Microstructuring of diamond bulk by IR femtosecond laser pulses

We report the fabrication of graphitic microstructures in the bulk of chemical vapor deposited (CVD) diamond using 120-fs laser pulses at 800-nm wavelength. The nature of the laser-modified region and generation of mechanical stresses in the surrounding diamond is studied with Raman spectroscopy. A spontaneous growth of the laser-modified region from the focal plane towards the laser has been visualized in the process of multipulse irradiation with different pulse energies. The formation of discrete or continuous graphitized structures is revealed depending on the varied local laser intensity. The physical processes governing the appearance of separate graphitic globules and continuous extension of the graphitized region are discussed. Controlling the laser irradiation conditions permits us to fabricate graphitic wires with typical length of 150 μm and diameter of 1.5 μm. The longer, 300-ps pulses, as applied to laser microstructuring of the CVD diamond bulk, are found to be inappropriate due to the stronger influence of structural defects on the damage threshold, the noticeable fluctuation of the structure diameter over the length and the pronounced cracking of the surrounding diamond. PACS 42.62.-b; 61.80.Ba     

Picosecond-laser-induced structural modifications in the bulk of single-crystal diamond

Arrays of through laser-graphitized microstructures have been fabricated in type IIa single-crystal 1.2-mm-thick diamond plates by multipulse laser irradiation with 10-ps pulses at λ=532 nm wavelength. Raman and photoluminescence (PL) spectroscopy studies of the bulk microstructures have evidenced the diamond transformation to amorphous carbon and graphitic phases and the formation of radiation defects pronounced in the PL spectra as the self-interstitial related center, the 3H center, at 504 nm. It is found that the ultrafast-laser-induced structural modifications in the bulk of single-crystal diamond plates occur along {111} planes, known as the planes of the lowest cleavage energy and strength in diamond.     

Stress-induced phase transitions in diamond

A phase transformation in diamond into an intermediate carbon phase (ICP) was revealed in regions of maximal shear stress of diamond anvils. The transition was stimulated by additional stresses supplied to the compressed anvils with torque by a rotation of the anvil around the anvil's axis; maximal shear stress approached 55 GPa during the rotation. Creation of an ICP is considered as a mechanism of the stress-induced stability loss of the diamond structure. The characteristic Raman bands of ICP near 250, 500, 650–850 and 1050–1390 cm^?1 were observed in the failure regions.     

Physical and mechanical properties of C60 under high pressures and high temperatures

The physical and mechanical properties of a C₆₀ fullerene sample have been investigated under high pressure–high temperature conditions using a designer Diamond Anvil Cell. Electrical resistance measurements show evidence of C₆₀ cage collapse at 20 GPa, which leads to the formation of an insulating phase at higher pressure. Energy dispersive X-ray diffraction (EDXD) data indicated that the characteristic fcc reflections gradually decrease in intensity and eventually disappear above 28 GPa. A C₆₀ sample was laser-heated at a pressure of 35 GPa to a temperature of 1910±100 K and, subsequently, decompressed to ambient conditions. The photoluminescence spectra and the Raman spectrum of the pressure–temperature-treated sample were measured at a low temperature of 80 K. Raman peak at 1322.3 cm^?1 with full-width half-maximum of 2.9 cm^?1 was observed from the sample, which is attributed to the hexagonal diamond phase in the sample. The room temperature photoluminescence spectra showed a symmetric emission band centered in the red spectral range with a peak at 690 nm. The structural analysis of the pressure–temperature-processed C₆₀ sample using EDXD method showed strong internal structure orientation and a phase close to hexagonal diamond. Mechanical properties such as hardness and Young’s modulus were measured by nanoindentation technique and the values were found to be 90±7 and 1215±50 GPa, respectively and these values are characteristic of sp³-bonded carbon materials.     

