Tailored ablation processing of advanced biomedical hydroxyapatite by femtosecond laser pulses

The micromachining of hydroxyapatite (HAp) is highly important for orthopedics and dentistry, since human bone and teeth consist mainly of HAp. We demonstrate ultrashort Ti:sapphire laser ablation of HAp, using pulse-widths of 50 fs, 500 fs, and 2 ps at a wavelength of 820 nm and at 1 kpps. The crucial medical issue is to preserve the chemical properties of the machined (ablated) surface. If the chemical properties of HAp change, the human bone or tooth cannot re-grow after laser processing. Using X-ray photoelectron spectroscopy, we observe chemical properties of HAp ablated in air. The HAp is ablated at laser fluences of 3.2 J/cm² (6.4×10¹³ W/cm² at 50 fs), 3.3 J/cm² (6.6×10¹² W/cm² at 500 fs), and 9.6 J/cm² (4.8×10¹² W/cm² at 2 ps), respectively. As a result it is found that the ablated surface is unchanged after laser ablation over the pulse-width range used in this experiment. Received: 7 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +81-45/566-1533, E-mail: obara@obara.elec.keio.ac.jp     

Wavelength-modulation spectroscopy using a frequency-doubled current-modulated diode laser

We have studied atomic absorption in an argon discharge by wavelength-modulation spectroscopy with a frequency-doubled diode laser. The tunable wavelength-modulated radiation at 430 nm was generated by frequency doubling a current-modulated 860-nm diode laser in a KNbO₃ crystal. 2f-, 4f- and 6f-harmonic spectra as a function of diode laser modulation depth were measured on a Doppler-broadened sample of excited argon atoms produced in a capacitively coupled plasma chamber. Characterisation of the harmonic signals was accomplished. Minimum detectable absorbances of 7.7×10^-5 and 1.9×10^-4 based on a 3σ criterion (σ being the standard deviation of the noise) were estimated for 2f- and 4f-harmonic detection of the frequency-doubled radiation with a time constant of 0.1 s. The concentrations of argon in the 1s₄ state were found to be in the range of 3×10⁸ to 1.2×10¹¹ cm^-3 for the experimental conditions studied. Received: 25 February 2002 / Revised version: 4 April 2002 / Published online: 14 May 2002     

Diode laser slit-jet spectra and analysis of the fundamental of 1-chloro-1,1-difluoroethane (HCFC-142b)

High resolution infrared spectra (0.001 cm^-1) have been measured for mixtures of 1-chloro-1,1-difluoroethane in Ne, expanded in a supersonic planar jet. The ν ₇ fundamental has been analyzed for both isotopic species, CH₃CF₂ ³⁵Cl and CH₃CF₂ ³⁷Cl. A weak b-type component has been observed for the first time. Received 20 May 2002 / Received in final form 10 July 2002 Published online 24 September 2002 RID="a" ID="a"Also: Dipartimento di Scienze Fisiche Universitá di Napoli “Federico II” Complesso Universitario di M.S. Angelo, 80126 Napoli, Italy. e-mail: m.snels@isac.cnr.it     

Picosecond time-resolved nonresonant ionization detected IR spectroscopy on 7-azaindole dimer

The picosecond time-resolved IR spectrum of the 7-azaindole dimer has been measured by picosecond time-resolved nonresonant ionization detected IR spectroscopy. This new time-resolved technique was developed by combining nonresonant ionization detected IR (NID-IR) spectroscopy with tunable picosecond IR and UV lasers. The time-resolved NID-IR spectrum from 2 600 cm^-1 to 3 800 cm^-1 shows a drastic change from 1.5 ps to 11 ps time evolution. A mode-specific vibrational redistribution has been suggested. Received 14 May 2002 / Received in final form 11 June 2002 Published online 13 September 2002     

红外扫描和频振动光谱系统的激光线宽与光谱分辨率

本文报道了一个简化的利用可见光和红外光带宽来计算和频光谱分辨率的公式. 公式显示和频振动光谱的Voigt线宽可以通过振动模式的均匀线宽(洛伦兹线宽)、非均匀线宽(高斯线宽)、红外光与可见光的高斯线宽计算获得. 利用本实验室新搭建的频率分辨及偏振分辨的皮秒和频光谱系统验证了该公式的准确性. 实验结果显示,本激光系统获取的红外光的高斯线宽为1.5 cm^-1. 本激光系统的光谱分辨率约为4.6 cm^-1,结果与胆固醇单层膜光谱获取的光谱分辨率(3.5~5 cm^-1)基本一致.     

