便携式高光谱感应器在有机胶料无损分析中的应用初探

文物和艺术品的无损分析是文化遗产科技保护的重点和难点。该研究使用了一种遥感领域的地物光谱仪--便携式全波段高光谱感应器（Analytical Spectral Devices FieldSpec FR Pro 3）分析文物中常用的有机胶料。这种高光谱感应器可以在0.2 s内获得一个350～2 500 nm全波段反射光谱,其波段涵盖了可见光、近红外和短波红外三个区域。该研究选取蛋黄、兔皮胶、亚麻籽油三种中西方古代、现代常用的胶结物作为研究对象,分别以单组分、与不同颜料的混合物两种形式来验证该设备无损分析的可靠性和实用性。首先按照传统绘画技法,使用四种不同颜料与上述胶结物的组合制备彩绘样品。待样品完全干燥后,使用探头直接接触法获取光谱信息,并利用相关软件进行数据处理。实验发现,由于物化本质不同,这三种胶结物的反射光谱在波长1 100～2 400 nm范围内的特征信息差异最为显著。当胶料与无机颜料混合后,这三种有机物的吸收峰位置相对于单组分出现了相同的三种变化：（1）波长1 507 nm处的肩峰消失;（2）波长约为1 943～1 922 nm处的宽峰偏移;（3）位于波长2 050 nm处的原N-H伸展和弯曲合频峰向右移动了约(20～2 070 nm)。值得注意的是,C-H合频和倍频峰在单组分与混合物光谱中的位置保持一致。这一系列谱图变化规律使得从混合物中鉴别胶料具有了可能性。尽管在某些情况下,和其他光谱分析技术类似,混合后无机颜料和有机胶料吸收峰之间的相互干扰会影响胶料的鉴定,但利用其一阶导数光谱能够协助各组分的准确表征。结果表明,该高光谱感应器能够有效鉴别有机胶料;这种快速、无损的分析方法不仅在实验室成分分析中具有可行性,而且其便携的特点也适用于文物保护与修复现场的快速分析,具有较好的实用性。     

Highlights of synchrotron radiation

The applications of the electromagnetic radiation generated by relativistic electrons circulating in synchrotrons and storage rings have rapidly extended into many scientific disciplines. This article first briefly reviews the history of synchrotron radiation, and recapitulates its properties. The available sources are listed, and some aspects of the facilities that are required to make use of the radiation are discussed, with particular emphasis on the optical elements. Several noteworthy examples of scientific research conducted with synchrotron radiation are described. These are drawn principally from the X-ray region, and comprise X-ray fluorescence, small-angle scattering, powder profile refinement, extended X-ray absorption fine structure, topography, time-resolved spectroscopy, and VUV and photoelectron spectroscopy of solids. In conclusion, a few topics are mentioned relating to the future expansion and application of synchrotron radiation research facilities.     

Vacuum ultraviolet spectroscopy of U:LiF, Cu, and U:NaF, Cu crystals

Luminescence and excitation spectra of doped LiF and NaF crystals are studied by time-resolved optical and luminescent vacuum ultraviolet (VUV) spectroscopy (2–40 eV energy range, T=10–295 K) with the use of synchrotron radiation of the X-ray and the VUV ranges and pulsed electron beams. Spectral kinetic parameters of luminescence and energies of excited states of U⁶⁺ ions are determined. The dominant role of the electron-hole mechanism for energy transfer to impurity centers is established. The effect of multiplication of electronic excitations is clearly manifested for E > 25 eV in NaF:U, Cu crystals and determines their high scintillation yield (137% relative to Tl:CsI when detected in the current regime).     

Time-resolved luminescence of LaBr3-Ce scintillation crystals upon selective UV-VUV-XUV excitation

The time-resolved photoluminescence (PL) of LaBr₃-Ce scintillation spectrometric crystals produced in Russia is measured upon excitation using synchrotron radiation with photon energies of 3.7–21 and 45–290 eV at temperatures of 295 and 7.5 K. The PL spectra and decay curves are measured for excitation in the transparency range, at the edge of fundamental absorption, at the interband transitions, and in the range of inner-shell absorption. It is demonstrated that the PL yield is not proportional to the excitation energy, and that the PL decay curves are modified in the range of photoionization of the 3d (Br) and 4d (La) inner shells and, especially, in the range of giant resonance.     