Synthesis of Ge-Sn at high pressure and high temperature in a laser-heated diamond anvil cell

Ge–Sn compound is predicted to be a direct band gap semiconductor with a tunable band gap. However, the bulk synthesis of this material by conventional methods at ambient pressure is unsuccessful due to the poor solubility of Sn in Ge. We report the successful synthesis of Ge–Sn in a laser-heated diamond anvil cell (LHDAC) at ~7.6 GPa &; ~2000 K. In situ Raman spectroscopy of the sample showed, apart from the characteristic Raman modes of Ge TO (Г) and β-Sn TO (Г), two additional Raman modes at ~225 cm^?1 (named Ge–Sn₁) and ~133 cm^?1 (named Ge–Sn₂). When the sample was quenched, the Ge–Sn₁ mode remained stable at ~215 cm^?1, whereas the Ge–Sn₂ mode had diminished in intensity. Comparing the Ge–Sn Raman mode at ~225 cm^?1 with the one observed in thin film studies, we interpret that the observed phonon mode may be formed due to Sn-rich Ge–Sn system. The additional Raman mode seen at ~133 cm^?1 suggested the formation of low symmetry phase under high P–T conditions. The results are compared with Ge–Si binary system.     

Crystal → nematic phase transition in the liquid crystalline system 1‐isothiocyanato‐4‐(trans‐4‐propylcyclohexyl) benzene (3CHBT) probed by temperature‐dependent micro‐Raman study and DFT calculations

Raman spectra of 3CHBT in unoriented form were recorded at 14 different temperature measurements in the range 25–55 °C, which covers the crystal → nematic (N) phase transition, and the Raman signatures of the phase transition were identified. The wavenumber shifts and linewidth changes of Raman marker bands with varying temperature were determined. The assignments of important vibrational modes of 3CHBT were also made using the experimentally observed Raman and infrared spectra, calculated wavenumbers, and potential energy distribution. The DFT calculations using the B3LYP method employing 6‐31G functional were performed for geometry optimization and vibrational spectra of monomer and dimer of 3CHBT. The analysis of the vibrational bands, especially the variation of their peak position as a function of temperature in two different spectral regions, 1150–1275 cm⁻¹ and 1950–2300 cm⁻¹, is discussed in detail. Both the linewidth and peak position of the ( C H ) in‐plane bending and ν(NCS) modes, which give Raman signatures of the crystal → N phase transition, are discussed in detail. The molecular dynamics of this transition has also been discussed. We propose the co‐existence of two types of dimers, one in parallel and the other in antiparallel arrangement, while going to the nematic phase. The structure of the nematic phase in bulk has also been proposed in terms of these dimers. The red shift of the ν(NCS) band and blue shift of almost all other ring modes show increased intermolecular interaction between the aromatic rings and decreased intermolecular interaction between two  NCS groups in the nematic phase. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of crystal orientation on picosecond-laser bulk microstructuring and Raman lasing in diamond

In the paper we report on picosecond-laser bulk microstructuring and stimulated Raman scattering (SRS) in type IIa single-crystal diamond in the course of multipulse irradiation at λ=532 nm wavelength using an advanced ps-laser system equipped with additional setups for on-line video imaging and photoluminescence spectra measurements. The effect of crystal orientation (relative to the incident laser beam) on (i) optical breakdown thresholds, (ii) character of bulk modifications, and (iii) generation of stimulated Raman scattering in diamond during irradiation with picosecond pulses of different durations (τ ₁=10 ps and τ ₂=44 ps) is studied. It is shown that the processes of laser-induced breakdown in the bulk of diamond (at the backside of the crystals) and bulk microstructure growth are governed by the dielectric breakdown mechanism. It is found that generation of high-order stimulated Raman scattering in diamond crystals has a considerable effect on the threshold of laser-induced breakdown and bulk microstructuring. Conditions of the efficient SRS lasing are determined, depending on the pulse duration and the direction ([100] and [110]) of the laser beam incidence. A method of local temperature measurements in the bulk of diamond based on the Stokes-to-anti-Stokes intensity ratio in the recorded SRS spectra is proposed, its applicability to determine a “pre-breakdown” temperature of diamond during multipulse ps-laser irradiation is discussed.     

