Conductive and resistive nanocrystalline diamond films studied by Raman spectroscopy

This paper shows what structural properties of amorphous non-diamond phases in nanocrystalline diamond films are responsible for the transition from resistive to conductive films. The films incorporated with nitrogen, oxygen, and hydrogen are prepared by microwave plasma chemical vapor deposition using Ar-rich gas mixtures. The amount, composition, and bonding properties of non-diamond phases are studied mainly by Raman spectroscopy and compared with the electrical resistivity of the films. The addition of N₂ gas decreases the resistivity down to the order of 10^− 2 Ω cm for deposition temperatures above a threshold of ∼ 1100 K. Non-diamond phases for high n-type conductivity are characterized by graphitic components with improved sp² bond angle order for trivalent carbon atoms in addition to CN bonds. The addition of O₂ or H₂ gas promotes incorporation of oxygen or hydrogen into the films, not preferential etching of non-diamond phases. The resistivity increases or decreases largely by oxygen or hydrogen incorporation, respectively, then inversely changes by thermal annealing due to the deoxidization and dehydrogenation.     

Subgap photoluminescence spectroscopy of nanocrystalline diamond films

We report on the effect of ambient conditions and UV irradiation on the subgap photoluminescence of nanocrystalline diamond prepared by microwave plasma enhanced chemical vapour deposition. We measured the photoluminescence of self-supporting membranes of thickness about 290 nm with the grain size up to 40 nm under variable ambient conditions – pressure, temperature, air, nitrogen and helium atmospheres. We have found that intensity of photoluminescence of samples kept under low pressure increases during the time. The photoluminescence intensity of samples under low pressure depends on sample temperature with maximum at about 260 K. The photoluminescence increase can be enhanced substantially by UV irradiation (325 nm) of the sample under certain conditions: temperature greater than ~ 280 K, low pressure of ambient atmosphere. We interpret the experimental results in terms of desorption of water molecules and their interaction with the of individual diamond nanocrystals in the membrane.     

Heterogeneous diamond phases in compressed graphite studied by electron energy-loss spectroscopy

Chemical mapping imaged by electron energy-loss spectroscopy based on scanning transmission electron microscopy was conducted on a compressed graphite specimen containing different carbon allotropes (hexagonal diamond, cubic diamond, and graphite phases). This imaging process allows visualization of the complex spatial distribution of different diamond phases, and their coexistence was confirmed using dark field (DF) imaging. The chemical mapping images showed spatial distribution of local bonding state for hexagonal and cubic diamond phases in the whole specimen, while the DF images showed only a part of crystalline segments with long-range order. Thus, the chemical mapping method has an advantage for the purpose of observing locally the existence of individual carbon allotropes in the whole specimen. The size distribution of the hexagonal diamond phase is approximately 10–100 nm. These findings indicate that the compressing method can potentially synthesize ~ 100 nm large diamond phases.     

Estimating band gap of amorphous diamond and nanocrystalline diamond powder by electron energy loss spectroscopy

Electronic properties such as band gap and density of states were estimated by electron energy loss spectroscopy for amorphous diamond synthesized from C₆₀ fullerene by shock compression. The imaginary part of the dielectric function, ε₂, obtained showed that the magnitude of the gap was 3.5 to 4.5 eV, a little smaller than that of crystalline diamond (5.5 eV), and that excitation of interband transition was not observed at X and L points but only at Γ points. The density of states around the gap was rather broad. These characteristic electronic properties observed can be explained by the unique atomic configuration of this material examined by radial distribution function (RDF) analysis.     

Ultrafast photoluminescence spectroscopy of H- and O-terminated nanocrystalline diamond films

We use femtosecond photoluminescence spectroscopy to study the light-induced changes in the sub-gap energy states of nanocrystalline diamond samples (thickness ~ 500 and 1000 nm) prepared on a spectral-grade fused silica substrate by microwave plasma enhanced chemical vapour deposition technique. The decay of photoluminescence in the visible spectral interval excited by blue femtosecond light pulses (405 nm,70 fs) shows that photoexcited charge carrier dynamics depend strongly on the ambient air pressure and on the light irradiation by the laser pulses. Specifically, at lower ambient air pressure (0.5-300 Pa) the irradiation leads to the peak photoluminescence intensity increase and to its faster decay. At higher air pressures (> 600 Pa) the photoluminescence intensity slightly decreases with no change in decay rates. O- and H-termination of nanocrystalline diamond films had negligible effect on their photoluminescence dynamics. The photoluminescence decay curves are described very well by the power-law decay reflecting the importance of the carrier trapping in the dynamics. Based on our results we propose a model of surface and sub-surface structure of nanodiamond films.     

