Very high temperature chemical vapor deposition of new carbon thin films using organic semiconductor molecular beam sources

We carried out the preparation and characterization of new carbon films deposited using an organic molecular beam deposition apparatus with very high substrate temperature (from room temperature to 2670 K), which we newly developed. When we irradiated molecular beam of organic semiconductor perylene tetracarboxylic acid dianhydride (PTCDA) on Y_0.07Zr_0.93O₂ (111) at 2170 K, a new carbon material was formed via decomposition and fusing of the molecules. The films were characterized with an atomic force microscope (AFM), Raman spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Zirconium carbide (ZrC) films were identified beneath the topmost carbon layer by XRD and XPS analyses, which results from chemical reactions of the substrate and the molecules. Partially graphitized aromatic rings of PTCDA were observed from Raman spectroscopy. The present technique – very high temperature chemical vapor deposition using organic semiconductor sources – will be useful to study a vast unexplored field of covalent carbon solids.     

分子束研究气体分子在表面吸脱附动力学

分子束技术与表面电子谱、气体质谱分析技术相结合,形成分子束-表面散射谱,它是研究气体-表面相互作用动力学的有力工具.它的主要突破在于从分子(原子)量度来揭示诸如表面吸附、脱附、催化、腐蚀和能量适应等气体-表面作用过程.本文首先概述了表面吸附、脱附过程及类型,接着叙述了本实验室自行研制的分子束-表面散射装置的总体设计及用来研究表面吸脱附的实验技术.最后举例说明分子束技术在研究表面吸脱附中的应用.     

Metal-free silicon-molecule-nanotube testbed and memory device

Work from several laboratories has shown that metal nanofilaments cause problems in some molecular electronics testbeds. A new testbed for exploring the electrical properties of single molecules has been developed to eliminate the possibility of metal nanofilament formation and to ensure that molecular effects are measured. This metal-free system uses single-crystal silicon and single-walled carbon nanotubes as electrodes for the molecular monolayer. A direct Si-arylcarbon grafting method is used. Use of this structure with pi-conjugated organic molecules resulted in a hysteresis loop with current-voltage measurements that are useful for an electronic memory device. The memory is non-volatile for more than 3 days, non-destructive for more than 1,000 reading operations and capable of more than 1,000 write-erase cycles before device breakdown. Devices without pi-conjugated molecules (Si-H surface only) or with long-chain alkyl-bearing molecules produced no hysteresis, indicating that the observed memory effect is molecularly relevant.     

Electrospray ion beam deposition of clusters and biomolecules

An ion beam source using electrospray ionization is presented for nondestructive vacuum deposition of mass-selected large organic molecules and inorganic clusters. Electrospray ionization is used to create an ion beam from a solution containing the nanoparticles or molecules to be deposited. To form and guide the ion beam, radio frequency and electrostatic ion optics are utilized. The kinetic energy distribution of the particles is measured to control the beam formation and the landing process. The particle mass-to-charge ratio is analyzed by in situ time-of-flight mass spectrometry. To demonstrate the performance of the setup, deposition experiments with gold nanoclusters and bovine serum albumin proteins on graphite surfaces were performed and analyzed by ex situ atomic force microscopy. The small gold clusters are found to form three-dimensional agglomerations at the surface, preferentially decorating the step edges. In contrast, bovine serum albumin creates two-dimensional fractal nanostructures on the substrate terraces due to strong intermolecular interactions.     

Light-controlled molecular resistive switching ferroelectric heterojunction

Molecular ferroelectrics have attained significant advancement as a promising approach towards the development of next-generation non-volatile memory devices. Herein, the semiconducting-ferroelectric heterojunctions which is composed of molecular ferroelectrics (R)-(−)-3-hydroxlyquinuclidinium chloride together with organic charge transfer complex is reported. The molecular ferroelectric domain provides polarization and bistability while organic charge transfer phase allows photo-induced charge generation and transport for photovoltaic effect. By switching the direction of the polarization in the ferroelectric phase, the heterojunction-based devices show non-volatile resistive switching under external electric field and photocurrent/voltage induced by light excitation, stable fatigue properties and long retention time. Overall, the photovoltaic controlled resistive switching provides a new route for all-organic multiphase non-volatile memories.     