Sum frequency generation at 309 nm using a violet and a near-IR DFB diode laser for detection of OH

We have used a violet diode laser at 404 nm and a distributed feedback diode laser at 1320 nm to produce 0.8 nW of radiation at 309 nm by sum frequency generation in beta-barium borate. The UV radiation was tuned mode-hop-free over 30 GHz and used to detect OH radicals produced in a microwave discharge. By chopping the UV light at 500 Hz, we observed a concentration of 2×10¹² cm^-3 with a signal to noise ratio of 30:1. Received: 16 November 2001 / Revised version: 23 January 2002 / Published online: 14 March 2002     

Photoacoustic gas sensing employing fundamental and frequency-doubled radiation of a continuously tunable high-pressure CO2 laser

We present the first photoacoustic spectrometer for gas sensing employing both the fundamental and the frequency-doubled radiation of a continuously tunable high-pressure CO₂ laser with room temperature operation. A quasi-phase-matched diffusion-bonded GaAs crystal is used in the system for second-harmonic generation. A pulsed photoacoustic detection scheme with a non-resonant cell, equipped with an 80-microphone array, is employed. The wide continuous tuning range in the fundamental (9.2–10.7 μm) and the frequency-doubled (4.6–5.35 μm) regimes, together with the narrow linewidth of 540 MHz (0.018 cm^-1) for the 10-μm region and of 1050 MHz (0.0315 cm^-1) for the 5-μm region, allow the measurement of gas mixtures, individual species and isotope discrimination. This is illustrated with measurements on NO and CO₂. The measured isotope ratio ¹⁵ NO/¹⁴ NO=(3.58±0.55)×10^-3 agrees well with the literature (3.700×10^-3) and demonstrates the good selectivity of the system. Received: 30 April 2002 / Revised version: 10 June 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax: +41-1/633-1077, E-mail: sigrist@iqe.phys.ethz.ch     

Infrared-visible sum frequency generation (SFG) spectra of formate and formic acid on Ni(110) surface

Infrared-visible sum frequency generation (SFG) spectroscopy is applied to the study of structures of adsorbed formate and formic acid on the Ni(110) surface. Vibrational resonance by the CH stretching band of formate was observed at 2948 cm⁻¹ for p-polarized visible and infrared lights. Adsorption of formic acid on the formate-covered Ni(110) surface gave SFG peaks at 2968 and 2900 cm⁻¹ for both p- and s-polarized visible and p-polarized infrared light. These peaks were assigned to the CH and OH stretching modes, respectively. The orientation of the CH axis of adsorbed formate and formic acid is discussed.     

High-speed vertical-cavity surface-emitting laser (VCSEL) absorption spectroscopy of ammonia (NH<Subscript>3</Subscript>) near 1.54 μm

A single-frequency VCSEL has been used for the first time for high-resolution spectroscopy near 1.5 μm. The incorporated buried-tunnel-junction technology enabled the realization of a long-wavelength InGaAlAs/InP VCSEL with low threshold current (0.925 mA), high output powers (0.576 mW) and low series resistance (60 Ω). The high-speed tuning capability of the long-wavelength VCSEL was investigated and used to conduct high-speed absorption spectroscopy. The peak tuning speed was measured to be 3.4 cm^-1/μs and a 4.5-cm^-1-wide NH₃ spectrum was recorded in 2 μs. The VCSEL was used to measure highly resolved low-pressure spectra for pressures ranging from 9.6 mbar to 1 bar. The measured Doppler-broadened linewidth of 0.02 cm^-1 agrees within 3% with the theoretical calculations. The availability and various advantages of 1.3–2-μm single-frequency VCSELs as compared to edge-emitting diode lasers, such as a large current tuning range even at very high tuning frequencies, and low production costs, should significantly expand the application fields for near-infrared laser gas sensors. Received: 17 July 2002 / Revised version: 4 December 2002 / Published online: 12 May 2003 RID="*" ID="*"Corresponding author. Fax: +43-1/58801-15999, E-mail: Gerhard@Totschnig.com     

Powerful tunable infrared generation by stimulated Raman scattering

We report the generation of powerful infrared radiation continuously tunable between 14 000 and 2 300 cm^-1. The beam is either the output of a dye laser (with a linewidth of 0.07 cm^-1 and a full angle divergence of 0.2 mrd) or its Raman shifted components. We have obtained 20 to 60 MW peak power between 14 000 and 9 700 cm^-1, 5 to 20 MW between 9 700 and 5 500 cm^-1 and 0.5 to 2 MW between 5 500 and 2 300 cm^-1. As an application we measured the hyperpolarizability of some organic molecules.     