Low voltage electrodeposition of diamond like carbon (DLC)

Attempt has been made to deposit diamond like carbon (DLC) films from ethanol through electrodeposition at low voltages (80-300 V) at 1 mm interelectrode separation. The films were characterized by atomic force microscopy (AFM), Scanning electron microscopy (SEM), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy and Auger electron Spectroscopy (AES). AFM investigations revealed the grain sizes are of tens of nanometers. The films were found to be continuous, smooth and close packed. Presence of peaks at 2958, 2929 and 2869 cm⁻¹ in FTIR spectrum indicates the bonding states to be of predominantly sp³ type (C-H). Raman spectroscopy analysis revealed two broad bands at ∼1350 and ∼1570 cm⁻¹. The downshift of the G-band of graphite is indicative of presence of DLC. Analysis of the Raman spectra for the samples revealed an improvement in the film quality with increase in the voltage. Micro Raman investigations indicate the formation of diamond phase at the deposition potential of 80 V. The sp² contents the films calculated from Auger electron spectra were calculated and were found to be 31, 19 and 7.8% for the samples prepared at 80, 150 and 300 V, respectively. A tentative mechanism for the formation of DLC has been proposed. These results indicate the possibility of deposition of DLC at low voltage.     

Structural phenomena in glassy carbon induced by cobalt ion implantation

Glassy carbon (GC) was implanted by 150 keV Co⁺ ions to the doses of 1×10¹⁶ (low dose) and 1×10¹⁷ ions/cm² (high dose). The low dose implantation results in GC structure disordering with formation of amorphous carbon (a-C). Analysis of Rutherford backscattering (RBS) and Raman spectra has revealed 15 at.% of sp³-bonded C atoms in the a-C structure. The in-pane size of sp² clusters was estimated to be 1.1 nm. On the contrary, the high dose ion implantation results in ordering of the a-C structure. Content of the sp³ atoms in a-C was reduced to about 5% and, respectively, the in-plane sp² cluster size was increased up to 2.8 nm. Together with the a-C structure ordering the Raman spectra identifies formation of transpolyacetylene (TPA)-like chains after the high-dose Co⁺ implantation. In parallel, RBS suggests an enhanced diffusion of the implanted cobalt within the modified carbon layer. Correlation of the RBS and Raman results argues a driving role of cobalt diffusion in the TPA-like chains formation and a-C ordering. Great surface roughening observed after the high dose Co⁺ implantation suggests also the pronounced cobalt clustering causing large flux of “free volume” to the surface.     

Raman spectroscopy of melamine at high pressures up to 60 GPa

In this work, the Raman scattering of melamine was studied under high pressure up to 60 GPa. The behavior of the most intensive peaks of the Raman spectrum of melamine, 677 cm^?1 and 985 cm^?1 modes, and their line widths do not show any phase transition or indication of formation of sp ³ bonds. Comparing the behavior of the line width of the Raman peaks of graphite under pressure and that of melamine leads us to conclude that the s-triasine (C–N) ring is more rigid than the C–C graphite ring. High pressure results with melamine suggest that the direct phase transition g-C₃N₄ to dense C₃N₄ phase should occur above 60 GPa.     

A Vibrational Spectroscopic Study of the So-Called Healing Mineral Papagoite CaCuAlSi2O6(OH)3

ABSTRACT

Papagoite is a silicate mineral named after an American Indian tribe and was used as a healing mineral. Papagoite CaCuAlSi₂O₆(OH)₃ is a hydroxy mixed anion compound with both silicate and hydroxyl anions in the formula. The structural characterization of the mineral papagoite remains incomplete. Papagoite is a four-membered ring silicate with Cu²⁺ in square planar coordination.

The intense sharp Raman band at 1053 cm^?1 is assigned to the ν₁ (A _1g) symmetric stretching vibration of the SiO₄ units. The splitting of the ν₃ vibrational mode offers support to the concept that the SiO₄ tetrahedron in papagoite is strongly distorted. A very intense Raman band observed at 630 cm^?1 with a shoulder at 644 cm^?1 is assigned to the ν₄ vibrational modes.

Intense Raman bands at 419 and 460 cm^?1 are attributed to the ν₂ bending modes.

Intense Raman bands at 3545 and 3573 cm^?1 are assigned to the stretching vibrations of the OH units. Low-intensity Raman bands at 3368 and 3453 cm^?1 are assigned to water stretching modes. It is suggested that the formula of papagoite is more likely to be CaCuAlSi₂O₆(OH)₃ · xH₂O. Hence, vibrational spectroscopy has been used to characterize the molecular structure of papagoite.     