Laser desorption combined with hyperthermal surface ionization time-of-flight mass spectrometry

A setup combining laser desorption of nonvolatile molecules and their aerodynamic acceleration in a supersonic molecular beam followed by hyperthermal surface ionization in a reflectron time-of-flight mass spectrometer is described. While laser desorption performs the intact transfer of the analyte molecules into the gas phase, hyperthermal surface ionization opens up the possibility to efficiently ionize even larger molecules with a small and potentially controlled degree of fragmentation. Being an ionization technique, which is particularly effective for aromatic and heterocyclic compounds, the selectivity can further be increased by tuning the kinetic energy to which the molecules are accelerated in the supersonic beam. The results obtained for several polycyclic aromatic hydrocarbons and biochemical substances show that sufficient acceleration can be achieved even for molecules with a molecular weight above 5000 amu and that HSI preserves its advantageous features even for thermally labile large molecules such as insulin.     

Isotope Substitution Extends the Lifetime of Organic Molecules in Transmission Electron Microscopy

Structural characterisation of individual molecules by high‐resolution transmission electron microscopy (HRTEM) is fundamentally limited by the element and electron energy‐specific interactions of the material with the high energy electron beam. Here, the key mechanisms controlling the interactions between the e‐beam and C–H bonds, present in all organic molecules, are examined, and the low atomic weight of hydrogen—resulting in its facile atomic displacement by the e‐beam—is identified as the principal cause of the instability of individual organic molecules. It is demonstrated theoretically and proven experimentally that exchanging all hydrogen atoms within molecules with the deuterium isotope, and therefore doubling the atomic weight of the lightest atoms in the structure, leads to a more than two‐fold increase in the stability of organic molecules in the e‐beam. Substitution of H for D significantly reduces the amount of kinetic energy transferred from the e‐beam to the atom (main factor contributing to stability) and also increases the barrier for bond dissociation, primarily due to the changes in the zero‐point energy of the C–D vibration (minor factor). The extended lifetime of coronene‐d₁₂, used as a model molecule, enables more precise analysis of the inter‐molecular spacing and more accurate measurement of the molecular orientations.     

激光-分子束-表面散射装置的研制

介绍了自行设计和加工的激光-分子束-表面散射装置，并对超高真空转动密封结构作了详细描述。差分泵浦的超音速分子束对准样品中心，射入超高真空主室。样品架安放在主室中央，四极质谱检测器可绕样品转动，用来测量表面散射分子的平动能及角分布。三个石英窗口作为激光窗口，可用LIF或MPI方法来测量表面散射分子的内能态分布，也可用于研究表面光化学。最后给出了分子束发散角及室温时CH2I2在Ag（110）表面用308um激光光解碎片碘的TOF谱的测量结果。     

Determination of Thermophysical Properties for Polymer Films using Conduction Analysis of Laser Heating

Determination of the thermophysical properties of thin film materials is important for modeling and optimizing laser microvia drilling of organic substrates in microelectronics applications. Techniques to measure the density, thermal conductivity, thermal diffusivity, thermal decomposition point, and specific ablation heat of thin polymer films are described. An experimental apparatus was set up for laser heating of the sample. To measure the thermal diffusivity, an analytic heat transfer model is developed. One-dimensional heat conduction is assumed due to the small thickness of the film compared to the radius of the laser beam. The value of thermal diffusivity is obtained by fitting the experimental data to the theory. The specific ablation heat is obtained by measuring the mass loss during laser ablation. The experimental apparatus and the property determination methodology can also be applied to thin samples of other materials.     

