Analysis of femtosecond laser surface patterning on bulk single-crystalline diamond

Preliminary work is reported on 2-D and 3-D microstructures written directly with a Yb:YAG 1026 nm femtosecond (fs) laser on bulk chemical vapour deposition (CVD) single-crystalline diamond. Smooth graphitic lines and other structures were written on the surface of a CVD diamond sample with a thickness of 0.7mm under low laser fluences. This capability opens up the opportunity for making electronic devices and micro-electromechanical structures on diamond substrates. The fabrication process was optimised through testing a range of laser energies at a 100 kHz repetition rate with sub-500fs pulses. These graphitic lines and structures have been characterised using optical microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy. Using these analysis techniques, the formation of sp2 and sp3 bonds is explored and the ratio between sp2 and sp3 bonds after fs laser patterning is quantified. We present the early findings from this study and characterise the relationship between the graphitic line formation and the different fs laser exposure conditions. © 2012 Taylor & Francis.

Growth, Characterization, and Properties of Hybrid Graphene-Carbon Nanotube Films and Related Carbon Nanostructures

Graphene, first isolated in 2004 and the subject of the 2010 Nobel Prize in physics, has generated a tremendous amount of research interest in recent years due to its incredible mechanical and electrical properties. However, difficulties in large-scale production and low as-prepared surface area have hindered commercial applications. In this dissertation, a new material is described incorporating the superior electrical properties of graphene edge planes into the high surface area framework of carbon nanotube forests using a scalable and reproducible technology.

The objectives of this research were to investigate the growth parameters and mechanisms of a graphene-carbon nanotube hybrid nanomaterial termed “graphenated carbon nanotubes” (g-CNTs), examine the applicability of g-CNT materials for applications in electrochemical capacitors (supercapacitors) and cold-cathode field emission sources, and determine materials characteristics responsible for the superior performance of g-CNTs in these applications. The growth kinetics of multi-walled carbon nanotubes (MWNTs), grown by plasma-enhanced chemical vapor deposition (PECVD), was studied in order to understand the fundamental mechanisms governing the PECVD reaction process. Activation energies and diffusivities were determined for key reaction steps and a growth model was developed in response to these findings. Differences in the reaction kinetics between CNTs grown on single-crystal silicon and polysilicon were studied to aid in the incorporation of CNTs into microelectromechanical systems (MEMS) devices. To understand processing-property relationships for g-CNT materials, a Design of Experiments (DOE) analysis was performed for the purpose of determining the importance of various input parameters on the growth of g-CNTs, finding that varying temperature alone allows the resultant material to transition from CNTs to g-CNTs and finally carbon nanosheets (CNSs): vertically oriented sheets of few-layered graphene. In addition, a phenomenological model was developed for g-CNTs. By studying variations of graphene-CNT hybrid nanomaterials by Raman spectroscopy, a linear trend was discovered between their mean crystallite size and electrochemical capacitance. Finally, a new method for the calculation of nanomaterial surface area, more accurate than the standard BET technique, was created based on atomic layer deposition (ALD) of titanium oxide (TiO2).

Stimuli-Responsive Microneedle Arrays For On-Demand Drug Delivery

Pulsatile, or “on-demand”, delivery systems have the capability to deliver a therapeutic molecule at the right time/site of action and in the right amount (1). Pulsatile delivery systems present multiple benefits over conventional dosage forms and provide higher patient compliance. The combination of stimuli-responsive materials with the drug delivery capabilities of hydrogel-forming MN arrays (2) opens an interesting area of research. In the present work we describe, a stimuli-responsive hydrogel-forming microneedle (MN) array that enable delivery of a clinically-relevant model drug (ibuprofen) upon application of UV radiation (Figure 1A). MN arrays were prepared using a micromolding technique using a polymer prepared from 2-hydroxyethyl methacrylate (HEMA) and ethylene glycol dimethacrylate (EGDMA) (Figure 1B). The arrays were loaded with up to 5% (w/w) ibuprofen included in a light-responsible conjugate (3,5-dimethoxybenzoin conjugate) (2). The presence of the conjugate inside the MN arrays was confirmed by Raman spectroscopy measurements. MN arrays were tested in vitro showing that they were able to deliver up to three doses of 50 mg of ibuprofen after application of an optical trigger (wavelength of 365 nm) over a long period of time (up to 160 hours) (Figure 1C and 1D). The work presented here is a probe of concept and a modified version of the system should be used as UV radiation is shown to be the major etiologic agent in the development of skin cancers. Consequently, for future applications of this technology an alternative design should be developed. Based on the previous research dealing with hydrogel forming MN arrays a suitable strategy will be to use hydrogel-forming MN arrays containing a backing layer made with the material described in this work as the drug reservoir (2). Finally, a porous layer of a material that blocks UV radiation should be included between the MN array and the drug reservoir. Therefore radiation can be applied to the system without reaching the skin surface. Therefore after modification, the system described here interesting properties as “on-demand” release system for prolonged periods of time. This technology has potential for use in “on-demand” delivery of a wide range of drugs in a variety of applications relevant to enhanced patient care.

