here we present a low temperature (105 °C) thermal atomic layer deposition approach for depositing gold nanoparticles on TiO2 with controlled size and loading using trimethylphosphino-trimethylgold(iii) and two co-reactants (ozone and water) in a fluidized bed reactor. We show that the exposure time of the precursors is a variable that can be used to decouple the Au particle size from the loading. Longer exposures of ozone narrow the particle size distribution, while longer exposures of water broaden it. By studying the photocatalytic activity of Au/TiO2 nanocomposites, we show how the ability to control particle size and loading independently can be used not only to enhance performance but also to investigate structure-property relationships. This study provides insights into the mechanism underlying the formation and evolution of Au nanoparticles prepared for the first time via vapor phase atomic layer deposition. Employing a vapor deposition technique for the synthesis of Au/TiO2 nanocomposites eliminates the shortcomings of conventional liquid-based processes opening up the possibility of highly controlled synthesis of materials at large scale.

Volatile and Thermally Stable Polymeric Tin Trifluoroacetates.

Tin trifluoroacetates are effective vapor phase single-source precursors for F-doped SnO2, but their structures have been poorly understood for decades. Here we undertook a comprehensive structural analysis of these compounds in both the solid and gas phases through a combined single-crystal X-ray crystallography, gas phase electron diffraction, and density functional theory investigation. Tin(II) bis(trifluoroacetate) (1) thermally decomposes into a 1:1 mixture of 1 and ditin(II) µ-oxybis(µ-trifluoroacetate) (2) during sublimation, which then polymerize into hexatin(II)-di-µ3-oxyoctakis(µ-trifluoroacetate) (3) upon solidification. Reversible depolymerization occurred readily upon heating, making 3 a useful vapor phase precursor itself. Tin(IV) tetrakis(trifluoroacetate) (5) was also found to be polymeric in the solid state, but it evaporated as a monomer over 130 °C lower than 3. This counterintuitive improvement in volatility by polymerization was possibly due to the large entropy change during sublimation, which offers a strategic new design feature for vapor phase deposition precursors.

Plasma-Enhanced Atomic Layer Deposition of Nanostructured Gold Near Room Temperature.

A plasma-enhanced atomic layer deposition (PE-ALD) process to deposit metallic gold is reported, using the previously reported Me3Au(PMe3) precursor with H2 plasma as the reactant. The process has a deposition window from 50 to 120 °C with a growth rate of 0.030 ± 0.002 nm per cycle on gold seed layers, and it shows saturating behavior for both the precursor and reactant exposure. X-ray photoelectron spectroscopy measurements show that the gold films deposited at 120 °C are of higher purity than the previously reported ones (<1 at. % carbon and oxygen impurities and <0.1 at. % phosphorous). A low resistivity value was obtained (5.9 ± 0.3 µΩ cm), and X-ray diffraction measurements confirm that films deposited at 50 and 120 °C are polycrystalline. The process forms gold nanoparticles on oxide surfaces, which coalesce into wormlike nanostructures during deposition. Nanostructures grown at 120 °C are evaluated as substrates for free-space surface-enhanced Raman spectroscopy (SERS) and exhibit an excellent enhancement factor that is without optimization, only one order of magnitude weaker than state-of-the-art gold nanodome substrates. The reported gold PE-ALD process therefore offers a deposition method to create SERS substrates that are template-free and does not require lithography. Using this process, it is possible to deposit nanostructured gold layers at low temperatures on complex three-dimensional (3D) substrates, opening up opportunities for the application of gold ALD in flexible electronics, heterogeneous catalysis, or the preparation of 3D SERS substrates.

Designing Stability into Thermally Reactive Plumbylenes.

Lead analogues of N-heterocyclic carbenes (NHPbs) are the least understood members of this increasingly important class of compounds. Here we report the design, preparation, isolation, structure, volatility, and decomposition pathways of a novel aliphatic NHPb: rac- N 2, N 3-di- tert-butylbutane-2,3-diamido lead(II) (1Pb). The large steric bulk of the tert-butylamido moieties and rac-butane backbone successfully hinder redox decomposition pathways observed for diamidoethylene and -ethane backbone analogues, pushing the onset of thermal decomposition from below 0 °C to above 150 °C. With an exceptionally high vapor pressure of 1 Torr at 94 ± 2 °C and excellent thermal stability among Pb(II) complexes, 1Pb is a promising precursor for the chemical vapor deposition (CVD) and atomic layer deposition (ALD) of functional lead-containing materials.

Passivation of Plasmonic Colors on Bulk Silver by Atomic Layer Deposition of Aluminum Oxide.