Low energy electron beam for time-of-flight ionization measurements

A low energy electron gun was assembled in a crossed molecular beam apparatus in order to monitorize the effusive molecular beam density using the electron impact technique. Electrons were analised in both time-of-flight and Faraday cup detectors. The electrons coming directly from the gun were clearly identified, allowing those ones coming from the ionization impact to be distinguished in time-of-flight with a multichannel analyser working in PHA mode. This set-up allows to make an estimation of the electron impact cross-section ratios in CCl₄ and air.     

激光电离反射式串级飞行时间质谱仪的离子轨迹模拟和性能研究

通过离子轨迹模拟对用二阶空间聚焦条件设计的激光电离反射式串级飞行时间质谱仪的性能进行了研究 ,其中包括离子源在不同离子注入条件下的空间聚焦性能 ,有栅网和无栅网反射器的性能 ,栅丝效应 ,检测器平面位置以及质量门、光解点和后加速电极对性能的影响等。模拟结果对实际仪器的调试运行也提供了重要的参考依据     

硅基PtSi纳米薄膜制备及应用研究进展

PtSi红外探测器是一种重要的光电器件，在军事和民用方面均起着非常重要的作用。高质量硅基PtSi薄膜的制备是基础。本文介绍了溅射、分子束外延、脉冲激光沉积和激光分子束外延等制备PtSi薄膜的方法。并评述了PtSi红外探测器的最新应用研究进展及发展趋势。     

Optical power limiting with photoinduced anisotropy of azobenzene films

We study the power-limiting properties of photoanisotropic azobenzene films with low-power laser. The trans-cis photoisomerization and molecular reorientation of azobenzene molecules induced by polarized laser beams result in intensity-dependent anisotropic effects. Consequently, the transmittance of the input beam that passes through the film between two crossed polarizers becomes enhanced at low intensities and clamped at high intensities. The limiting threshold is adjustable by changing the intensity of excitation beam.     

在Cu_2O涂层上CH_4氧化反应的分子束研究

用分子束技术和电子能谱研究了在Cu_2O涂层上CH_4的氧化反应。实验得到,这个反应的发生需要具备下述条件:(1)Cu_2O表面对氧呈解离吸附,并提供出活性氧原子;(2)CH_4分子束的平动能必须超过59kJ/mol;(3)样品温度不能超过750K。     

Design and performance of an instrument for soft landing of biomolecular ions on surfaces

A new ion deposition apparatus was designed and constructed in our laboratory. Our research objectives were to investigate interactions of biomolecules with hydrophilic and hydrophobic surfaces and to carry out exploratory experiments aimed at highly selective deposition of spatially defined and uniquely selected biological molecules on surfaces. The apparatus includes a high-transmission electrospray ion source, a quadrupole mass filter, a bending quadrupole that deflects the ion beam and prevents neutral molecules originating in the ion source from impacting the surface, an ultrahigh vacuum (UHV) chamber for ion deposition by soft landing, and a vacuum lock system for introducing surfaces into the UHV chamber without breaking vacuum. Ex situ analysis of surfaces following soft landing of mass-selected peptide ions was performed using 15 keV Ga+ time-of-flight secondary ion mass spectrometry and grazing incidence infrared reflection-absorption spectroscopy. It is shown that these two techniques are highly complementary methods for characterization of surfaces prepared with a range of doses of mass-selected biomolecular ions. We also demonstrated that soft landing of peptide ions on surfaces can be utilized for controlled preparation of peptide films of known coverage for fundamental studies of matrix effects in SIMS.     