Surface modifications of nanocrystalline diamond films and their functionalization with phthalocyanines

Boron-doped diamond is a promising electrode material for a number of applications providing efficient carrier transport, a high stability of the electrolytic performance with time, a possibility for dye-sensitizing with photosensitive molecules, etc. It can be functionalized with electron donor molecules, like phthalocyanines or porphyrins, for the development of light energy conversion systems. For effective attachment of such molecules, the diamond surface has to be modified by plasma- or photo-chemical processes in order to achieve a desired surface termination. In the present work, the surface modifications of undoped and boron-doped nanocrystalline diamond (NCD) films and their functionalization with various phthalocyanines (Pcs) were investigated. The NCD films have been prepared by hot filament chemical vapor deposition (HFCVD) on silicon substrates and were thereafter subjected to modifications with O2 or NH3 plasmas or UV/O3 treatments for exchange of the H-termination of the as-grown surface. The effectiveness of the modifications and their stability with time during storage under different ambients were studied by contact angle measurements and X-ray photoelectron spectroscopy (XPS). Furthermore, the surface roughness after the modifications was investigated with atomic force microscopy (AFM) and compared to that of as-grown samples in order to establish the appearance of etching of the surface during the treatment. The as-grown and the modified NCD surfaces were exposed to phthalocyanines with different metal centers (Ti, Cu, Mn) or with different side chains. The results of the Pc grafting were investigated by XPS and Raman spectroscopy. XPS revealed the presence of nitrogen stemming from the Pc molecules and traces of the respective metal atoms with ratios close to those in the applied Pc. In a next step Raman spectra of Ti-Pc, Cu-Pc and Mn-Pc were obtained with two different excitation wavelengths (488 and 785 nm) from droplet samples on Si after evaporation of the solvent in order to establish their Raman fingerprints. The major differences in the spectra were assigned to the effect of the size of the metal ion on the structure of the phthalocyanine ring. The spectra obtained were used as references for the Raman spectra of NCD surfaces grafted with Pc. Finally, selected boron doped NCD samples were used after their surface modification and functionalization with Pc for the preparation of electrodes which were tested in a photoelectrochemical cell with a Pt counter electrode and an Ag/AgCl reference electrode. The light sources and electrolytes were varied to establish their influence on the performance of the dye-sensitized diamond electrodes. Cyclic voltammetry measurements revealed broad electrochemical potential window and high stability of the electrodes after several cycles. The open circuit potential (OCP) measurements performed in dark and after illumination showed fast responses of the electrodes to the illumination resulting in photocurrent generation.

