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1.
In this work, we investigated the bombardment of polymer surfaces (PC, PMMA) with very low energy (250 eV) Cs+ ions.In the positive mode, we observed many cations combining a molecular fragment of the polymer (M) with two Cs atoms, similar to the well-known MCs2+ clusters commonly observed in inorganic depth profiling with Cs. For example, Cs2COOH+ or Cs2C6H5O+ were measured on PC and Cs2CH3O+ or Cs2C4H5O2+ were measured on PMMA. In fact, most of the polymer characteristic fragments measured in negative spectra also appear in the positive spectra, combined with two Cs atoms. It is remarkable that stable negative ions tend to combine not with one Cs, but with two Cs atoms to create the MCs2+ cluster.This effect is, to some extent, similar to the well-known cationisation of polymers (with Ag or Au) although here few clusters with only one Cs atom are detected (MCs+ clusters), like in classical cationisation. The most abundant clusters are the MCs2+ clusters, but heavier clusters (MCs3+, MCs4+ and above) are also measured with high yields in the spectrum.Surprisingly, some of those MCs2+ clusters were still detected even after a very long sputtering fluence (above 1017 ions/cm2), proving that some molecular depth profiling is also possible in this “Cs2-cationisation” mode. In other words, this work could open the way to an extension of the MCsn+ cluster analysis, commonly used in inorganic depth profiling, to the in-depth molecular analysis of organic layers.  相似文献   

2.
Electron energy loss spectra (ELS) have been obtained from polycrystalline Cr and Cr2O3 before and after surface reduction by 2 keV Ar+ bombardment. The primary electron energy used in the ELS measurements was systematically varied from 100 to 1150 eV in order to distinguish surface versus bulk loss processes. Two predominant loss features in the ELS spectra obtained from Cr metal at 9.0 and 23.0 eV are assigned to the surface and bulk plasmon excitations, respectively, and a number of other features arising from single electron transitions from both the bulk and surface Cr 3d bands to higher-lying states in the conduction band are also present. The ELS spectra obtained from Cr2O3 exhibit features that originate from both interband transitions and charge-transfer transitions between the Cr and O ions as well as the bulk plasmon at 24.4 eV. The ELS feature at 4.0 eV arises from a charge-transfer transition between the oxygen and chromium ions in the two surface layers beneath the chemisorbed oxygen layer, and the ELS feature at 9.8 eV arises from a similar transition involving the chemisorbed oxygen atoms. The intensity of the ELS peak at 9.8 eV decreases after Ar+ sputtering due to the removal of chemisorbed oxygen atoms. Sputtering also increases the number of Cr2+ states on the surface, which in turn increases the intensity of the 4.0 eV feature. Furthermore, the ELS spectra obtained from the sputtered Cr2O3 surface exhibit features characteristic of both Cr0 and Cr2O3, indicating that Ar+ sputtering reduces Cr2O3. The fact that neither the surface- nor the bulk-plasmon features of Cr0 can be observed in the ELS spectra obtained from sputtered Cr2O3 while the loss features due to Cr0 interband transitions are clearly present indicates that Cr0 atoms form small clusters lacking a bulk metallic nature during Ar+ bombardment of Cr2O3.  相似文献   

3.
The damage characteristics of polyethylene terephthalate (PET) have been studied under bombardment by C60+, Au3+ and Au+ primary ions. The observed damage cross-sections for the three ion beams are not dramatically different. The secondary ion yields however were significantly enhanced by the polyatomic primary ions where the secondary ion yield of the [M + H]+ is on average 5× higher for C60+ than Au3+ and 8× higher for Au3+ than Au+. Damage accumulates under Au+ and Au3+ bombardment while C60+ bombardment shows a lack of damage accumulation throughout the depth profile of the PET thick film up to an ion dose of ∼1 × 1015 ions cm−2. These properties of C60+ bombardment suggest that the primary ion will be a useful molecular depth profiling tool.  相似文献   

4.
Metal cluster complexes are chemically synthesized organometallic compounds, which have a wide range of chemical compositions with high molecular weight. Using a metal cluster complex ion source, sputtering characteristics of silicon bombarded with normally incident Ir4(CO)7+ ions were investigated. Experimental results showed that the sputtering yield at 10 keV was 36, which is higher than that with Ar+ ions by a factor of 24. In addition, secondary ion mass spectrometry (SIMS) of boron-delta-doped silicon samples and organic films of poly(methyl methacrylate) (PMMA) was performed. Compared with conventional O2+ ion beams, Ir4(CO)7+ ion beams improved depth resolution by a factor of 2.5 at the same irradiation conditions; the highest depth resolution of 0.9 nm was obtained at 5 keV, 45° with oxygen flooding of 1.3 × 10−4 Pa. Furthermore, it was confirmed that Ir4(CO)7+ ion beams significantly enhanced secondary ion intensity in high-mass region.  相似文献   

