Analysis of Carbon Materials with Infrared Photoacoustic Spectroscopy.

Measurement of infrared spectroscopy has emerged as a significant challenge for carbon materials due to the sampling problem. To overcome this issue, in this work, we performed measurements of IR spectra for carbon materials including C60, C70, diamond powders, graphene, and carbon nanotubes (CNTs) using the photoacoustic spectroscopy (PAS) technique; for comparison, the vibrational patterns of these materials were also studied with a conventional transmission method, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, or Raman spectroscopy. We found that the IR photoacoustic spectroscopy (IR-PAS) scheme worked successfully for these carbon materials, offering advantages in sampling. Interestingly, the profiles of IR-PAS spectra for graphene and CNTs exhibit negative bands using carbon black as the reference; the negative spectral information may provide valuable knowledge about the storage energy, production, structure, defect, or impurity of graphene and CNTs. Thus, this approach may open a new avenue for analyzing carbon materials.

Thermal reaction and luminescence of long-lived N 2D in N2 ice.

Photochemistry of an N2 ice and thermal reaction of the irradiated sample were studied with vacuum-ultraviolet (VUV) light from a synchrotron. Concurrent detection of infrared absorption and visible emission spectra provide evidence for the generation of energetic products N (2D) and N (2P) atoms, N2 (A) molecule and linear-N3 (l-N3) radical after excitation of icy N2 at 121.6 nm. Irradiation at 190 nm is shown to be an effective way to eliminate the l-N3 radical. After the photolysis and photoelimination of the l-N3, we initiate synthesis of l-N3 via the thermal ramping of the sample in temperature range 3.5 to 20 K. In addition, the emission from the N (2D) atom was observed during the thermal ramping process. These behaviors indicate that a long-lived N (2Dlong) atom is generated in the VUV-photolyzed N2 ice. A comparison of the variations of the visible emission of N (2D) and the infrared absorption of l-N3 with time indicates that the long-lived N (2Dlong) dominated the thermal synthesis of l-N3 The results have enhanced suggestion and understanding of the conversion for nitrogen species in cold astrophysical environments with VUV irradiation.

Using an ATR-FTIR Technique to Detect Pathogens in Patients with Urinary Tract Infections: A Pilot Study.

Urinary tract infections (UTIs) are a leading hospital-acquired infection. Although timely detection of causative pathogens of UTIs is important, rapid and accurate measures assisting UTI diagnosis and bacterial determination are poorly developed. By reading infrared spectra of urine samples, Fourier-transform infrared spectroscopy (FTIR) may help detect urine compounds, but its role in UTI diagnosis remains uncertain. In this pilot study, we proposed a characterization method in attenuated total reflection (ATR)-FTIR spectra to evaluate urine samples and assessed the correlation between ATR-FTIR patterns, UTI diagnosis, and causative pathogens. We enrolled patients with a catheter-associated UTI in a subacute-care unit and non-UTI controls (total n = 18), and used urine culture to confirm the causative pathogens of the UTIs. In the ATR-FTIR analysis, the spectral variation between the UTI group and non-UTI, as well as that between various pathogens, was found in a range of 1800-900 cm-1, referring to the presence of specific constituents of the bacterial cell wall. The results indicated that the relative ratios between different area zones of vibration, as well as multivariate analysis, can be used as a clue to discriminate between UTI and non-UTI, as well as different causative pathogens of UTIs. This warrants a further large-scale study to validate the findings of this pilot research.

Photoluminescence of optical windows excited with extreme ultraviolet radiation.

Upon excitation with extreme ultraviolet (EUV) radiation, optical windows CaF2 and sapphire emit strong photoluminescence (PL) in the ultraviolet region 200-400 nm. The spectral profiles of the windows observed in the PL spectra appear strongly dependent on their temperature. We suggest the use of PL spectra of CaF2 and sapphire excited with EUV light to indicate the temperature for EUV applications such as nano-photolithography technology in manufacturing semiconductor devices; potentially, the method is applicable to a wide range of radiation including the vacuum-ultraviolet (VUV) and EUV regions and in all fields.

Photoluminescence of diamond containing nitrogen vacancy defects as a sensor of temperature upon exposure to vacuum- and extreme-ultraviolet radiation.