Functional surface chemistry of carbon-based nanostructures

The recently discovered abilities to synthesize single-walled carbon nanotubes and prepare single layer graphene have spurred interest in these sp2-bonded carbon nanostructures. In particular, studies of their potential use in electronic devices are many as silicon integrated circuits are encountering processing limitations, quantum effects, and thermal management issues due to rapid device scaling. Nanotube and graphene implementation in devices does come with significant hurdles itself. Among these issues are the ability to dope these materials and understanding what influences defects have on expected properties. Because these nanostructures are entirely all-surface, with every atom exposed to ambient, introduction of defects and doping by chemical means is expected to be an effective route for addressing these issues. Raman spectroscopy has been a proven characterization method for understanding vibrational and even electronic structure of graphene, nanotubes, and graphite, especially when combined with electrical measurements, due to a wealth of information contained in each spectrum. In Chapter 1, a discussion of the electronic structure of graphene is presented. This outlines the foundation for all sp2-bonded carbon electronic properties and is easily extended to carbon nanotubes. Motivation for why these materials are of interest is readily gained. Chapter 2 presents various synthesis/preparation methods for both nanotubes and graphene, discusses fabrication techniques for making devices, and describes characterization methods such as electrical measurements as well as static and time-resolved Raman spectroscopy. Chapter 3 outlines changes in the Raman spectra of individual metallic single-walled carbon nantoubes (SWNTs) upon sidewall covalent bond formation. It is observed that the initial degree of disorder has a strong influence on covalent sidewall functionalization which has implications on developing electronically selective covalent chemistries and assessing their selectivity in separating metallic and semiconducting SWNTs. Chapter 4 describes how optical phonon population extinction lifetime is affected by covalent functionalization and doping and includes discussions on static Raman linewidths. Increasing defect concentration is shown to decrease G-band phonon population lifetime and increase G-band linewidth. Doping only increases G-band linewidth, leaving non-equilibrium population decay rate unaffected. Phonon mediated electron scattering is especially strong in nanotubes making optical phonon decay of interest for device applications. Optical phonon decay also has implications on device thermal management. Chapter 5 treats doping of graphene showing ambient air can lead to inadvertent Fermi level shifts which exemplifies the sensitivity that sp2-bonded carbon nanostructures have to chemical doping through sidewall adsorption. Removal of this doping allows for an investigation of electron-phonon coupling dependence on temperature, also of interest for devices operating above room temperature. Finally, in Chapter 6, utilizing the information obtained in previous chapters, single carbon nanotube diodes are fabricated and characterized. Electrical performance shows these diodes are nearly ideal and photovoltaic response yields 1.4 nA and 205 mV of short circuit current and open circuit voltage from a single nanotube device. A summary and discussion of future directions in Chapter 7 concludes my work.

The'cave' mineral oxammite: a high resolution thermogravimetry and Raman spectroscopic study

The thermal decomposition of natural ammonium oxalate known as oxammite has been studied using a combination of high resolution thermogravimetry coupled to an evolved gas mass spectrometer and Raman spectroscopy coupled to a thermal stage. Three mass loss steps were found at 57, 175 and 188°C attributed to dehydration, ammonia evolution and carbon dioxide evolution respectively. Raman spectroscopy shows two bands at 3235 and 3030 cm-1 attributed to the OH stretching vibrations and three bands at 2995, 2900 and 2879 cm-1, attributed to the NH vibrational modes. The thermal degradation of oxammite may be followed by the loss of intensity of these bands. No intensity remains in the OH stretching bands at 100°C and the NH stretching bands show no intensity at 200°C. Multiple CO symmetric stretching bands are observed at 1473, 1454, 1447 and 1431cm-1, suggesting that the mineral oxammite is composed of a mixture of chemicals including ammonium oxalate dihydrate, ammonium oxalate monohydrate and anhydrous ammonium oxalate.

Raman spectroscopic characteristics of phthalocyanine and naphthalocyanine in sandwich-type phthalocyaninato and porphyrinato rare earth complexes Part 5. – Raman spectroscopic characteristics of naphthalocyanine in mixed [tetrakis(4-tert-butylphenyl)porphyrinato]-(naphthalocyaninato) rare earth double-deckers

Raman spectra were recorded in the range 400–1800 cm−1 for a series of 15 mixed \[tetrakis(4-tert-butylphenyl)porphyrinato](2,3-naphthalocyaninato) rare earth double-deckers M(TBPP)(Nc) (M = Y; La–Lu except Pm) using laser excitation at 632.8 and 785 nm. Comparisons with bis(naphthalocyaninato) rare earth counterparts reveal that the vibrations of the metallonaphthalocyanine M(Nc) fragment dominate the Raman features of M(TBPP)(Nc). When excited with radiation of 632.8 nm, the most intense vibration appears at about 1595 cm−1, due to the naphthalene stretching. These complexes exhibit the marker Raman band for Nc•− as a medium-intense band in the range 1496–1507 cm−1, attributed to the coupling of pyrrole and aza stretching, while the marker Raman band of Nc2− in intermediate-valence Ce(TBPP)(Nc) appears as a strong band at 1493 cm−1 and is due to the isoindole stretchings. By contrast, when excited with radiation of 785 nm that is in close resonance with the main Q absorption band of the naphthalocyanine ligand, the ring radial vibrations at ca 680 and 735 cm−1 for MIII(TBPP)(Nc) are selectively intensified and are the most intense bands. For the cerium double-decker, the most intense vibration also acting as the marker Raman band of Nc2− appears at 1497 cm−1 with contributions from both pyrrole CC and aza CN stretches. The same vibrational modes show weak to medium intensity scattering at 1506–1509 cm−1 for MIII(TBPP)(Nc) and this is the marker Raman band of Nc•− when thus excited. The scatterings due to the Nc breathings, ring radial vibration, aza group stretchings, naphthalene stretchings, benzoisoindole stretchings and the coupling of pyrrole CC and aza CN stretchings in MIII(TBPP)(Nc) are all slightly blue shifted along with the decrease in rare earth ionic radius, confirming the effects of increased ring–ring interactions on the Raman characteristics of naphthalocyanine in the mixed ring double-deckers.