We report the passivation of angle-independent plasmonic colors on bulk silver by atomic layer deposition (ALD) of thin films of aluminum oxide. The colors are rendered by silver nanoparticles produced by laser ablation and redeposition on silver. We then apply a two-step approach to aluminum oxide conformal film formation via ALD. In the first step, a low-density film is deposited at low temperature to preserve and pin the silver nanoparticles. In the second step, a second denser film is deposited at a higher temperature to provide tarnish protection. This approach successfully protects the silver and plasmonic colors against tarnishing, humidity, and temperature, as demonstrated by aggressive exposure trials. The processing time associated with deposition of the conformal passivation layers meets industry requirements, and the approach is compatible with mass manufacturing.

The Chemistry of Inorganic Precursors during the Chemical Deposition of Films on Solid Surfaces.

The deposition of thin solid films is central to many industrial applications, and chemical vapor deposition (CVD) methods are particularly useful for this task. For one, the isotropic nature of the adsorption of chemical species affords even coverages on surfaces with rough topographies, an increasingly common requirement in microelectronics. Furthermore, by splitting the overall film-depositing reactions into two or more complementary and self-limiting steps, as it is done in atomic layer depositions (ALD), film thicknesses can be controlled down to the sub-monolayer level. Thanks to the availability of a vast array of inorganic and metalorganic precursors, CVD and ALD are quite versatile and can be engineered to deposit virtually any type of solid material. On the negative side, the surface chemistry that takes place in these processes is often complex, and can include undesirable side reactions leading to the incorporation of impurities in the growing films. Appropriate precursors and deposition conditions need to be chosen to minimize these problems, and that requires a proper understanding of the underlying surface chemistry. The precursors for CVD and ALD are often designed and chosen based on their known thermal chemistry from inorganic chemistry studies, taking advantage of the vast knowledge developed in that field over the years. Although a good first approximation, however, this approach can lead to wrong choices, because the reactions of these precursors at gas-solid interfaces can be quite different from what is seen in solution. For one, solvents often aid in the displacement of ligands in metalorganic compounds, providing the right dielectric environment, temporarily coordinating to the metal, or facilitating multiple ligand-complex interactions to increase reaction probabilities; these options are not available in the gas-solid reactions associated with CVD and ALD. Moreover, solid surfaces act as unique "ligands", if these reactions are to be viewed from the point of view of the metalorganic complexes used as precursors: they are bulky and rigid, can provide multiple binding sites for a single reaction, and can promote unique bonding modes, especially on metals, which have delocalized electronic structures. The differences between the molecular and surface chemistry of CVD and ALD precursors can result in significant variations in their reactivity, ultimately leading to unpredictable properties in the newly grown films. In this Account, we discuss some of the main similarities and differences in chemistry that CVD/ALD precursors follow on surfaces when contrasted against their known behavior in solution, with emphasis on our own work but also referencing other key contributions. Our approach is unique in that it combines expertise from the inorganic, surface science, and quantum-mechanics fields to better understand the mechanistic details of the chemistry of CVD and ALD processes and to identify new criteria to consider when designing CVD/ALD precursors.

Effect of the nature of the substrate on the surface chemistry of atomic layer deposition precursors.

The thermal chemistry of Cu(I)-sec-butyl-2-iminopyrrolidinate, a promising copper amidinate complex for atomic layer deposition (ALD) applications, was explored comparatively on several surfaces by using a combination of surface-sensitive techniques, specifically temperature-programmed desorption and x-ray photoelectron spectroscopy (XPS). The substrates explored include single crystals of transition metals (Ni(110) and Cu(110)), thin oxide films (NiO/Ni(110) and SiO2/Ta), and oxygen-treated metals (O/Cu(110)). Decomposition of the pyrrolidinate ligand leads to the desorption of several gas-phase products, including CH3CN, HCN and butene from the metals and CO and CO2 from the oxygen-containing surfaces. In all cases dehydrogenation of the organic moieties is accompanied by hydrogen removal from the surface, in the form of H2 on metals and mainly as water from the metal oxides, but the threshold for this chemistry varies wildly, from 270 K on Ni(110) to 430 K on O/Cu(110), 470 K on Cu(110), 500 K on NiO/Ni(110), and 570 K on SiO2/Ta. Copper reduction is also observed in both the Cu 2p3/2 XPS and the Cu L3 VV Auger (AES) spectra, reaching completion by 300 K on Ni(110) but occurring only between 500 and 600 K on Cu(110). On NiO/Ni(110), both Cu(I) and Cu(0) coexist between 200 and 500 K, and on SiO2/Ta a change happens between 500 and 600 K but the reduction is limited, with the copper atoms retaining a significant ionic character. Additional experiments to test adsorption at higher temperatures led to the identification of temperature windows for the self-limiting precursor uptake required for ALD between approximately 300 and 450 K on both Ni(110) and NiO/Ni(110); the range on SiO2 had been previously determined to be wider, reaching an upper limit at about 500 K. Finally, deposition of copper metal films via ALD cycles with O2 as the co-reactant was successfully accomplished on the Ni(110) substrate.

