Comparison of Pd electron beam induced deposition using two precursors and an oxygen purification strategy.

Focused electron beam induced deposition (FEBID) allows the creation of nanoscale structures through dissociation of an organo-metallic precursor by electrons at the beam impact point. The deposition of Pd can be interesting for its catalytic behavior and ability to contact carbon based materials. Two precursors were investigated-Pd(hfac)2 and (Cp)Pd(allyl)-and two deposition methods: with and without an in situ oxygen purification process. The deposition parameters can be tuned for the Pd(hfac)2 precursor to provide a deposition with 23 ± 2 at.% of Pd and a main component of C at 51 ± 3 at.% and minor components of O and F. An in situ purification process using O2 was much faster than expected and improved the Pd content to up to >65 at.% while reducing the C to ∼20 at.%, and avoiding the oxidation of Pd. The resistivity was ∼100 µOhm · cm and compares favorably with a bulk value of 10 µOhm · cm. The (Cp)Pd(allyl) precursor is interesting because it does not release fluorine during the deposition and hence it does not etch a possible substrate. Its FEBID deposition had a composition of 26 ± 5 at.% of Pd with 74 ± 5 at.% of C. The O2 purification process can improve the Pd content up to ∼60 at.% while reducing C to <20 at.%, but also increasing the O content to 18 at%, which was released afterwards. The best resistivity was measured at ∼1000 µOhm · cm, although better values can be anticipated for longer post treatment times.

Towards a single step process to create high purity gold structures by electron beam induced deposition at room temperature.

Highly pure metallic structures can be deposited by electron beam induced deposition and they have many important applications in different fields. The organo-metallic precursor is decomposed and deposited under the electron beam, and typically it is purified with post-irradiation in presence of O2. However, this approach limits the purification to the surface of the deposit. Therefore, 'in situ' purification during deposition using simultaneous flows of both O2 and precursor in parallel with two gas injector needles has been tested and verified. To simplify the practical arrangements, a special concentric nozzle has been designed allowing deposition and purification performed together in a single step. With this new device metallic structures with high purity can be obtained more easily, while there is no limit on the height of the structures within a practical time frame. In this work, we summarize the first results obtained for 'in situ' Au purification using this concentric nozzle, which is described in more detail, including flow simulations. The operational parameter space is explored in order to optimize the shape as well as the purity of the deposits, which are evaluated through scanning electron microscope and energy dispersive x-ray spectroscopy measurements, respectively. The observed variations are interpreted in relation to other variables, such as the deposition yield. The resistivity of purified lines is also measured, and the influence of additional post treatments as a last purification step is studied.

Gas-assisted electron-beam-induced nanopatterning of high-quality titanium oxide.

Electron-beam-induced deposition of titanium oxide nanopatterns is described. The precursor is titanium tetra-isopropoxide, delivered to the deposition point through a needle and mixed with oxygen at the same point via a flow through a separate needle. The depositions are free of residual carbon and have an EDX determined stoichiometry of TiO2.2. High resolution transmission electron microscopy and Raman spectroscopy studies reveal an amorphous structure of the fabricated titanium oxide. Ellipsometric characterization of the deposited material reveals a refractive index of 2.2-2.4 RIU in the spectral range of 500-1700 nm and a very low extinction coefficient (lower than 10(-6) in the range of 400-1700 nm), which is consistent with high quality titanium oxide. The electrical resistivity of the titanium oxide patterned with this new process is in the range of 10-40 GΩ cm and the measured breakdown field is in the range of 10-70 V µm(-1). The fabricated nanopatterns are important for a variety of applications, including field-effect transistors, memory devices, MEMS, waveguide structures, bio- and chemical sensors.

Functional nickel-based deposits synthesized by focused beam induced processing.

Functional nanostructures fabricated by focused electron/ion beam induced processing (FEBIP/FIBIP) open a promising route for applications in nanoelectronics. Such developments rely on the exploration of new advanced materials. We report here the successful fabrication of nickel-based deposits by FEBIP/FIBIP using bis(methyl cyclopentadienyl)nickel as a precursor. In particular, binary compounds such as nickel oxide (NiO) are synthesized by using an in situ two-step process at room temperature. By this method, as-grown Ni deposits transform into homogeneous NiO deposits using focused electron beam irradiation under O2 flux. This procedure is effective in producing highly pure NiO deposits with resistivity of 2000 Ωcm and a polycrystalline structure with face-centred cubic lattice and grains of 5 nm. We demonstrate that systems based on NiO deposits displaying resistance switching and an exchange-bias effect could be grown by FEBIP using optimized parameters. Our results provide a breakthrough towards using these techniques for the fabrication of functional nanodevices.

Embedded purification for electron beam induced Pt deposition using MeCpPtMe3.