Spatially resolved near-infrared excited Raman spectroscopy of nanocrystalline diamond films

Scanning Raman spectroscopic measurements were performed on nanocrystalline diamond thin films with 0.5 μm lateral steps and excitation spot limited to 1 μm in diameter using 488 nm and 785 nm excitation wavelengths. The comparison of the spectra measured with different excitation energies showed that in contrast to the well-known five bands in the 488 nm excited Raman spectra of nanocrystalline diamond a number of narrow peaks appears in the spectra when using near-infrared excitation. The intensity and position of the latter vary when moving the excitation spot along the sample. The detailed analysis of the sequences showed that the 785 nm excited Raman spectroscopy allows the detection and identification of the Raman peaks arising from individual diamond crystallites of the nanocrystalline diamond films.     

Hydrogen adsorption on single-walled carbon nanotubes studied by core-level photoelectron spectroscopy and Raman spectroscopy

We have investigated the adsorption of atomic hydrogen on vertically aligned carbon nanotube (CNT) films using in situ synchrotron-radiation-based core-level (CL) photoelectron spectroscopy and Raman spectroscopy. From C 1s CL spectra, we identified a CL peak component due to C-H bonds of carbon atoms in single-walled carbon nanotubes (SWCNTs). We also found the suppression of π-plasmon excitation, indicating that the hydrogen adsorption deforms the bonding structure. Raman spectra of the SWCNT film indicated that the radial-breathing-mode intensities of SWCNTs decreased due to the adsorption-induced bonding-structure deformation. Moreover, the decrease for small-diameter SWCNTs was more severe than that for large-diameter SWCNTs. Our results strongly suggest that the hydrogen adsorption, which induces the structure deformation from sp² to sp³-like bonding, depends on the diameter of SWCNTs.     

Grazing angle reflectance spectroscopy of organic monolayers on nanocrystalline diamond films

The nanocrystalline diamond (NCD) layers were grown by the large area (linear plasma) MWCVD on polished silicon substrates with and without intermediate mirror-like metallic coatings. The optical reflectance and Raman spectroscopy in the ultraviolet, visible and near infrared region (UV-VIS-NIR) reveals the thickness and the optical quality of NCD layers. The modified grazing angle reflectance (GAR) spectroscopy is applied in the mid infrared region 800-4000/cm to detect the molecular vibrations (functional groups) at the functionalized NCD surface. The optical absorbance of functionalized NCD surface is evaluated from p-polarized reflectance spectra measured at Brewster angle of incidence (BAR) to eliminate the interference fringes. We report a significant enhancement of sensitivity of BAR using NCD growth on metal mirrors.     

Ambient contamination of poly-crystalline diamond surfaces studied by high-resolution electron energy loss spectroscopy and X-ray photoelectron spectroscopy

In this work we provide direct evidence of hydrogen, carbon and oxygen contamination of poly-crystalline diamond surfaces from ambient conditions and their thermal stability upon vacuum annealing. Deuterated diamond films were exposed to ambient conditions for ~ 3 months and then studied by high-resolution electron energy loss spectroscopy and X-ray photoelectron spectroscopy. Hydrocarbon contaminations posses at least two different binding states which desorb upon annealing to ~ 300 °C and ~ 600 °C. Oxygen contaminations gradually desorb upon annealing to 700–800 °C. It is shown that thermal desorption of contaminations creates sp² carbon atoms on the diamond film surface.     