Vibrational Spectroscopy of the Borate Mineral Priceite—Implications for the Molecular Structure

ABSTRACT

Priceite is a calcium borate mineral and occurs as white crystals in the monoclinic pyramidal crystal system. We have used a combination of Raman spectroscopy with complimentary infrared spectroscopy and scanning electron microscopy with Energy-dispersive X-ray Spectroscopy (EDS) to study the mineral priceite. Chemical analysis shows a pure phase consisting of B and Ca only. Raman bands at 956, 974, 991, and 1019 cm^?1 are assigned to the BO stretching vibration of the B₁₀O₁₉ units. Raman bands at 1071, 1100, 1127, 1169, and 1211 cm^?1 are attributed to the BOH in-plane bending modes. The intense infrared band at 805 cm^?1 is assigned to the trigonal borate stretching modes. The Raman band at 674 cm^?1 together with bands at 689, 697, 736, and 602 cm^?1 are assigned to the trigonal and tetrahedral borate bending modes. Raman spectroscopy in the hydroxyl stretching region shows a series of bands with intense Raman band at 3555 cm^?1 with a distinct shoulder at 3568 cm^?1. Other bands in this spectral region are found at 3221, 3385, 3404, 3496, and 3510 cm^?1. All of these bands are assigned to water stretching vibrations. The observation of multiple bands supports the concept of water being in different molecular environments in the structure of priceite. The molecular structure of a natural priceite has been assessed using vibrational spectroscopy.     

Carbonization in boron-ion-implanted polymethylmethacrylate as revealed from Raman spectroscopy and electrical measurements

ABSTRACT

The results of Raman spectroscopy and electrical measurements of 40 keV boron-ion-implanted polymethylmethacrylate with ion doses from 6.25 × 10¹⁴ to 5.0 × 10¹⁶ ions/cm² are reported for the first time. The Raman spectra recorded in the 400–3800 cm^?1 range, showing the formation of new carbon–carbon bands for the as-implanted samples at higher ion doses (>10¹⁶ ions/cm²), are found to be an additional support for carbonization processes earlier revealed by slow positrons. The current–voltage dependences at 360 K testify also that the as-implanted samples examined with higher fluences (3.75 × 10¹⁶ and 5.0 × 10¹⁶ ions/cm²) have created a very thin conductive layer or conductive joints due to carbonization.     

Raman Spectroscopic Study of the Molybdate Mineral Szenicsite and Comparison with Other Paragenetically Related Molybdate Minerals

Abstract

The molybdate‐bearing mineral szenicsite, Cu₃(MoO₄)(OH)₄, has been studied by Raman and infrared spectroscopy. A comparison of the Raman spectra is made with those of the closely related molybdate‐bearing minerals, wulfenite, powellite, lindgrenite, and iriginite, which show common paragenesis. The Raman spectrum of szenicsite displays an intense, sharp band at 898 cm^?1, attributed to the ν₁ symmetric stretching vibration of the MoO₄ units. The position of this particular band may be compared with the values of 871 cm^?1 for wulfenite and scheelite and 879 cm^?1 for powellite. Two Raman bands are observed at 827 and 801 cm^?1 for szenicsite, which are assigned to the ν₃(E _g ) vibrational mode of the molybdate anion. The two MO₄ ν₂ modes are observed at 349 (B _g ) and 308 cm^?1 (A _g ). The Raman band at 408 cm^?1 for szenicsite is assigned to the ν₄(E _g ) band. The Raman spectra are assigned according to a factor group analysis and are related to the structure of the minerals. The various minerals mentioned have characteristically different Raman spectra.     

Surface-enhanced Raman spectroscopy of hexabenzobenzene,C24H12, an analogue of a graphene nanostructure

While large scale fabrication of graphene nanoribbons remains a challenge, there exist materials which can be fabricated in quantities such as hexabenzobenzene,HBZB, (C₂₄H₁₂) and which have a two-dimensional (2D) carbon structure similar to graphene nanostructures. Using a 632 nm laser, no Raman spectra could be obtained from the solid material because of a strong luminescence produced by the laser. However, surface-enhanced Raman spectroscopy enabled the measurement of some of the Raman active modes. The G and D modes, which are characteristic fingerprints of a 2D graphene structure, were observed at 1331 and 1600 cm^?1, respectively. Density functional theory at the B3LYP/6-31G^* level was used to calculate the minimum energy structure and the Raman active vibrational frequencies of HBZB. The calculated minimum energy structure was 2D having D_6h symmetry in agreement with the experimental structure in the liquid phase. The calculated frequencies were in good agreement with the measured values.     