Time-resolved luminescence of complex wide-gap oxide crystals under inner-shell excitation

In order to investigate the soft X-ray energy transformation in oxide detectors the optical spectra of several wide-gap oxide crystals were analyzed. The time-resolved luminescence (2.5–10.5 eV) and luminescence excitation spectra (50–200 and 500–630 eV) as well as decay kinetics of luminescence at 10 and 295 K were recorded using the synchrotron radiation from BW3 channel (HASYLAB, DESY). Several analogous features were discovered in the excitation spectra of both intrinsic self-trapped exciton luminescence and recombination luminescence for BeO, BeAl₂O₄, Be₂SiO₄ and AlPO₄ crystals under inner-shell excitation. Simultaneously, the excitation of Ce³⁺-luminescence in scintillating Be₂La₂O₅-Ce crystals significantly differs.     

X-ray absorption investigations of copper resinate blackening in a XV century Italian painting

Investigations of the darkening phenomenon of copper resinate observed in a XV century easel painting were carried out by X-ray absorption spectroscopy (XAS) at the GILDA beamline of the European synchrotron radiation facility (ESRF, Grenoble, France). X-ray absorption near edge structure and extended X-ray absorption fine structure (EXAFS) measurements were collected at the Cu K-edge on an original painting sample, as well as on fresh pigment standards and on painting models. The study was aimed at providing structural information of the oxidation states and the local chemical environment (neighbouring atoms and bond distances) of copper in the unaltered and blackened pigments in order to elucidate the discoloration mechanism. Complementary information on optical and molecular properties of copper resinate were obtained by UV-vis and Fourier transform infrared spectroscopies. EXAFS analysis evidenced that the local chemical environment of Cu in copper resinate can be described using neutral copper acetate as a model. It consists, essentially, of bimetal Cu²⁺ carboxylate complexes with a distorted octahedral coordination. Such a structure is retained in the blackened pigment, although some differences were observed. It has been found that the alteration takes place without change of the valence state of Cu(II) ions, while the formation of the copper oxides CuO and Cu₂O responsible for the embrownment is excluded. On the basis of the XAS results we deduced that discoloration of copper resinate may be related to local modification of the copper coordination structure as evidenced by the observation of an increase of the Cu–Cu and Cu–C distances in the EXAFS spectra. PACS  78.70.Dm; 61.10.Ht     

Electronic excitations and luminescence of SrMgF4 single crystals

The electronic and crystal structures of SrMgF₄ single crystals grown by the Bridgman method have been investigated. The undoped SrMgF₄ single crystals have been studied using low-temperature (T = 10 K) time-resolved fluorescence optical and vacuum ultraviolet spectroscopy under selective excitation by synchrotron radiation (3.7–36.0 eV). Based on the measured reflectivity spectra and calculated spectra of the optical constants, the following parameters of the electronic structure have been determined for the first time: the minimum energy of interband transitions E _g = 12.55 eV, the position of the first exciton peak E _n = 1 = 11.37 eV, the position of the maximum of the “exciton” luminescence excitation band at 10.7 eV, and the position of the fundamental absorption edge at 10.3 eV. It has been found that photoluminescence excitation occurs predominantly in the region of the low-energy fundamental absorption edge of the crystal and that, at energies above E _g , the energy transfer from the matrix to luminescence centers is inefficient. The exciton migration is the main excitation channel of photoluminescence bands at 2.6–3.3 and 3.3–4.2 eV. The direct photoexcitation is characteristic of photoluminescence from defects at 1.8–2.6 and 4.2–5.5 eV.     

Intrinsic luminescence in oriented BeO crystals under VUV and inner-shell excitation

Beryllium oxide (BeO) crystals were investigated by time-resolved low temperature VUV-spectroscopy at the SUPERLUMI station and BW3 beam line of HASYLAB (DESY, Hamburg). Photoluminescence spectra (3–10.5 eV), luminescence decay kinetics upon selective photoexcitation, as well as luminescence excitation (50–650 eV) and reflectivity (9–35 eV) spectra were measured and analyzed for oriented BeO crystals. It was shown that study of oriented crystals makes the traditional time-resolved spectroscopy method essentially more informative. Formation of the self-trapped exciton excited states of different multiplicity was found to sensitively depend on excitation energy and mutual orientation of the crystal's C optical axis and electric vector E of exciting polarized synchrotron radiation.     