5.
H-terminated Si samples were preloaded with Cs by performing ToF-SIMS depth profiles (250 eV Cs+, 15 keV Ga+) until the steady state was reached both with and without a bias of +40 V applied to the ion extraction electrode. Xe+ depth profiles (350 eV Xe+, 15 keV Ga+) were obtained inside and around the Cs craters with and without applying the 40 V bias. The results indicate that the maximum of the Cs+ signal of the Xe+ depth profiles shifts to the surface if no bias is applied, either during the Cs+ sputtering or during the Xe+ sputtering (i.e., the profiles are broadest with both biases (Cs+ and Xe+) on and narrowest and closest to the surface if both biases are off). This effect can be explained by the electric field, caused by the bias, deflecting the sputtered low energy Cs+ ions back to the surface.  相似文献   

6.
The effects of C60 cluster ion beam bombardment in sputter depth profiling of inorganic-organic hybrid multiple nm thin films were studied. The dependence of SIMS depth profiles on sputter ion species such as 500 eV Cs+, 10 keV C60+, 20 keV C602+ and 30 keV C603+ was investigated to study the effect of cluster ion bombardment on depth resolution, sputtering yield, damage accumulation, and sampling depth.  相似文献   

7.
Polyimide (PMDA-ODA) surface was irradiated by low energy reactive atomic beam with energy 160-180 eV to enhance the adhesion with metal Cu film. O2+ and N2+ ions were irradiated at the fluence from 5 × 1015 to 1 × 1018 cm−2. Wetting angle 78° of distilled deionized (DI) water for bare PI was greatly reduced down to 2-4° after critical ion flounce, and the surface energy was increased from 37 to 81.2 erg/cm. From the analysis of O 1s core-level XPS spectra, such improvement seemed to result from the increment of hydrophilic carbonyl oxygen content on modified PI surface. To see more carefully correlation of the peel strength with interfacial reaction between Cu and PI, flexible copper clad laminate with Cu (9 μm)/Cu (200 nm) on modified PI substrate (25 μm) was fabricated by successive sputtering and electroplating. Firstly, peel strength was measured by using t-test and it was largely increased from 0.2 to 0.5 kgf/cm for Ar+ only irradiated PI to 0.72-0.8 kgf/cm for O2+ or N2O+ irradiated PI. Chemical reaction at the interface was reasoned by analyzing C 1s, O 1s, N 1s, and Cu 2p core-level X-ray photoelectron spectroscopy over the as-cleaved Cu-side and PI side surface through depth profiling. From the C 1s spectra of cleaved Cu-side, by the electron transfer from Cu to carbonyl oxygen, carbonyl carbon atom became less positive and as a result shifted to lower binding energy not reaching the binding energy of C2 and C3. The binding energy shift of the peak C4 as small as 1.7 eV indicates that carbonyl oxygen atoms were not completely broken. From the analysis of the O 1s spectra, it was found that new peak at 530.5 eV (O3) was occurred and the increased area of the peak O3 was almost the same with reduced area of the peak carbonyl oxygen peak O1. Since there was no change in the relative intensity of ether oxygen (O2) to carbonyl oxygen (O1), and thus O3 was believed to result from Cu oxide formation via a local bonding of Cu with carbonyl oxygen atoms. Moreover, from X-ray induced Auger emission spectra Cu LMM which was very sensitive to chemical bonding, Cu oxide or CuOC complex formation instead of CuNO complex was clearly identified by the observation of the peak at 570 eV at higher 2 eV than that of metal Cu. In conclusion, when Cu atoms were sputtered on modified PI by low energy ion beam irradiation, it can be suggested that two Cu atoms locally reacted with carbonyl oxygen in PMDA units and formed Cu+OC complex linkage without being broken from carbon atoms and thus the chemically bound Cu was in the form of Cu2O.  相似文献   