Effect of XeF laser treatment on structure of nanocrystalline diamond films

Nanocrystalline diamond (NCD) films were deposited on Si substrates by microwave plasma-enhanced chemical vapor deposition (MPECVD) using methane/hydrogen/oxygen (30/169/0.2 sccm) as process gases. Subsequently a thin (0.33 μm) and a thick (1.01 μm) NCD films were irradiated with XeF excimer laser (λ = 351 nm) with 300 and 600 mJ cm^? 2 of energy densities in air. The NCD films became rougher after laser irradiations. Fraction of graphitic clusters decreased but oxygen content increased in the thin NCD film after laser irradiation. Opposite phenomena were observed for the thick NCD films. Effect of laser irradiation to oxygenation and graphitization of NCD films was correlated with structural properties of free surface and grain boundaries of the thin and thick NCD films.     

Protein adsorption dynamics in cation-exchange chromatography quantitatively studied by confocal laser scanning microscopy

A self-contained research system based on the technique of confocal laser scanning microscopy (CLSM) was put up to quantitatively analyze the dynamics of protein adsorption to porous cation exchanger by mathematical modeling. Bovine serum albumin adsorption to the cation exchanger SP Sepharose FF was performed by batch adsorption and micro-flow cell in which protein concentration in single absorbent was visualized by CLSM. The effects of ionic strength and the protein concentration in liquid phase (50 mmol/L acetate buffer, pH 5.0) on the adsorption dynamics were examined. The intraparticle concentration profile data experimentally obtained from CLSM were quantitatively analyzed by three diffusive mass transfer models (i.e., pore diffusion, surface diffusion and Maxwell-Stefan models (MSM)) in virtue of the attenuation equation for the CLSM visualization developed earlier. The nuance between the model simulations and experimental results of the developing protein distribution in a single adsorbent particle could thus be found out. Without salt addition to the buffer, the adsorption isotherm was strongly favorable, and the pore diffusion model (PorDM) and MSM gave similarly good simulations of the experiments, whereas the surface diffusion model was unreasonable in the model presumption. Moreover, it was observed that the experimentally obtained adsorption front was relative flatter as compared with the calculated results from the PorDM, which implied the possible existence of surface diffusion. With increasing salt concentration, the simulations became to deviate from the experiments. Especially, when the salt concentration approached 50 mmol/L, all the three mass transfer models could hardly give good simulation of the experiment. This was considered due to the difference in adsorption behavior between the fluorescence labeled and unlabeled proteins therein.     

Microfabrication of vacuum-sealed cavities with nanocrystalline and ultrananocrystalline diamond membranes and their characteristics

Vacuum-sealed cavities featuring diamond membranes are fabricated using plasma-activated direct bonding technology. A chemical mechanical polished (CMP) silicon dioxide interlayer, deposited on diamond with a high temperature oxide (HTO) process at 850 °C in a low pressure chemical vapor deposition (LPCVD) furnace, is employed for successful direct bonding and vacuum cavity formation. The circular cavities are defined on the thermally grown oxide of the phosphorus-doped Si wafer (4-in, < 100>, 1.2 Ω/sq) using reactive ion etching (RIE). The same microfabrication steps are applied for low residual stress (i.e. < 50 MPa) nanocrystalline (NCD) and ultrananocrystalline (UNCD) diamonds to determine and compare membrane characteristics. For both diamond types, successful microfabrication of membranes is demonstrated using the optimized process flow. Profilometer measurements of membrane deflection are compared with finite element modeling (FEM), and indicate a Young's modulus of 1000 GPa for NCD and 850 GPa for UNCD. Furthermore, FEM analysis suggests the residual stress of UNCD membrane is approximately 100 MPa tensile, whereas NCD one does not show any significant residual stress (< 50 MPa). Our results show that NCD is a more promising choice than UNCD as a membrane material for electromechanical transducers.     

Investigation of fatigue-type processes in polycrystalline diamond tools using Raman spectroscopy

Polycrystalline diamond (PCD) cylindrical tool-bits used in oil well drilling are susceptible to fracture due to the hostile environment of randomly occurring impact loads to which they are subjected. The fact that the tool-bits fail after repeated use suggests the possibility of fatigue type processes in PCD. The study of stress fields on the surface of the PCD thus becomes crucial in the quest to have extended lives for these tool-bits. Since the diamond Raman peak reveals both the nature and magnitude of the stress present in the material, this technique can be employed as a non-destructive measurement tool to investigate these stress fields. Raman stress measurements at room temperature were carried out using a 36 point mapping array in area close to the size of the PCD samples. The mapping points provided histograms of the magnitude and nature of these small individually stressed regions showing a general compressive stress for the lower numbers of fatigue cycles which deteriorates to a high proportion of tensile regions. The data are also illustrated by 2-D surface maps as an alternative mode of presentation again confirming the change from surface stresses being dominantly compressive to dominantly tensile with exposure to the higher numbers of fatigue cycles. Whereas a general compressive stress is desirable in the PCD layer as it inhibits the propagation of cracks, on the contrary tensile stresses facilitate the formation of cracks ultimately leading to catastrophic failure of the tool-bits.     