Raman spectroscopic study of vivianites of different origins

Raman spectroscopy has been used to study a selection of vivianites from different origins. A band is identified at around 3480 cm-1 whose intensity is sample dependent. The band is attributed to the stretching vibration of Fe3+ OH units which are formed through the autooxidation of the vivianite minerals either by self-oxidation or by photocatalytic oxidation according to the reaction: (Fe2+)3(PO4)2·8H2O + 1/2O2 (Fe2+)3– x(Fe3+)x(PO4)2(OH)x·(8–x)H2O in which some of the water of crystallization is converted to hydroxyl anions. Complexity of the OH stretching region through the overlap of broad bands is reflected in the water HOH deformation modes at 1660 cm–1. Using the infrared bands at 3281, 3105 and 3025 cm–1, hydrogen bond distances of 2.734(5), 2.675(2) and 2.655(2) Å are calculated. Vivianites are characterised by an intense band at 950 cm–1 assigned to the PO4 symmetric stretching vibration. Low Raman intensity bands are observed at ~1077, ~1050, 1015 and ~ 985 cm–1 assigned to the phosphate PO4 antisymmetric stretching vibrations. Multiple antisymmetric stretching vibrations are due to the reduced tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Two bands are observed at ~ 423 and ~ 456 cm–1 assigned to the2bending modes. For the vivianites four bands are observed at ~ 584, ~ 571, ~ 545 and ~ 525 cm–1 assigned to the 4modes of vivianite.

Thermal treatment of weddellite—a Raman and infrared emission spectroscopic study

Thermal transformations of natural calcium oxalate dihydrate known in mineralogy as weddellite have been undertaken using a combination of Raman microscopy and infrared emission spectroscopy. The vibrational spectroscopic data was complimented with high resolution thermogravimetric analysis combined with evolved gas mass spectrometry. TG–MS identified three mass loss steps at 114, 422 and 592 °C. In the first mass loss step water is evolved only, in the second and third steps carbon dioxide is evolved. The combination of Raman microscopy and a thermal stage clearly identifies the changes in the molecular structure with thermal treatment. Weddellite is the phase in the temperature range up to the pre-dehydration temperature of 97 °C. At this temperature, the phase formed is whewellite (calcium oxalate monohydrate) and above 114 °C the phase is the anhydrous calcium oxalate. Above 422 °C, calcium carbonate is formed. Infrared emission spectroscopy shows that this mineral decomposes at around 650 °C. Changes in the position and intensity of the C=O and C---C stretching vibrations in the Raman spectra indicate the temperature range at which these phase changes occur.

Raman spectroscopic study of the mixed anion mineral Yecoraite Bi5Fe3O9(Te4+O3)(Te6+O4)2•9H2O

Tellurates are rare minerals as the tellurate anion is readily reduced to the tellurite ion. Often minerals with both tellurate and tellurite anions in the mineral are found. An example of such a mineral containing tellurate and tellurite is yecoraite. Raman spectroscopy has been used to study this mineral, the exact structure of which is unknown. Two Raman bands at 796 and 808 cm-1 are assigned to the ν1 (TeO4)2- symmetric and ν3 (TeO3)2- antisymmetric stretching modes and Raman bands at 699 cm-1 are attributed to the the ν3 (TeO4)2- antisymmetric stretching mode and the band at 690 cm-1 to the ν1 (TeO3)2- symmetric stretching mode. The intense band at 465 cm-1 with a shoulder at 470 cm-1 is assigned the (TeO4)2- and (TeO3)2- bending modes. Prominent Raman bands are observed at 2878, 2936, 3180 and 3400 cm-1. The band at 3936 cm-1 appears quite distinct and the observation of multiple bands indicates the water molecules in the yecoraite structure are not equivalent. The values for the OH stretching vibrations listed provide hydrogen bond distances of 2.625 Å (2878 cm-1), 2.636 Å (2936 cm-1), 2.697 Å (3180 cm-1) and 2.798 Å (3400 cm-1). This range of hydrogen bonding contributes to the stability of the mineral. A comparison of the Raman spectra of yecoraite with that of tellurate containing minerals kuranakhite, tlapallite and xocomecatlite is made.