A spectroscopic study of M@C82 metallofullerenes: Raman, far-infrared, and neutron scattering results

82 metallofullerenes have been studied at room temperature by Raman (for M=La, Y, Ce, Gd), far-infrared (FIR) (for M=La, Y, Ce), and inelastic neutron scattering (INS) (for M=La, Y) spectroscopy. Raman and FIR spectra suggest that these metallofullerenes have a common dominant, if not a single, structure of the C₈₂ cage and a similar bonding of the encapsulated metal ion, i.e. the bonding is primarily electrostatic and the metal atoms are in the same oxidation state (+3). The metal ion vibrations are located around 160 and 50 cm^-1. INS reveals no gap between internal vibrational and external vibrational and rotational modes in the range ∼50–200 cm^-1 as is typically observed for other fullerides and also predicted by our model calculations. Presumably this is due to strong intermolecular interactions between M@C₈₂ units in the bulk sample. The studied metallofullerenes are air sensitive, and degradation in air could be followed by changes in the Raman spectra. Received: 24 August 1997/Accepted: 26 September 1997     

Growth and annealing study of hydrogen-doped single diamond crystals under high pressure and high temperature

A series of diamond crystals doped with hydrogen is successfully synthesized using LiH as the hydrogen source in a catalyst-carbon system at a pressure of 6.0 GPa and temperature ranging from 1255 C to 1350 C.It is shown that the high temperature plays a key role in the incorporation of hydrogen atoms during diamond crystallization.Fourier transform infrared micro-spectroscopy reveals that most of the hydrogen atoms in the synthesized diamond are incorporated into the crystal structure as sp 3-CH 2-symmetric(2850 cm-1) and sp 3 CH 2-antisymmetric vibrations(2920 cm-1).The intensities of these peaks increase gradually with an increase in the content of the hydrogen source in the catalyst.The incorporation of hydrogen impurity leads to a significant shift towards higher frequencies of the Raman peak from 1332.06 cm-1 to 1333.05 cm-1 and gives rise to some compressive stress in the diamond crystal lattice.Furthermore,hydrogen to carbon bonds are evident in the annealed diamond,indicating that the bonds that remain throughout the annealing process and the vibration frequencies centred at 2850 and 2920 cm-1 have no observable shift.Therefore,we suggest that the sp 3 C-H bond is rather stable in diamond crystals.     

Raman spectral features of longer polyynes HC2 nH ({\sf n=4}–8) in SWNTs

Size-selected linear hydrocarbon molecules, polyynes HC_2nH, were contacted in solutions with single-wall carbon nanotubes (SWNTs) prepared from laser-ablated metal/carbon composite rods (Rh/Pt/C) to produce polyyne-encapsulating SWNTs, HC_2nH@SWNT(RhPt). New Raman spectral features were observed at 2120, 2061, 2017, 1982, and 1963 cm^-1 for five polyynes of n=4–8, respectively, and identified as the vibrational excitation of symmetric stretching modes of the molecules inside the SWNTs. The Raman spectra were compared with those observed for polyynes on Ag islands (SERS) and in solutions. The filling factor was investigated from the concentration dependence of the Raman intensity for HC₁₀H@SWNT(NiCo) to give an estimate of one polyyne molecule per ~350 carbon atoms of SWNTs, providing a picture for head-to-tale filling of aligned C₁₀H₂ molecules inside the SWNTs.     

Spectral analysis of the structure of ultradispersed diamonds

The structure of ultradispersed diamonds (UDD) is studied by spectral methods. The presence of diamond crystal phase in the UDD is found based on x-ray analysis and Raman spectra. The Raman spectra also show sp²-and sp³-hybridized carbon. Analysis of IR absorption spectra suggests that the composition of functional groups present in the particles changes during the treatment. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 524–528, July–August, 2008.     

Vibrational Assignment of 2-Benzoyl Pyridine and its 18O Labelled Isomer

Abstract

Vibrational spectra of 2-benzoyl pyridine and 2-benzoyl pyridine-¹⁸O have been recorded in the solid and molten state in the infrared (4000–100 cm^?1) and in the Raman (4000–50 cm^?1). Polarized Raman spectra in the molten state have also been measured. The assignment of the vibrational bands is performed using the group vibrational concept, isotopic shifts and polarization features of the normal modes.