Improvements in CVD/CVI processes for optimizing nanocrystalline diamond growth into porous silicon

This paper reports a novel procedure to infiltrate nanocrystalline diamond films (NCD) on porous silicon (PS) substrate. The NCD/PS films resulted in a composite material, with great potential for electrochemical application, mainly due to its high active surface area. The Hot Filament Chemical Vapor Deposition reactor was changed to Hot Filament Chemical Vapor Infiltration reactor in order to grow NCD films infiltrated into deep holes of PS substrate. This procedure allowed the infiltration of the reacting gases into the porous structure where the nucleation takes place, followed by the coalescence and film formation at pore bottoms and walls. In this configuration an additional entrance of CH₄ was located next to the PS substrate using two distinct positions called “underneath” and “above”, with the use of the additional flow accurately underneath or above of the samples. In general, the combination of these two configurations with additional carbon sources provided NCD film infiltration in PS substrate with success with only 60 min of growing time. Particularly, the films obtained from the positions called “above” presented the best morphology, with high quality and crystallinity, confirmed from its scanning electron microscopy, Raman scattering spectroscopy and high resolution X-ray diffraction spectra, respectively.     

The correlation between surface conductivity and adsorbate coverage on diamond as studied by infrared spectroscopy

A high-resolution analysis of CH vibrational modes on a single crystal diamond(100) surface using Fourier-transform infrared (FTIR) spectroscopy in combination with conductivity measurements is reported. On a plasma-hydrogenated diamond(100) surface, the IR spectra measured in the multiple internal reflection mode reveal three absorption lines. Two of them at 2921 and 2854 cm⁻¹ vanish in air at an annealing temperature of 190°C and are assigned to the antisymmetric and symmetric CH₂ stretching modes of a physisorbed hydrocarbon species, respectively. The third band at 2897 cm⁻¹ has a width of 16 cm⁻¹, is stable up to 230°C and is associated with the stretching frequency of C₂H₂ monohydride units on the C(100) 2×1:2H surface. Upon annealing in air at temperatures lower than 200°C, the surface conductivity is reversibly reduced by up to five orders of magnitude. After cooling down to room temperature, it recovers the value of 1×10⁻⁵ Ω⁻¹ measured immediately after the plasma hydrogenation with a time constant of several days. Annealing at 230°C destroys the surface conductivity irreversibly and yields conductance values below the measurement limit of 5×10⁻¹² Ω⁻¹. We show that the chemisorbed hydrogen in the C₂H₂ configuration, together with at least one physisorbed species, is responsible for the surface conductivity of hydrogen-terminated diamond(100).     

Low temperature processes in a bituminous coal studied by in situ electron spin resonance spectroscopy

The free spin concentrations in a whole and extracted bituminous coal, were measured by electron spin resonance spectroscopy (e.s.r.). In situ high temperature measurements of spin populations were made with a novel flow cell which enables volatiles formed to be swept clear of the e.s.r. active zone. The development of the spin population profile with temperature was measured up to 400 °C, and three regions, delimiting different processes taking place in the coal, can be defined. The interpretation of these profiles was made in conjunction with thermogravimetric and differential thermal analysis. It is suggested that the regions, in order of ascending temperature, correspond with desorption, recombination and thermal bond-breaking processes, respectively. A very simple model of coal pyrolysis suggests that more bonds are broken than are detected by e.s.r., in agreement with the estimated lifetimes of radicals expected to be formed on pyrolysis. These calculations, and the stability of spin concentration measurements over long time periods, cast doubt on efforts to establish a direct relationship between e.s.r. spin counts and the pyrolytic reactivity of the coal.     