Two different room-temperature processes for the electron beam induced deposition of high purity platinum (Pt), using the standard MeCpPtMe3 precursor and oxygen for purification, have been investigated. The first process is a sequential method, which uses two independent gas injector systems (GIS) in order to perform a standard Pt deposition, followed by an e-beam post-irradiation under oxygen flux. The second process is a parallel, single-step process that includes a simultaneous flow of both precursor and oxygen, using an add-on device that can be mounted on the standard GIS needle. Both processes are effective in producing high purity Pt depositions close to 100 at%. The first method requires a high current and irradiation dose in the clean-up phase, and provides Pt structures with small voids, a maximum thickness of around 100 nm and resistivity of 88 ± 10 µΩ cm. The second method requires a high oxygen/precursor flux ratio and produces void-free structures with resistivity of 60 ± 5 µΩ cm, only six times the bulk value for Pt. The second method is easier to use and produces a void-free deposition of high purity Pt.

Gold complexes for focused-electron-beam-induced deposition.

Four gold complexes were tested as a precursor for focused-electron-beam-induced deposition: [ClAu(III)Me2]2, ClAu(I)(SMe2), ClAu(I)(PMe3), and MeAu(I)(PMe3). Complexes [ClAu(III)Me2]2 and MeAu(I)(PMe3) are volatile, have sufficient vapor pressure at room temperature for deposition experiments, and were found to yield deposits that contain gold (29-41 and 19-25 atom %, respectively). Electrons easily remove the Cl ligand from [ClAu(III)Me2]2, and predominantly both methyl ligands are incorporated into the deposit. Electrons remove at least one methyl group from MeAu(I)(PMe3). Complexes ClAu(I)(SMe2) and ClAu(I)(PMe3) are not suitable as a precursor. They dissociate in vacuum, and the only volatile components are Cl, SMe2, and PMe3, respectively.

Gas-assisted electron-beam-induced nanopatterning of high-quality Si-based insulator.

An oxygen-assisted electron-beam-induced deposition (EBID) process, in which an oxygen flow and the vapor phase of the precursor, tetraethyl orthosilicate (TEOS), are both mixed and delivered through a single needle, is described. The optical properties of the SiO(2+δ) (- 0.04 ≤ δ ≤ +0.28) are comparable to fused silica. The electrical resistivity of both single-needle and double-needle SiO(2+δ) are comparable (greater than 7 GΩ cm) and a measured breakdown field is greater than 400 V µm(-1). Compared to the double-needle process the advantage of the single-needle technique is the ease of alignment and the proximity to the deposition location, which facilitates fabrication of complex 3D structures for nanophotonics, photovoltaics, micro- and nano-electronics applications.

A new sequential EBID process for the creation of pure Pt structures from MeCpPtMe3.

Electron beam induced deposition (EBID) is a process used for the fabrication of three-dimensional nanostructures of a variety of materials, but direct deposition of pure metallic structures has rarely been achieved. Typically, MeCpPtMe3 as a precursor for Pt leads to a carbon rich deposit with ~15 at.% Pt, which negatively affects its application as an electrical contact. We report a new process for Pt purification: in situ annealing with electron beam post-irradiation under oxygen flux, which can completely purify a thin (<100 nm) Pt EBID structure at substrate temperatures as low as 120 °C. We have developed a sequential method in which a thin Pt EBID structure is deposited on a previously purified structure and subsequently purified. The resistivity of the contact grown by this sequential procedure is observed to be ~70 ± 8 µΩ cm-only six times higher than that of pure bulk Pt. Thus, sequential deposition and purification proves to be an effective method for fabricating pure Pt structures of desired dimensions.

Subunits of the translation initiation factor eIF2B are mutant in leukoencephalopathy with vanishing white matter.

Leukoencephalopathy with vanishing white matter (VWM) is an inherited brain disease that occurs mainly in children. The course is chronic-progressive with additional episodes of rapid deterioration following febrile infection or minor head trauma. We have identified mutations in EIF2B5 and EIF2B2, encoding the epsilon- and beta-subunits of the translation initiation factor eIF2B and located on chromosomes 3q27 and 14q24, respectively, as causing VWM. We found 16 different mutations in EIF2B5 in 29 patients from 23 families. We also found two distantly related individuals who were homozygous with respect to a missense mutation in EIF2B2, affecting a conserved amino acid. Three other patients also had mutations in EIF2B2. As eIF2B has an essential role in the regulation of translation under different conditions, including stress, this may explain the rapid deterioration of people with VWM under stress. Mutant translation initiation factors have not previously been implicated in disease.

Electron beam induced deposition at elevated temperatures: compositional changes and purity improvement.