8.
In this study, a series of random copolymers of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) were prepared as surface-initiated polymer (SIP) films on silicon substrates using atom transfer radical polymerization. Positive and negative ion static time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to characterize SIP films with different MMA/EGDMA monomer ratios in an attempt to quantify their surface composition. However, matrix effects in the positive and negative ion modes led to preferential secondary ion generation from the EGDMA monomer and suppression of secondary ions characteristic of the MMA monomer, precluding accurate quantification using standard linear quantification methods. Ion-induced degradation of these films under 5 keV SF5+ bombardment was also examined to determine the effect of cross-linking on the accumulation of ion-induced damage. Increasing incorporation of the EGDMA cross-linker in the SIP films decreased the sputter rate and increased the rate of damage accumulation under extended (>1014 ions/cm2) 5 keV SF5+ bombardment. Comparison of the ion bombardment data with thermal degradation of cross-linked PMMA suggests that the presence of the cross-linker impedes degradation by depolymerization, resulting in ion-induced damage accumulation. The increased rate of ion-induced damage accumulation with increased cross-link density also suggests that polymers that can form cross-links during ion bombardment are less amenable to depth profiling using polyatomic primary ions.  相似文献   

9.
Effects of platinum silicon, graphite and PET substrates on the secondary ion yield of sub-monolayer and multilayer samples of Cyclosporin A following 20 keV Au+, Au3+and C60+ impacts have been investigated. The obtained results of sub-monolayer samples show that platinum enhances the yield of the pseudo-molecular ion following Au+ and Au3+ impacts due to the high density of the substrate that enables the energy of the primary ions to be deposited near the surface. C60+ impacts on sub-monolayer samples are less effective, but there is an enhancement on PET substrates. Impacts of 20 keV Au+ and Au3+ are not very efficient on multilayer samples. 20 keV C60+ impacts enhance the yields significantly, especially for the relatively high molecular weight [M+H]+ ion.  相似文献   

10.
In this paper, a H-terminated silicon wafer was bombarded by low energy cesium ions during ToF-SIMS analysis and work function variations of the target were measured for different analysis conditions. This measurement was performed by measuring the shift of the secondary ions energy distributions with a reflectron type analyzer. At first, the silicon’s work function change was found to be −2.3 eV during 500 eV Cs+ bombardment at 45°. This effect is due to the creation of a dipolar layer at the surface of the silicon by the implanted cesium. Then the work function variation was measured at 300 eV for varying cesium surface concentrations. The work function was found to decrease monotonously with the increasing cesium surface concentration, as during cesium adsorption experiments. The results were modeled following three different approaches and the value of the effective polarizability α of cesium was found to be equal to 1.9 × 10−39 C m2/V. Finally, the effect of the bombardment energy on the work function variation was studied for beams with energies ranging from 250 to 2000 eV. The effective polarizability of cesium was found to increase with increasing Cs beam energy.  相似文献   

11.
Two luminescence bands in the UV range were detected in crystalline α-quartz under electron beam excitation (6 kV, 3-5 μA). One band is situated at 5 eV and could be observed in pure samples. Its intensity increases with cooling below 100 K and undergoes saturation below 40 K alongside a slow growth with the time of irradiation at 9 K. The decay curve of the band at 5 eV contains two components, a fast (<10 ns) and a slow one in the range of 200 μs. The photoluminescence band at 5 eV with a similar temperature dependence was found in previously neutron-irradiated crystalline α-quartz. Therefore, the band at 5 eV was attributed to host material defects in both irradiation cases. The creation mechanism of such defects by electrons, the energy of which is lower than the threshold for a knock-out mechanism of defect creation, is discussed. Another band at 6 eV, containing subbands in different samples, appears in the samples containing aluminum, lithium and sodium ions. This luminescence is ascribed to a tunnel radiative transition in an association of (alkali atom)0-[AlO4]+ that is formed after the trapping of an electron and a hole by Li+ (or Na+) and AlO4.  相似文献   

12.
We deposited SrCu2O2 (SCO) films on sapphire (Al2O3) (0 0 0 1) substrates by pulsed laser deposition. The crystallographic orientation of the SCO thin film showed clear dependence on the growth temperature. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis showed that the film deposited at 400 °C was mainly oriented in the SCO [2 0 0] direction, whereas when the growth temperature was increased to 600 °C, the SCO film showed a dominant orientation of SCO [1 1 2]. The SCO film deposited at 500 °C was obvious polycrystalline, showing multi peaks from (2 0 0), (1 1 2), and (2 1 1) diffraction in the XRD spectrum. The SCO film deposited at 600 °C showed a band gap energy of 3.3 eV and transparency up to 80% around 500 nm. The photoluminescence (PL) spectra of the SCO films grown at 500 °C and 600 °C mainly showed blue-green emission, which was attributed to the intra-band transition of the isolated Cu+ and Cu+–Cu+ pairs according to the temperature dependent-PL analysis.  相似文献   