Design of luminescent inorganic materials: new photophysical processes studied by optical spectroscopy

Recent spectroscopic results in the emerging area of transition-metal NIR-to-visible upconversion are related. The examples of Ti(2+)-, Re(4+)-, and Os(4+)-doped materials showing upconversion illustrate GSA/ESA, GSA/ETU, and photon avalanche multiphoton excitation mechanisms, respectively. Strategies for manipulation of such upconversion processes using the spectroscopic or magnetic properties of the host material are described. High-resolution low-temperature continuous-wave absorption and emission and time-resolved emission experiments combine to yield information about energy splittings, intensities, and excited-state dynamics, and assist in the design and development of luminescent materials showing novel multiphoton excitation properties.     

Relaxation dynamics of Au25L18 nanoclusters studied by femtosecond time-resolved near infrared transient absorption spectroscopy

The relaxation dynamics of electronically excited [Au(25)(SR)(18)](q), where q = 0 or -1 and SR = S(CH(2))(2)Ph, were studied using femtosecond time-resolved transient absorption spectroscopy. Nanoclusters excited by 400 nm light were probed using temporally delayed broad-bandwidth continuum probe pulses. Continuum pulses were generated in both the visible and near infrared (NIR) spectral regions, providing access to a wide range of transient spectral features. The use of NIR probe pulses allowed the relaxation dynamics of the excited states located near the HOMO-LUMO energy gap to be monitored in the probe step via the sp ← LUMO and sp ← LUMO+1 transitions. These NIR measurements yielded excited state absorption (ESA) data that were much less congested than the typical visible transient spectrum. For the neutral nanocluster, the time-domain data were composed of three components: (1) a few-picosecond decay, (2) a slower decay taking a few hundred picoseconds and (3) a non-decaying plateau function. Component 1 reflected energy relaxation to semi-ring ligand states; component 2 was attributed to relaxation via a manifold of states located near the HOMO-LUMO energy gap. Component 3 arose from slow radiative recombination. The dynamics of the anion depended upon the identity of the excited state from which the particle was relaxing. The LUMO+1 state of the anion exhibited relaxation dynamics that were similar to those observed for the neutral nanocluster. By comparison, the time-domain data observed for the LUMO state contained only two components: (1) a 3.3 ± 0.2 ps decay and (2) a 5 ± 1 ns decay. The amplitude coefficients of each component were also analyzed. Taken together, the amplitude coefficients and lifetimes were indicative of an activation barrier located approximately 100 meV above the HOMO-LUMO energy gap, which mediated a previously unobserved excited state decay process for [Au(25)(SR)(18)](0). These data suggested that NIR ESA measurements will be instrumental in describing the relaxation processes of quantum-confined nanoclusters.     

Surface defects induced by in-situ annealing of hydrogenated polycrystalline diamond studied by high resolution electron energy loss spectroscopy

Plasma hydrogenation of polycrystalline diamond films results in a fully hydrogenated well-ordered diamond surface and etching of the amorphous phase located at grain boundaries. Vacuum annealing to 1000 °C followed by in-situ hydrogenation by thermal activated hydrogen of the bared diamond surface results in the formation of sp³-CH_x adsorbed groups located on the top surface. Annealing of the in-situ hydrogenated surface to 600 °C results in desorption of these species and partial reconstruction of the film surface. Some irreversible surface degradation was detected in the in-situ annealed and hydrogenated surface compared to the state of the surface obtained upon plasma hydrogenation.     

Confinement effects in irradiation of nanocrystalline diamond

Swift heavy ion irradiation does not generate amorphous tracks in diamond, contrary to what happens in graphite or in diamond-like carbon. Since nanocrystalline diamond is of interest for several technological applications we investigate the reason for this difference, by means of large scale atomistic simulations of ion tracks in nanocrystalline diamond, using a thermal spike model, with up to 2.5 million atoms, and grain sizes in the range 5–10 nm. We conclude that tracking can be achieved under these conditions, when it is absent in single crystal diamond: for 5 nm samples the tracking threshold is below 15 keV/nm. Point defects are observed below this threshold. As the energy loss increases the track region becomes amorphous, and graphitic-like, with predominant sp² hybridization. This higher sensitivity to irradiation can be related to a very large decrease in thermal conductivity of nanocrystalline diamond, due to grain boundary confinement of the heat spike which enhances localized heating of the lattice.