Upon excitation with vacuum-ultraviolet (VUV) and extreme-ultraviolet (EUV) radiation, diamond with nitrogen vacancies (DNV) emits strong photoluminescence (PL) in the wavelength region of 550-800 nm. The spectral profiles of the DNV in the PL spectra appear to be strongly dependent on the temperature of the diamond. Moreover, all PL spectra intersect at one isosbestic point, 570 nm; this result is evidence that the NV0 and NV- defects in diamond interconvert with each other upon VUV and EUV radiation. We suggest the use of PL spectra of DNV excited with VUV or EUV light to indicate the temperature for applications such as in nano-photolithography technology for the manufacture of semiconductor devices.

Photolysis of O2 dispersed in solid neon with far-ultraviolet radiation.

Irradiation at 173 or 143 nm of samples of 16O2 or 18O2 in solid Ne near 4 K produced many new spectral lines in absorption and emission from the mid-infrared to the near-ultraviolet regions. The major product was ozone, O3, that was identified with its mid-infrared and near-ultraviolet absorption lines. Oxygen atoms were formed on photolysis of O2 and stored in solid neon until the temperature of a sample was increased to 9 K, which enabled their migration and combination to form O3 and likely also O2. O2 in five excited states and O in two excited states detected through the emission spectra indicate that complicated processes occurred in solid Ne after far-ultraviolet excitation. For the transition 1D2 → 3P1,2 of O, the lifetime was determined to be 5.87 ± 0.10 s; the lifetime of the upper state of an unidentified transition associated with an emission feature at 701.7 nm was determined to be 2.34 ± 0.07 s.

Thresholds of photolysis of O2 and of formation of O3 from O2 dispersed in solid neon.

Irradiation of O2 dispersed in solid Ne with ultraviolet light produced infrared absorption lines of O3 and emission lines from atomic O (1D2 → 3P1,2), molecular O2 (A' 3Δu → X 3Σg) and radical OH (A 2Σ+ → X 2ΠI) in the visible and near-ultraviolet regions. The threshold wavelength for the formation of O3 was determined to be 200 ± 4 nm, corresponding to energy 6.20 ± 0.12 eV, which is hence the threshold for dissociation of O2. The thresholds of emission from excited O (1D2), O2 (A' 3Δu) and OH (A 2Σ+) were all observed to be 200 ± 4 nm, the same as for the formation of O3 in this photochemical system. The results indicate that, once O3 was generated, it was readily photolyzed to produce the long-lived atom O (1D2). Further reactions of O (1D2) with O3 produced excited O2 (A' 3Δu); reaction with water yielded radical OH (A 2Σ+). These results enhance our understanding of the evolution of the transformation of oxygen and open a window for the understanding of complicated processes in the solid phase.

Ultraviolet and Infrared Spectra of Diboron in Solid Neon at 4 K.

Apart from products H, B, BH, BH2 and BH3 identified from their emission spectra in the UV/Vis region, photolysis of diborane(6) dispersed in solid neon at 4 K with far-ultraviolet light from a synchrotron led to observation of absorption line (0,0) of the electronic transition A 3 Σu- ←X 3 Σg- of B2 at 326.39 nm. Absorption lines (1,0) of 11 B2 , 11 B10 B and 10 B2 were recorded at 316.63, 316.40 and 316.15 nm, respectively. ΔG1/2 of state A 3 Σu- for 11 B2 , 11 B10 B and 10 B2 in solid neon are accordingly derived to be 945, 968 and 993 cm-1 , respectively. Weak lines (0,1) of 11 B2 at 29586 cm-1 and of 11 B10 B at 29560 cm-1 , corresponding to 1042±30 and 1068±30 cm-1 for vibrational modes in the electronic ground state, were recorded in emission. An absorption line recorded at 1066.5±0.5 cm-1 in infrared spectra after photolysis of either B2 H6 in Ne or B2 D6 with D2 in Ne is thus attributed to 11 B10 B.

Far-UV-Excited Luminescence of Nitrogen-Vacancy Centers: Evidence for Diamonds in Space.

The nitrogen-vacancy (NV) centers in diamond are among the most thoroughly investigated defects in solid-state matter; however, our understanding of their properties upon far-UV excitation of the host matrix is limited. This knowledge is crucial for the identification of NV as the carrier of extended red emission (ERE) bands detected in a wide range of astrophysical environments. Herein, we report a study on the photoluminescence spectra of NV-containing nanodiamonds excited with synchrotron radiation over the wavelength range of 125-350 nm. We observed, for the first time, an emission at 520-850 nm with a quantum yield greater than 20 %. Our results share multiple similarities with the ERE phenomena, suggesting that nanodiamonds are a common component of dust in space.