The electronic structures of epitaxial CrSi2 film prepared on Si(111) substrate

The valence band (VB) electronic structures of CrSi₂ were studied by synchrotron radiation photoemission. Overall features of the VB photoemission spectra measured at room temperature (RT) and 20 K by using synchrotron radiation (photon energy, hν=20–120 eV) were similar. Two characteristic emissions were observed corresponding to the bonding and the nonbonding Cr-d partial density of states (PDOS) in the CrSi₂. The onset of the VB photoemission measured at 20 K was located at about 0.32 eV below Fermi level, due to the energy band gap of CrSi₂ more than 0.32 eV.     

Spectroscopy of defects in irradiated alpo 4 and GaPO 4 crystals

The time-resolved luminescence spectra in energy region of 2.0-6.0 v eV, as well as the excitation spectra (4-35 v eV), reflectivity and the decay kinetics were studied at T =10 v K and 295 v K using selective vacuum ultraviolet excitation in nominally pure crystals as well as crystals with intrinsic defects and radiation defects induced by fast electrons.     

X‐ray absorption near‐edge structure anomalous behaviour in structures with buried layers containing silicon nanocrystals

Substructure and phase composition of silicon suboxide films containing silicon nanocrystals and implanted with carbon have been investigated by means of the X‐ray absorption near‐edge structure technique with the use of synchrotron radiation. It is shown that formation of silicon nanocrystals in the films' depth (more than 60 nm) and their following transformation into silicon carbide nanocrystals leads to abnormal behaviour of the X‐ray absorption spectra in the elementary silicon absorption‐edge energy region (100–104 eV) or in the silicon oxide absorption‐edge energy region (104–110 eV). This abnormal behaviour is connected to X‐ray elastic backscattering on silicon or silicon carbide nanocrystals located in the silicon oxide films depth.     

Relaxation of electronic excitations in beryllium oxide: A time-resolved vacuum-UV spectroscopy study

Beryllium oxide crystals are studied by time-resolved optical and luminescence vacuum-UV spectroscopy. The low-temperature luminescence spectra and the luminescence decay kinetics (2.5–10 eV, 1–500 ns) upon selective photoexcitation, and also the luminescence excitation and reflectivity spectra (8–35 eV), are analyzed for BeO crystals with the optic axis aligned parallel and perpendicular to the electric vector of exciting polarized synchrotron radiation. It is found that the radiative relaxation of electronic excitations proceeds through a large number of channels. The excited states of self-trapped excitons are characterized by different multiplicity depending on the excitation energy and the sample orientation.     

Low-temperature time-resolved vacuum ultraviolet spectroscopy of self-trapped excitons in KH<Subscript>2</Subscript> PO<Subscript>4</Subscript> crystals

A complex investigation of the dynamics of electronic excitations in potassium dihydrophosphate (KDP) crystals is performed by low-temperature time-resolved vacuum ultraviolet optical luminescence spectroscopy with subnanosecond time resolution and with selective photoexcitation by synchrotron radiation. For KDP crystals, data on the kinetics of the photoluminescence (PL) decay, time-resolved PL spectra (2–6.2 eV), and time-resolved excitation PL spectra (4–24 eV) at 10 K were obtained for the first time. The intrinsic character of the PL of KDP in the vicinity of 5.2 eV, which is caused by the radiative annihilation of self-trapped excitons (STEs), is ascertained; σ and π bands in the luminescence spectra of the STEs, which are due to singlet and triplet radiative transitions, are resolved; and the shift of the σ band with respect to the π band in the spectra of the STEs is explained.     

Investigation of luminescence processes in YAG single crystals irradiated by 50 MeV electron beam

Absorption, emission and excitation spectra of 50 MeV electron beam irradiated and as-grown YAG single crystals were studied and compared in the 10–300 K temperature range using time-resolved luminescence spectroscopy under UV/VUV/XUV excitation by synchrotron radiation and cathodoluminescence. The emission spectra consist of intrinsic (excitonic) and defect related non-elementary bands in the VIS/UV range. It is shown that fast electrons create stable F and F⁺ color centers with characteristic emission and absorption bands in the visible/UV range. Induced absorption caused from these defects starts at 4.2 eV. Energy transfer from host to color centers is not an efficient process.     

Luminescence of Ce doped LaPO4 nanophosphors upon Ce 4f-5d and band-to-band excitation

Luminescence spectral-kinetic studies have been performed for pure and Ce-doped LaPO₄ micro- and nanosized phosphates using synchrotron radiation for the excitation within 5-20 eV energy range at T=8-300 K. Mechanisms for the excitation of Ce³⁺ 5d-4f emission as well as the quenching processes are discussed. The influence of surface defects has been considered to modify considerably the luminescent properties of nanosized phosphors upon the excitation in the energy range of Ce³⁺ 4f-5d transitions and LaPO₄ host absorption.     

