Imaging Extreme Ultraviolet Radiation Using Nanodiamonds with Nitrogen-Vacancy Centers.

Extreme ultraviolet (EUV) radiation with wavelengths of 10-121 nm has drawn considerable attention recently for its use in photolithography to fabricate nanoelectronic chips. This study demonstrates, for the first time, fluorescent nanodiamonds (FNDs) with nitrogen-vacancy (NV) centers as scintillators to image and characterize EUV radiations. The FNDs employed are ∼100 nm in size; they form a uniform and stable thin film on an indium-tin-oxide-coated slide by electrospray deposition. The film is nonhygroscopic and photostable and can emit bright red fluorescence from NV0 centers when excited by EUV light. An FND-based imaging device has been developed and applied for beam diagnostics of 50 nm and 13.5 nm synchrotron radiations, achieving a spatial resolution of 30 µm using a film of ∼1 µm thickness. The noise equivalent power density is 29 µW/(cm2 Hz1/2) for the 13.5 nm radiation. The method is generally applicable to imaging EUV radiation from different sources.

Excited state photochemically driven surface formation of benzene from acetylene ices on Pluto and in the outer solar system.

NASA's New Horizons mission unveiled a diverse landscape of Pluto's surface with massive regions being neutral in color, while others like Cthulhu Macula range from golden-yellow to reddish comprising up to half of Pluto's carbon budget. Here, we demonstrate in laboratory experiments merged with electronic structure calculations that the photolysis of solid acetylene - the most abundant precipitate on Pluto's surface - by low energy ultraviolet photons efficiently synthesizes benzene and polycyclic aromatic hydrocarbons via excited state photochemistry thus providing critical molecular building blocks for the colored surface material. Since low energy photons deliver doses to Pluto's surface exceeding those from cosmic rays by six orders of magnitude, these processes may significantly contribute to the coloration of Pluto's surface and of hydrocarbon-covered surfaces of Solar System bodies such as Triton in general. This discovery critically enhances our perception of the distribution of aromatic molecules and carbon throughout our Solar System.

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.

Electroluminescence from h-BN by using Al2O3/h-BN multiple heterostructure.

Two-dimensional (2-D) hexagonal boron nitride (h-BN) has attracted considerable attention for deep ultraviolet optoelectronics and visible single photon sources, however, realization of an electrically-driven light emitter remains challenging due to its wide bandgap nature. Here, we report electrically-driven visible light emission with a red-shift under increasing electric field from a few layer h-BN by employing a five-period Al2O3/h-BN multiple heterostructure and a graphene top electrode. Investigation of electrical properties reveals that the Al2O3 layers act as potential barriers confining injected carriers within the h-BN wells, while suppressing the electrostatic breakdown by trap-assisted tunneling, to increase the probability of radiative recombination. The result highlights a promising potential of such multiple heterostructure as a practical and efficient platform for electrically-driven light emitters based on wide bandgap two-dimensional materials.

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.

Communication: vacuum ultraviolet photoabsorption of interstellar icy thiols.

Following the recent identification of ethanethiol in the interstellar medium (ISM) we have carried out Vacuum UltraViolet (VUV) spectroscopy studies of ethanethiol (CH3CH2SH) from 10 K until sublimation in an ultrahigh vacuum chamber simulating astrochemical conditions. These results are compared with those of methanethiol (CH3SH), the lower order thiol also reported to be present in the ISM. VUV spectra recorded at higher temperature reveal conformational changes in the ice and phase transitions whilst evidence for dimer production is also presented.

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.

Possible detection of hydrazine on Saturn's moon Rhea.

We present the first analysis of far-ultraviolet reflectance spectra of regions on Rhea's leading and trailing hemispheres collected by the Cassini Ultraviolet Imaging Spectrograph during targeted flybys. In particular, we aim to explain the unidentified broad absorption feature centred near 184 nm. We have used laboratory measurements of the UV spectroscopy of a set of candidate molecules and found a good fit to Rhea's spectra with both hydrazine monohydrate and several chlorine-containing molecules. Given the radiation-dominated chemistry on the surface of icy satellites embedded within their planets' magnetospheres, hydrazine monohydrate is argued to be the most plausible candidate for explaining the absorption feature at 184 nm. Hydrazine was also used as a propellant in Cassini's thrusters, but the thrusters were not used during icy satellite flybys and thus the signal is believed to not arise from spacecraft fuel. We discuss how hydrazine monohydrate may be chemically produced on icy surfaces.