13.
Sn doped In2O3 films are deposited by rf-magnetron sputtering at 300 °C under Ar, Ar + O2 and Ar + H2 gas ambients. For the film prepared under argon ambient, electrical resistivity 6.5 × 10−4 Ω cm and 95% optical transmission in the visible region have been achieved optimizing the power and chamber pressure during the film deposition. X-ray diffraction spectra of the ITO film reveal (2 2 2) and (4 0 0) crystallographic planes of In2O3. With the introduction of 1.33% oxygen in argon, (2 2 2) peak of In2O3 decreases and resistivity increases for the deposited film. With further increase of oxygen in the sputtering gas mixture crystallinity in the film deteriorates and both the peaks disappeared. On the other hand, when 1.33% hydrogen is mixed with argon, the resistivity of the deposited film decreases to 5.5 × 10−4 Ω cm and the crystallinity remains almost unchanged. In case of reactive sputtering, the deposition rate is lower compared to that in case of non-reactive sputtering. HRTEM and first Fourier patterns show the highly crystalline structure of the samples deposited under Ar and Ar + H2 ambients. Crystallinity of the film becomes lower with the introduction of oxygen in argon but refractive index increases from 1.86 to 1.9. The surface morphology of the ITO films have been studied by high resolution scanning electron microscopy.  相似文献   

14.
In order to investigate the secondary cluster ion emission process of organo-metallic compounds under keV ion bombardment, self-assembled monolayers (SAMs) of alkanethiols on gold are ideal model systems. In this experimental study, we focussed on the influence of the primary ion species on the emission processes of gold-alkanethiolate cluster ions from a hexadecanethiol SAM on gold. For this purpose, we carried out time-of-flight secondary ion mass spectrometry (TOF-SIMS) measurements using the following primary ion species and acceleration voltages: Ar+, Xe+, SF5+ (10 kV), Bi+, Bi3+(25 kV), Bi32+, Bi52+, Bi72+ (25 kV).It is well known that molecular ions M and gold-alkanethiolate cluster ions AuxMy with M = S-(CH2)15-CH3, x − 3 ≤ y ≤ x + 1, x, y > 0, show intense peaks in negative mass spectra. We derived yields YSI exemplarily for the molecular ions M and the gold-hexadecanethiolate cluster ions Auy+1My up to y = 8 and found an exponentially decreasing behaviour for increasing y-values for the cluster ions.In contrast to the well-known increase in secondary ion yield for molecular secondary ions when moving from lighter to heavier (e.g. Ar+ to Xe+) or from monoatomic to polyatomic (e.g. Xe+ to SF5+) primary ions, we find a distinctly different behaviour for the secondary cluster ions. For polyatomic primary ions, there is a decrease in secondary ion yield for the gold-hexadecanethiolate clusters whereas the relative decrease of the secondary ion yield ξY with increasing y remains almost constant for all investigated primary ions.  相似文献   

15.
Intensities of positive and negative ion species emitted from thermally oxidized and plasma-enhanced chemical vapor deposited (PECVD) SiO2 films were analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and the Saha-Boltzmann equation. Intensities of positive and negative secondary ion species were normalized to those of 28Si+ and 28Si ions, respectively, and an effective temperature of approximately (7.2 ± 0.1) × 103 K of the sputtered region bombarded with pulsed 22 kV Au3+ primary ions was determined. Intensity spectra showed polarity dependence on both n and m values of SinOm fragments, and a slight shift to negative polarity for PECVD SiO2 compared to thermally oxidized SiO2 films. By dividing the intensity ratios of negative-to-positive ions for PECVD SiO2 by those for thermally oxidized SiO2 films to cancel statistical factors, the difference in absolute electronegativity (half the sum of ionization potential and electron affinity of fragments) between both films was obtained. An increase in electronegativity for SiOm (m = 1, 2) and Si2Om (m = 1-4) fragments for PECVD SiO2 films compared to thermally oxidized films was obtained to be 0.1-0.2 Pauling units, indicating a more covalent nature of Si-O bonds for PECVD SiO2 films compared to the thermally oxidized SiO2 films.  相似文献   

16.
Fluorophosphate glasses of composition, P2O5 + K2O + KF + MO + Al2O3 + xEu2O3 (M = Mg, Sr and Ba; x = 0.01, 0.05, 0.1, 1.0, 2.0, 4.0 and 6.0 mol%) were prepared and characterized their optical properties. Crystal-field (CF) analysis revealed a relatively weak CF strength around Eu3+ ions in the Ba based fluorophosphate glasses. The Judd-Ofelt parameters have been estimated from the oscillator strengths of 7F0 → 5D2, 7F0 → 5D4 and 7F0 → 5L6 absorption transitions of Eu3+ ions and were used to evaluate the radiative properties of the 5D0 → 7FJ (J = 0-4) transitions. Considerable variation has been observed in the relative intensity ratio of 5D0 → 7F2 to 5D0 → 7F1 transitions of Eu3+ ions due to change in the alkaline earth metal ions. The decay of the 5D0 level shows single exponential and less sensitive to Eu3+ ions concentration as well as MgO/SrO/BaO modifiers.  相似文献   