Cultural heritage and archaeology materials studied by synchrotron spectroscopy and imaging

The use of synchrotron radiation techniques to study cultural heritage and archaeological materials has undergone a steep increase over the past 10–15 years. The range of materials studied is very broad and encompasses painting materials, stone, glass, ceramics, metals, cellulosic and wooden materials, and a cluster of organic-based materials, in phase with the diversity observed at archaeological sites, museums, historical buildings, etc. Main areas of investigation are: (1) the study of the alteration and corrosion processes, for which the unique non-destructive speciation capabilities of X-ray absorption have proved very beneficial, (2) the understanding of the technologies and identification of the raw materials used to produce archaeological artefacts and art objects and, to a lesser extent, (3) the investigation of current or novel stabilisation, conservation and restoration practices. In terms of the synchrotron methods used, the main focus so far has been on X-ray techniques, primarily X-ray fluorescence, absorption and diffraction, and Fourier-transform infrared spectroscopy. We review here the use of these techniques from recent works published in the field demonstrating the breadth of applications and future potential offered by third generation synchrotron techniques. New developments in imaging and advanced spectroscopy, included in the UV/visible and IR ranges, could even broaden the variety of materials studied, in particular by fostering more studies on organic and complex organic–inorganic mixtures, while new support activities at synchrotron facilities might facilitate transfer of knowledge between synchrotron specialists and users from archaeology and cultural heritage sciences.     

平面镜反射率的标定及修正

 研究了用同步辐射源标定软X光掠入射平面镜的反射率。实验采用北京同步辐射装置(BSRF)-3W1B束线及反射率计靶室，在50~1 500 eV能区，做了C，Si，Ni和Au材料平面镜在1°~7°掠射角下的反射率标定曲线。由于3W1B束线的单色器采用变间距光栅作色散元件，光栅分光必然存在高次谐波，高次谐波严重影响光源的单色性，从而给平面镜的反射率标定值带来误差。前置滤片虽然能有效抵制高次谐波，但不能完全消除高次谐波。为此，利用透射光栅对光源做了单色性研究，给出高次谐波在不同能区所占光源强度的比例，从而对平面镜反射率标定值做出修正。     

A time-resolved luminescence spectroscopy study of non-linear optical crystals K2Al2B2O7

We report the results of complex study of luminescence and dynamics of electronic excitations in K₂Al₂B₂O₇ (KABO) crystals obtained using low-temperature luminescence-optical vacuum ultraviolet spectroscopy with sub-nanosecond time resolution under selective photoexcitation with synchrotron radiation. The paper discusses the decay kinetics of photoluminescence (PL), the time-resolved PL emission spectra (1.2–6.2 eV), the time-resolved PL excitation spectra and the reflection spectra (3.7–21 eV) measured at 7 K. On the basis of the obtained results three absorption peaks at 4.7, 5.8 and 6.5 eV were detected and assigned to charge-transfer absorption from O^2? to Fe³⁺ ions; the intrinsic PL band at 3.28 eV was revealed and attributed to radiative annihilation of self-trapped excitons, the defect luminescence bands at 2.68 and 3.54 eV were separated; the strong PL band at 1.72 eV was revealed and attributed to a radiative transition in Fe³⁺ ion.     

Electron excitations in LiB3O5 crystals with defects: Low-temperature time-resolved luminescence VUV spectroscopy

The dynamics of electron excitations and luminescence of LiB₃O₅ (LBO) single crystals was studied using low-temperature luminescence vacuum ultraviolet spectroscopy with a subnanosecond time resolution under photoexcitation with synchrotron radiation. The kinetics of the photoluminescence (PL) decay, the time-resolved PL emission spectra, and the time-resolved PL excitation spectra of LBO were measured at 7 and 290 K, respectively. The PL emission bands peaking at 2.7 eV and 3.3 eV were attributed to the radiative transitions of electronic excitations connected with lattice defects of LBO. The intrinsic PL emission bands at 3.6 and 4.2 eV were associated with the radiative annihilation of two kinds of self-trapped electron excitations in LBO. The processes responsible for the formation of localized electron excitations in LBO were discussed and compared with those taking place in wide-gap oxides.