A Raman spectroscopic study of the uranyl mineral rutherfordine – revisited

The molecular structure of the uranyl mineral rutherfordine has been investigated by the measurement of the NIR and Raman spectra and complemented with infrared spectra including their interpretation. The spectra of the rutherfordine show the presence of both water and hydroxyl units in the structure as evidenced by IR bands at 3562 and 3465 cm-1 (OH) and 3343, 3185 and 2980 cm-1 (H2O). Raman spectra show the presence of four sharp bands at 3511, 3460, 3329 and 3151 cm-1. Corresponding molecular water bending vibrations were only observed in both Raman and infrared spectra of one of two studied rutherfordine samples. The second rutherfordine sample studied contained only hydroxyl ions in the equatorial uranyl plane and did not contain any molecular water. The infrared spectra of the (CO3)2- units in the antisymmetric stretching region show complexity with three sets of carbonate bands observed. This combined with the observation of multiple bands in the (CO3)2- bending region in both the Raman and IR spectra suggests that both monodentate and bidentate (CO3)2- units may be present in the structure. This cannot be exactly proved and inferred from the spectra; however, it is in accordance with the X-ray crystallographic studies. Complexity is also observed in the IR spectra of (UO2)2+ antisymmetric stretching region and is attributed to non-identical UO bonds. U-O bond lengths were calculated using wavenumbers of the 3 and 1 (UO2)2+ and compared with data from X-ray single crystal structure analysis of rutherfordine. Existence of solid solution having a general formula (UO2)(CO3)1-x(OH)2x.yH2O ( x, y  0) is supported in the crystal structure of rutherfordine samples studied.

Synthesis and characterisation of cobalt hydroxide, cobalt oxyhydroxide and cobalt oxide nanodiscs

Cobalt hydroxide, cobalt oxyhydroxide and cobalt oxide nanomaterials were synthesized through simple soft chemistry. The cobalt hydroxide displays hexagonal morphology with clear edges 20 nm long. This morphology and nanosize is retained through to cobalt oxide Co3O4 through a topotactical relationship. Cobalt oxyhydroxide and cobalt oxide nanomaterials were synthesized through oxidation and low temperature calcination from the as-prepared cobalt hydroxide. Characterisation of these cobalt-based nanomaterials were fully developed, including X-ray diffraction, transmission electron microscopy combined with selected area electron diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and thermal gravimetric analysis. Bonding of the divalent cobalt hydroxide from the oxyhydroxide and oxides by studying their high resolution XPS spectra for Co 2p3/2 and O 1s. Raman spectroscopy of the as-prepared Co(OH)2, CoO(OH) and Co3O4 nanomaterials characterised each material. The thermal stability of the materials Co(OH)2 and CoO(OH) were established. This research has developed methodology for the synthesis of cobalt oxide and cobalt oxyhydroxide nanodiscs at low temperatures.

A Review of the Vibrational Spectroscopic Studies of Arsenite, Antimonite, and Antimonate Minerals

This review focuses on the vibrational spectroscopy of the compounds and minerals containing the arsenite, antimonite and antimonate anions. The review collects and correlates the published data.

Optical absorption, infrared, Raman and EPR spectral studies on natural Iowaite mineral

Natural iowaite, magnesium–ferric oxychloride mineral having light green color originating from Australia has been characterized by EPR, optical, IR, and Raman spectroscopy. The optical spectrum exhibits a number of electronic bands due to both Fe(III) and Mn(II) ions in iowaite. From EPR studies, the g values are calculated for Fe(III) and g and A values for Mn(II). EPR and optical absorption studies confirm that Fe(III) and Mn(II) are in distorted octahedral geometry. The bands that appear both in NIR and Raman spectra are due to the overtones and combinations of water and carbonate molecules. Thus EPR, optical, and Raman spectroscopy have proven most useful for the study of the chemistry of natural iowaite and chemical changes in the mineral.