Laser-based photoacoustic ammonia sensors for industrial applications

An industrial trace-ammonia sensor based on photoacoustic spectroscopy and CO₂ lasers has been developed for measuring ammonia with a 1σ detection limit of 220 parts-per-trillion (ppt) in an integration time of 30 s. The instrument response time for measuring ammonia was 200 s, limited by adsorption effects due to the polar nature of ammonia. The minimum detectable fractional absorbance was 2.0×10^-7, and the minimum normalized detectable absorption coefficient for this system was 2.4×10^-7 W cm^-1/z. The 9R(30) transition of the CO₂ laser at 9.22 μm with 2 W of output power was used to probe the strong sR(5,K) multiplet of ammonia at the same wavelength. This sensor was demonstrated with an optically multiplexed configuration for simultaneous measurement in four cells. Received: 3 April 2002 / Revised version: 31 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-310/458-0171, E-mail: webber@pranalytica.com     

A laser infrared source of nanosecond pulses tunable from 1.4 to 22 μm

A reliable source of coherent ns pulses of infrared radiation continuously tunable between 1.4 and 22 m has been designed and built with the aim of developing a time-resolved infrared vibrational spectroscopy for species adsorbed on surfaces. The system is based on a Nd: YAG-laser and dye-laser combination which drive difference mixing processes in a sequence of nonlinear optical crystals (two LiNbO₃, and a CdSe or AgGaS₂). The system operates at MW peak power levels above 2500 cm^–1, at kW power levels from 1000–2500 cm^–1 and at 10–100 W levels down to 450 cm^–1. These power levels are certainly sufficient for spectroscopic purposes, and at shorter wavelengths molecular pumping and applications requiring high-power should be possible. Vibrational spectra of a monolayer of CO adsorbed on Pt in an electrochemical cell have been obtained in an initial application of this source.     

Optical study of RE 1 + x Ba 2 - x Cu 3 O 6 (RE = Nd, Sm) aaand YBa 2 Cu 3 O 6 in the mid infrared range

Infrared reflectance, and transmission measurements as well as Raman scattering have been used to study the RE_1+xBa_2-xCu₃O₆ (RE = Nd, Sm) and YBa₂Cu₃O₆ absorption bands in the 1100-1500 cm^-1 infrared range as a function of temperature and beam polarization. In addition to two-phonon absorption between 1100 and 1170 cm^-1, we observe excitations around 1400 cm^-1, occurring in oxygen rich enclosures within the samples, and assign them to an excitation involving two-phonons plus the 270 cm^-1 local mode related to Cu-O broken chains. Thus, the previously reported possible magnetic origin of the 1436 cm^-1 sharp absorption band in YBa₂Cu₃O₆ is contested. Received 14 February 2001 and Received in final form 12 April 2001     

Cavity-enhanced absorption spectroscopy with a rapidly swept diode laser

Cavity-enhanced absorption spectroscopy is explained in terms of the transmission function of a rapidly swept interferometer, and the integrated transmission is shown to be proportional to the cavity ringdown time. The technique is demonstrated on the b¹Σ_g ⁺-X³Σ_g ^-  (1,0) band in molecular oxygen at 687 nm using a tunable diode laser and a relative-ly high-Q optical cavity (finesse ≈4000). A detection limit of 3×10^-8 cm^-1 s^1/2 is achieved for a 0.8 cm^-1 scanning range. Received: 24 June 2002 / Revised version: 5 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: peverall@physchem.ox.ac.uk     

The Electronic and Infrared Absorption Spectra of Toluene-d

Abstract

The infrared and ultraviolet absorption spectra of toluene-d have been investigated for the first time in the regions 400 - 4000 cm^?1 and 2350 ?2750 A° respectively. The intense band at 2666.3 A°(37494 cm^?1) in the u.v. vapour absorption spectrum has been identified as the o,o band and others have been interpreted in terms of the three (519,632 and 785 cm^?1) ground state and the six (454,526,743,935,963 and 1180 cm^?1 excited state fundamentals. The correlation of the various frequencies of the ground and excited states of toluene and toluene-d has been done. The observed isotopic shift for toluene-d is 14 cm^?1.     