17.
Unintentionally doped and zinc-doped indium nitride (U-InN and InN:Zn) films were deposited on (0 0 0 1) sapphire substrates by radio-frequency reactive magnetron sputtering, and all samples were then treated by annealing to form In2O3 films. U-InN and InN:Zn films have similar photon absorption characteristics. The as-deposited U-InN and InN:Zn film show the absorption edge, ∼1.8-1.9 eV. After the annealing process at 500 °C for 20 min, the absorption coefficient at the visible range apparently decreases, and the absorption edge is about 3.5 eV. Two emission peaks at 3.342 eV (371 nm) and 3.238 eV (383 nm) in the 20 K photoluminescence (PL) spectrum of In2O3:Zn films were identified as the free-exciton (FE) or the near band-to-band (B-B) and conduction-band-to-acceptor (C-A) recombination, respectively.  相似文献   

18.
The oxidation of the Pd(1 1 1) surface was studied by in situ XPS during heating and cooling in 3 × 10−3 mbar O2. A number of adsorbed/dissolved oxygen species were identified by in situ XPS, such as the two dimensional surface oxide (Pd5O4), the supersaturated Oads layer, dissolved oxygen and the R 12.2° surface structure.Exposure of the Pd(1 1 1) single crystal to 3 × 10−3 mbar O2 at 425 K led to formation of the 2D oxide phase, which was in equilibrium with a supersaturated Oads layer. The supersaturated Oads layer was characterized by the O 1s core level peak at 530.37 eV. The 2D oxide, Pd5O4, was characterized by two O 1s components at 528.92 eV and 529.52 eV and by two oxygen-induced Pd 3d5/2 components at 335.5 eV and 336.24 eV. During heating in 3 × 10−3 mbar O2 the supersaturated Oads layer disappeared whereas the fraction of the surface covered with the 2D oxide grew. The surface was completely covered with the 2D oxide between 600 K and 655 K. Depth profiling by photon energy variation confirmed the surface nature of the 2D oxide. The 2D oxide decomposed completely above 717 K. Diffusion of oxygen in the palladium bulk occurred at these temperatures. A substantial oxygen signal assigned to the dissolved species was detected even at 923 K. The dissolved oxygen was characterised by the O 1s core level peak at 528.98 eV. The “bulk” nature of the dissolved oxygen species was verified by depth profiling.During cooling in 3 × 10−3 mbar O2, the oxidised Pd2+ species appeared at 788 K whereas the 2D oxide decomposed at 717 K during heating. The surface oxidised states exhibited an inverse hysteresis. The oxidised palladium state observed during cooling was assigned to a new oxide phase, probably the R 12.2° structure.  相似文献   

19.
H.Y. Hu 《Applied Surface Science》2008,254(24):8029-8034
The chemical structure and site location of sulfur atoms on n-GaAs (1 0 0) surface treated by bombardment of S+ ions over their energy range from 10 to 100 eV have been studied by X-ray photoelectron spectroscopy and low energy electron diffraction. The formation of Ga-S and As-S species on the S+ ion bombarded n-GaAs surface is observed. An apparent donor doping effect is observed for the n-GaAs by the 100 eV S+ ion bombardment. It is found that the S+ ions with higher energy are more effective in the formation of Ga-S species, which assists the n-GaAs (1 0 0) surface in reconstruction into an ordered (1 × 1) structure upon subsequent annealing. The treatment is further extended to repair Ar+ ion damaged n-GaAs (1 0 0) surface. It is found that after a n-GaAs (1 0 0) sample is damaged by 150 eV Ar+ ion bombardment, and followed by 50 eV S+ ion treatment and subsequent annealing process, finally an (1 × 1) ordering GaAs (1 0 0) surface with low surface states is obtained.  相似文献   

20.
Y2O3:Yb3+ nanocrystals codoping with Li+ ions were synthesized by glycine combustion method. Codoping with Li+ ions leads to about 12 times enhancement of the photoluminescence (PL) intensity around 1 μm, in terms of the increased lifetimes at 1026 nm from 0.384 ms to 1.42 ms at room temperature. The enhancement in the PL intensity could be mostly attributed to the modification of the local symmetry around Yb3+ ions by codoping with Li+ ions.  相似文献   

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