Surface chemistry of group 11 atomic layer deposition precursors on silica using solid-state nuclear magnetic resonance spectroscopy.

The use of chemical vapour deposition (CVD) and atomic layer deposition (ALD) as thin film deposition techniques has had a major impact on a number of fields. The deposition of pure, uniform, conformal thin films requires very specific vapour-solid reactivity that is largely unknown for the majority of ALD and CVD precursors. This work examines the initial chemisorption of several thin film vapour deposition precursors on high surface area silica (HSAS) using 13C, 31P, and quantitative 29Si nuclear magnetic resonance spectroscopy (NMR). Two copper metal precursors, 1,3-diisopropyl-imidazolin-2-ylidene copper (I) hexamethyldisilazide (1) and 1,3-diethyl-imidazolin-2-ylidene copper(I) hexamethyldisilazide (2), and one gold metal precursor, trimethylphosphine gold(III) trimethyl (3), are examined. Compounds 1 and 2 were found to chemisorb at the hydroxyl surface-reactive sites to form a ||-O-Cu-NHC surface species and fully methylated silicon (||-SiMe3, due to reactivity of the hexamethyldisilazane (HMDS) ligand on the precursor) at 150 °C and 250 °C. From quantitative 29Si solid-state NMR (SS-NMR) spectroscopy measurements, it was found that HMDS preferentially reacts at geminal disilanol surface sites while the copper surface species preferentially chemisorbed to lone silanol surface species. Additionally, the overall coverage was strongly dependent on temperature, with higher overall coverage of 1 at higher temperature but lower overall coverage of 2 at higher temperature. The chemisorption of 3 was found to produce a number of interesting surface species on HSAS. Gold(III) trimethylphosphine, reduced gold phosphine, methylated phosphoxides, and graphitic carbon were all observed as surface species. The overall coverage of 3 on HSAS was only about 10% at 100 °C and, like the copper compounds, had a preference for lone silanol surface reactive sites. The overall coverage and chemisorbed surface species have implications to the overall growth rate and purity of metal films grown with these precursors.

The effect of ALD-grown Al2O3 on the refractive index sensitivity of CVD gold-coated optical fiber sensors.

The combined effect of nanoscale dielectric and metallic layers prepared by atomic layer deposition (ALD) and chemical vapor deposition (CVD) on the refractometric properties of tilted optical fiber Bragg gratings (TFBG) is studied. A high index intermediate layer made up of either 50 nm or 100 nm layers of Al2O3 (refractive index near 1.62) was deposited by ALD and followed by thin gold layers (30-65 nm) deposited from a known single-source gold (I) iminopyrrolidinate CVD precursor. The fabricated devices were immersed in different surrounding refractive indices (SRI) and the spectral transmission response of the TFBGs was measured. Preliminary results indicate that the addition of the dielectric Al2O3 pre-coating enhances the SRI sensitivity by up to 75% but this enhancement is highly dependent on the polarization and dielectric thickness. In fact, the sensitivity decreases by up to 50% for certain cases. These effects are discussed with support from TFBG simulations and models, by quantifying the penetration of the evanescently coupled light out of the fiber through the various coating layers. Additional characterization studies have been carried out on these samples to further correlate the optical behaviour of the coated TFBGs with the physical properties of the gold and Al2O3 layers, using atomic force microscopy x-ray photoelectron spectroscopy and an ensemble of other optical and x-ray absorption spectroscopy techniques. The purity, roughness, and morphology of gold thin films deposited by CVD onto the dielectric-TFBG surface are also provided.

Absolute near-infrared refractometry with a calibrated tilted fiber Bragg grating.

The absolute refractive indices (RIs) of water and other liquids are determined with an uncertainty of ±0.001 at near-infrared wavelengths by using the tilted fiber Bragg grating (TFBG) cladding mode resonances of a standard single-mode fiber to measure the critical angle for total internal reflection at the interface between the fiber and its surroundings. The necessary condition to obtain absolute RIs (instead of measuring RI changes) is a thorough characterization of the dispersion of the core mode effective index of the TFBG across the full range of its cladding mode resonance spectrum. This technique is shown to be competitive with the best available measurements of the RIs of water and NaCl solutions at wavelengths in the vicinity of 1550 nm.