Sub-part-per-billion detection of nitric oxide in air using a thermoelectrically cooled mid-infrared quantum cascade laser spectrometer

Non-cryogenic, laser-absorption spectroscopy in the mid-infrared has wide applications for practical detection of trace gases in the atmosphere. We report measurements of nitric oxide in air with a detection limit less than 1 nmole/mole (<1 ppbv) using a thermoelectrically cooled quantum cascade laser operated in pulsed mode at 5.26 μm and coupled to a 210-m path length multiple-pass absorption cell at reduced pressure (50 Torr). The sensitivity of the system is enhanced by operating under pulsing conditions which reduce the laser line width to 0.010 cm^-1 (300 MHz) HWHM, and by normalizing pulse-to-pulse intensity variations with temporal gating on a single HgCdTe detector. The system is demonstrated by detecting nitric oxide in outside air and comparing results to a conventional tunable diode laser spectrometer sampling from a common inlet. A detection precision of 0.12 ppb Hz^-1/2 is achieved with a liquid-nitrogen-cooled detector. This detection precision corresponds to an absorbance precision of 1×10^-5 Hz^-1/2 or an absorbance precision per unit path length of 5×10^-10 cm^-1 Hz^-1/2. A precision of 0.3 ppb Hz^-1/2 is obtained using a thermoelectrically cooled detector, which allows continuous unattended operation over extended time periods with a totally cryogen-free instrument. Received: 1 May 2002 / Revised version: 6 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-978/663-4918, E-mail: ddn@aerodyne.com     

ZrO2 films deposited by photo-CVD at low temperatures

Zirconium oxide layers have been successfully deposited by photo-CVD at low temperatures. ZrO₂ growth was observed at temperatures as low as 100 °C. When deposited at 250 °C and above, these films exhibited a polycrystalline structure with a mixture of different crystal phases. Deposition at 300 °C was found to form moisture-free ZrO₂ films with a high refractive index of 2.1, a very low effective density of trapped electrons of ∼8.8×10⁸ cm^-2 and an interface trap density of 6.6×10⁹ cm^-2 eV^-1 being readily obtained. Received: 17 December 2001 / Accepted: 6 January 2002 / Published online: 3 June 2002     

Sensitive absorption measurements in the near-infrared region using off-axis integrated-cavity-output spectroscopy

A novel instrument that employs a high-finesse optical cavity as an absorption cell has been developed for sensitive measurements of gas mixing ratios using near-infrared diode lasers and absorption-spectroscopy techniques. The instrument employs an off-axis trajectory of the laser beam through the cell to yield an effective optical path length of several kilometers without significant unwanted effects due to cavity resonances. As a result, a minimum detectable absorption of approximately 1.4×10^-5 over an effective optical path of 4.2 km was obtained in a 1.1-Hz detection bandwidth to yield a detection sensitivity of approximately 3.1×10^-11 cm^-1 Hz^-1/2. The instrument has been used for sensitive measurements of CO, CH₄, C₂H₂ and NH₃. Received: 6 May 2002 / Revised version: 31 May 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-650/965-7074, E-mail: d.baer@lgrinc.com     

Removal of oxygen atoms from a SiO2 surface by incoherent vacuum ultraviolet excimer irradiation

We have demonstrated the non-thermal removal of oxygen atoms from an oxidized silicon surface (SiO₂) on a silicon wafer by the use of a low-power (0.3 mW cm^-2) incoherent vacuum ultraviolet (VUV) light source at 126 nm. X-ray photoelectron spectroscopy (XPS) has shown that a maximum Si concentration of 80% appears at the surface after a 20-h irradiation with 9.8 eV photons, as a result of oxygen removal from the SiO₂ matrix. The surface morphology, however, indicates no damage or melting on the surface even after the irradiation. Received: 15 April 2002 / Accepted: 17 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Permanent address: Nano-Tech Photon Inc., Shimotomita 4132-1, Shintomi, Miyazaki, 889-1404, Japan RID="**" ID="**"Corresponding author. Fax: +81-985/583-899, E-mail: kubodera@opt.miyazaki-u.jp     

Three-dimensional structuring of sapphire by sequential He+ ion-beam implantation and wet chemical etching

We present a method for the selective two- and three-dimensional patterning of sapphire using light ion-beam implantation to generate severe lattice damage to depths exceeding 1 μm and subsequent selective wet chemical etching of the damaged regions by hot H₃PO₄. C-cut sapphire crystals were implanted through contact masks using ion fluences of 1×10¹⁶ to 5×10¹⁷ He⁺/cm² and energies up to 400 keV. The etching process is characterized by a high selectivity and a rate of approximately 19 nm/min. Whereas an implantation that produces a continuously damaged pathway results in complete etching from the surface, sole in-depth implantation using only high-energy ions leads to under-etching of the crystalline surface layer. By a combination of these processes we have fabricated three-dimensional structures such as channels and bridges in sapphire. Received: 14 October 2002 / Accepted: 15 October 2002 / Published online: 26 February 2003 RID="*" ID="*"Corresponding author. Fax +41-21/693-3701, E-mail: aurelian.crunteanustanescu@epfl.ch