Electron beam irradiation for structuring of molecular assemblies

Nontraditional applications of electron beam irradiation for patterning of molecular assemblies are considered. The electron beam can have the following effects on molecular layers: destruction of molecular structure under e-beam irradiation with a successive formation of new molecular system when the irradiation is stopped; variation of the properties of the layer after e-beam irradiation; crosslinking of molecules in the layer under irradiation; modification of the templates for the successive film growth, providing different growing conditions in irradiated and nonirradiated areas; and activation of the solid support surface and molecular systems in the film resulting in the increased adhesion of the layer to the substrate in irradiated areas. All these effects were used for patterning of thin layers of different compounds. Five classes of molecular systems were considered, namely, films of simple surfactant molecules, layers of charge-transfer complexes, films of conducting polymers, aggregated nanoparticulate layers and films of nanoengineered polymeric capsules. Characteristic features of patterning processes in each particular case are discussed.     

Role of kinetic energy of impinging molecules in the α-sexithiophene growth

We report on the α-sexithiophene sub-monolayer growth with supersonic molecular beam deposition by investigating how the kinetic energy of the impinging molecules influences the growth on substrates with different surface wettabilities and temperatures. The results show that the energy of the impinging molecules affects the morphology of the molecular film increasing the coverage and the island size, and reducing the fractality of the sub-monolayer islands. The possibility of directing growth of more ordered islands could improve the performances of electronic devices, which are greatly affected by the structure of the first monolayers.     

Vapor Pressure of Water at Its Triple Point

The vapor pressure of water at its triple point was measured with exceptionally high accuracy by realizing it with a special apparatus and measuring the pressure with the NBS precision mercury manometer. The vapor pressure apparatus had a system for circulating the liquid water. Actual triple point conditions were established with a thin sheet of freshly distilled liquid flowing down over an exposed mantle of ice frozen on a vertical well. This technique reduced non-volatile contaminants and the vapor was repeatedly pumped to remove accumulated volatile contaminants. A diaphragm pressure transducer was used to separate the water vapor from the helium used to transmit the pressure to the manometer. The value found for the vapor pressure of water at its triple point was 611.657 Pa with an uncertainty of ± 0.010 Pa from random errors, computed at 99 percent confidence limits. The systematic errors are estimated to be insignificant relative to the random errors.     

Die Molekularstrahleptaxie — vom Forschungsinstrument zum Industriellen Produktionswerkzeug

High technology molecular beam epitaxy (MBE) is a complex chemo‐physical crystal growth process for deposition of ultra thin monocrystalline layers on monocrystalline wafers. The goal is to obtain the crystal growth with precision of an atom in both, vertical as well as in horizontal direction. One most important condition is to achieve ultra high vacuum environment, it means, that in the deposition chamber is a background pressure in the range of 10^‐10 Torr or even better. Then the mean free path of the evaporated species is in the range of several hundred kilometers and there are no interactions between the molecules in the beams. The molecular beams come typically from thermally evaporated sources (effusion cells), but also different techniques are often used (chemical beam epitaxy — CBE, metal‐organic molecular beam epitaxy — MOMBE, gas‐source molecular beam epitaxy — GSMBE). Normally the molecular beams can be abrupted by individual source shutters with open‐close cycles of a few hundred milliseconds. Together with the natural very low growth rate of a few Ångstroms per second it is possible to composite atomically layers from one material to another.     

Depth resolution during C60+ profiling of multilayer molecular films

Time-of-flight secondary ion mass spectrometry is utilized to characterize the response of Langmuir-Blodgett (LB) multilayers under the bombardment by buckminsterfullerene primary ions. The LB multilayers are formed by barium arachidate and barium dimyristoyl phosphatidate on a Si substrate. The unique sputtering properties of the C60 ion beam result in successful molecular depth profiling of both the single component and multilayers of alternating chemical composition. At cryogenic (liquid nitrogen) temperatures, the high mass signals of both molecules remain stable under sputtering, while at room temperature, they gradually decrease with primary ion dose. The low temperature also leads to a higher average sputter yield of molecules. Depth resolution varies from 20 to 50 nm and can be reduced further by lowering the primary ion energy or by using glancing angles of incidence of the primary ion beam.