Infrared and Ultraviolet Spectra of Diborane(6): B2H6 and B2D6.

We recorded absorption spectra of diborane(6), B2H6 and B2D6, dispersed in solid neon near 4 K in both mid-infrared and ultraviolet regions. For gaseous B2H6 from 105 to 300 nm, we report quantitative absolute cross sections; for solid B2H6 and for B2H6 dispersed in solid neon, we measured ultraviolet absorbance with relative intensities over a wide range. To assign the mid-infrared spectra to specific isotopic variants, we applied the abundance of (11)B and (10)B in natural proportions; we undertook quantum-chemical calculations of wavenumbers associated with anharmonic vibrational modes and the intensities of the harmonic vibrational modes. To aid an interpretation of the ultraviolet spectra, we calculated the energies of electronically excited singlet and triplet states and oscillator strengths for electronic transitions from the electronic ground state.

Analysis of Nickel Defect in Diamond with Photoluminescence upon Excitation near 200 nm.

Photoluminescent (PL) spectra of synthetic diamond powders at temperatures between 10 and 300 K were excited with synchrotron radiation in the wavelength range 125-375 nm. Prominent spectral PL features were detected at 484.6 and 489.0 nm (2.559 and 2.535 eV), associated with nickel defect. During our measurement of PL excitation (PLE) spectra of Ni defect in diamond, we observed a distinct PLE line at 215 nm for the first time. We thereby suggest the use of UV-PL spectra excited in the region 200-220 nm to analyze and to identify nickel defect in diamonds.

Quantitative analysis of nitrogen defect N4 in diamond with photoluminescence excited in the 170-240 nm region.

Upon excitation at 170-240 nm, diamonds emit strong luminescence in wavelength range of 300-700 nm. The spectral features observed in the photoluminescence excitation (PLE) spectra show two vibrational progressions, A and B, related to nitrogen defects N2 and N4, respectively. We used PLE spectra excited in region 170-240 nm to identify the type of diamond and demonstrate quantitative analysis of the B center as a N4 nitrogen defect in diamonds; the least detectable concentration of the N4 nitrogen defect is about 13 ppb, and the sensitivity of PLE is about 30 times than that practicable with infrared absorption spectra.

Vacuum-ultraviolet photolysis of methane at 3 K: synthesis of carbon clusters up to C20.

Samples of pure methane and of methane dispersed in solid neon at 3 K subjected to irradiation at wavelengths less than 165 nm with light from a synchrotron yielded varied products that were identified through their infrared absorption spectra, including CH3, C2H2, C2H3, C2H4, C2H6, C4H2, C4H4, C5H2, C8H2, CnH with n = 1-5, and carbon chains Cn with n = 3-20. The efficiency of photolysis of methane and the nature of the photoproducts depended on the concentration of methane and the wavelength selected for irradiation; an addition of H2 into solid neon enhanced the formation of long carbon chains.

Production of N3 upon photolysis of solid nitrogen at 3 K with synchrotron radiation.

The photodissociation of gaseous molecular nitrogen has been investigated intensively, but the corresponding knowledge in a solid phase is lacking. Irradiation of pure solid nitrogen at 3 K with vacuum-ultraviolet light from a synchrotron produced infrared absorption lines of product l-N3 at 1657.8 and 1652.6 cm(-1). The threshold wavelength to generate l-N3 was determined to be (143.7±1.8) nm, corresponding to an energy of (8.63±0.11) eV. Quantum-chemical calculations support the formation of l-N3 from the reaction N2 +N2, possibly through an activated complex l-N4 upon photoexcitation with energy above 8.63 eV. The results provide a possible application to an understanding of the nitrogen cycle in astronomical environments.

Identification of nitrogen defects in diamond with photoluminescence excited in the 160-240 nm region.

Photoluminescence (PL) spectra of natural diamond powders of type IaAB at 300 and 13 K were excited with synchrotron radiation in the wavelength range of 150-260 nm. The spectral features observed in the excitation spectra at 13 K show four vibrational progressions related to nitrogen defects in diamond: A, B, B', and N3. Progression A has a spacing of 1258 ± 40 cm(-1), associated with the N2 (or A) center; progression B has a spacing of 1181 ± 40 cm(-1) and progression B' has a spacing of 744 ± 40 cm(-1) related to the N4 (or B) center; and progression N3 has a spacing of 1417 ± 40 cm(-1) associated with the N3 center. The PL of these defects comprise continuous emission with two broad lines with maxima of ∼420 and 469 nm at 300 K. Upon excitation with light at wavelengths of <200 nm, the distinct zero-phonon lines of N3 and N4 centers in diamond at a temperature of 13 K become prominent at 416.0 and 491.2 nm, respectively. The vibrational progressions in the photoluminescence excitation (PLE) spectra of N2, N3, and N4 centers in diamond of type IaAB at 13 K are identified for the first time. We suggest the use of PL spectra excited in the region of 160-240 nm to analyze and identify the type of diamond.

Analysis of nitrogen defects in diamond with VUV photoluminescence.

Various diamonds were analyzed with photoluminescence (PL) spectra excited with synchrotron radiation in the wavelength range 160-250 nm. The emission of type IaAB diamond begins near 300 nm and extends to 700 nm; two broad lines with maximums about 419 and 469 nm correspond to energies 2.96 and 2.64 eV, respectively. The spectral features observed in the PL excitation spectra show two vibrational progressions, A and B, related to nitrogen defects in diamond. Progression A has a spacing 1266 ± 20 cm(-1) and is associated with the N2 (or A) center of a nitrogen defect, whereas progression B has a spacing 1177 ± 20 cm(-1) related to the N4 (or B) center of a nitrogen defect. These vibrational progressions in PL excitation spectra of N2 and N4 centers in type IaAB diamond are here identified for the first time. We suggest the use of PL spectra excited in the region 170-240 nm to analyze and to identify the type of diamond.

Nitrogen-Vacancy Centers in Diamond for High-Performance Detection of Vacuum Ultraviolet, Extreme Ultraviolet, and X-rays.

Fluorescent nanodiamonds (FNDs) containing nitrogen-vacancy (NV) centers as built-in fluorophores exhibit a nearly constant emission profile over 550-750 nm upon excitation by vacuum-ultraviolet (VUV), extreme ultraviolet (EUV), and X-radiations from a synchrotron source over the energy (wavelength) range of 6.2-1450 eV (0.86-200 nm). The photoluminescence (PL) quantum yield of FNDs increases steadily with the increasing excitation energy, attaining a value as great as 1700% at 700 eV (1.77 nm). Notably, the yield curve is continuous, having no gap in the VUV to X-ray region. In addition, no significant PL intensity decreases were observed for hours. Applying the FND sensor to measure the absorption cross-sections of gaseous O2 over 110-200 nm and comparing the measurements with the sodium-salicylate scintillator, we obtained results in agreement with each other within 5%. The superb photostability and broad applicability of FNDs offer a promising solution for the long-standing problem of lacking a robust and reliable detector for VUV, EUV, and X-radiations.

Electronic and Vibrational Absorption Spectra of NH2 in Solid Ne.

Irradiation of ammonia dispersed in solid neon near 4 K with tunable far-ultraviolet light from a synchrotron yielded amidogen, NH2, and imidogen, NH, radicals as products. The electronic absorption spectra of amidogen radicals in isotopic variants NH2, NHD, and ND2 were recorded in the visible and near-ultraviolet regions after photolysis of NH3 and ND3. The infrared absorption lines of NH2 associated with vibration-rotational levels of vibrational modes ν1 at 3234.3 (00,0-10,1), 3244.9 (00,0-11,1), and 3249.3 cm-1 (00,0-11,0), and ν2 at 1498.7 (10,1-11,1), 1509.5 (11,0-10,1), 1516.5 (00,0-10,1), 1528.6 (00,0-11,1), and 1533.7 cm-1 (00,0-11,0) were unambiguously identified according to the results of experiments with deuterium isotopes. The 00,0-00,0 lines of ν1 and ν2 for NH2 were derived to be at 3213.5 and 1494.6 cm-1 in solid neon.

Absorption spectra in the vacuum ultraviolet region of small molecules in condensed phases.

With radiation from a synchrotron we measured the spectra of several small molecular species, in the solid phase at 10K, either pure--O2, NO, CO2, N2O, H2O and NH3--or, for NH3, also dispersed in Ar at molar ratio 1/250, from the onset of absorption in the ultraviolet region until the limits of transmission by crystalline LiF or solid Ar. In a quantitative treatment of spectral data, we fitted the total absorption profile divided by wavenumber to Gaussian curves of minimal number, and made tentative assignments of electronic transitions and vibrational structure by comparison with spectra of gaseous species. These results illuminate the nature of electronic spectra of samples in solid phases in the vacuum ultraviolet region.