Thermally assisted electron beam induced deposition can result in an improvement of the purity of nano-scale depositions. Six commonly used organic precursors were examined: W(CO)(6), TEOS (tetraethylorthosilicate), MeCpPtMe(3), Co(CO)(3)NO, Co(2)(CO)(8), and Me(2)Auacac. The last two precursors were also tested on two different instruments to confirm reproducibility of the results. The influence of the substrate temperature on the composition of the deposition has been quantified systematically in the temperature range 25-360 °C. It has been shown that most purities improve when applying an elevated temperature, while the shape of the deposition remains intact. The purity improvement is achieved at the cost of a lower deposition yield. The amount of improvement is different for each precursor. Within the maximum temperature range of 360 °C, the best improvement was found for W(CO)(6): from 36.7 at.% at 25 °C to 59.2 at.% at 280 °C. For both cobalt precursors an additional transition region between patterned electron beam induced deposition (EBID) and thermal thin film growth has been identified. In this region seeded growth occurs with strongly increased growth rates.

Rapid electron beam assisted patterning of pure cobalt at elevated temperatures via seeded growth.

A new method of direct, rapid nano- to micro-scale patterning of high purity cobalt is presented. The method utilizes a combination of electron beam induced deposition (EBID) and seeded growth at elevated temperatures below the temperature of spontaneous thermal decomposition. Dicobalt octacarbonyl Co2(CO)8 is used as the precursor and carbon as a seed layer. Seeded deposition is carried out in the substrate temperature range from 55 to 75 °C. Deposition yield is significantly higher than conventional EBID and magnetotransport measurements indicate that resistivity, 22 µΩ cm, and saturation magnetization, 1.55 T, are much closer to the corresponding values for bulk Co than those for standard EBID.

Fe:O:C grown by focused-electron-beam-induced deposition: magnetic and electric properties.

We systematically study the effect of oxygen content on the magneto-transport and microstructure of Fe:O:C nanowires deposited by focused-electron-beam-induced (FEBID) deposition. The Fe/O ratio can be varied with an Fe content varying between ∼ 50 and 80 at.% with overall low C content (≈16 ± 3 at.%) by adding H(2)O during the deposition while keeping the beam parameters constant as measured by energy dispersive x-ray (EDX) spectroscopy. The room-temperature magnetic properties for deposits with an Fe content of 66-71 at.% are investigated using the magneto-optical Kerr effect (MOKE) and electric magneto-transport measurements. The nanostructure of the deposits is investigated through cross-sectional high-resolution transmission electron microscopy (HRTEM) imaging, allowing us to link the observed magneto-resistance and resistivity to the transport mechanism in the deposits. These results demonstrate that functional magnetic nanostructures can be created, paving the way for new magnetic or even spintronics devices.

Combined Focused Electron Beam-Induced Deposition and Etching for the Patterning of Dense Lines without Interconnecting Material.

High resolution dense lines patterned by focused electron beam-induced deposition (FEBID) have been demonstrated to be promising for lithography. One of the challenges is the presence of interconnecting material, which is often carbonaceous, between the lines as a result of the Gaussian line profile. We demonstrate the use of focused electron beam-induced etching (FEBIE) as a scanning electron microscope (SEM)-based direct-write technique for the removal of this interconnecting material, which can be implemented without removing the sample from the SEM for post processing. Secondary electron (SE) imaging has been used to monitor the FEBIE process, and atomic force microscopy (AFM) measurements confirm the fabrication of well separated FEBID lines. We further demonstrate the application of this technique for removing interconnecting material in high resolution dense lines using backscattered electron (BSE) imaging to monitor the process.

Heat shock response of the rat lens.

The sequence relationship between the small heat shock proteins and the eye lens protein alpha-crystallin (Ingolia, T. D., and E. E. Craig, 1982, Proc. Natl. Acad. Sci. USA, 79: 2360-2364) prompted us to subject rat lenses in organ culture to heat shock and other forms of stress. The effects on protein synthesis were followed by labeling with [35S]methionine and analysis by one- and two-dimensional gel electrophoresis and fluorography. Heat shock gave a pronounced induction of a protein that could be characterized as the stress protein SP71. This protein probably corresponds to the major mammalian heat shock protein hsp70. Also two minor proteins of 16 and 85 kD were induced, while the synthesis of a constitutive heat shock-related protein, P73, was considerably increased. The synthesis of SP71 started between 30 and 60 min after heat shock, reached its highest level after 3 h, and had stopped again after 8 h. In rat lenses that were preconditioned by an initial mild heat shock, a subsequent shock did not cause renewed synthesis of SP71. This effect resembles the thermotolerance phenomenon observed in cultured cells. The proline analogue azetidine-2-carboxylic acid, zinc chloride, ethanol, and calcium chloride did not, under the conditions used, induce stress proteins in the rat lens. Sodium arsenite, however, had very much the same effects as heat shock. Calcium ionophore A23187 specifically and effectively induced the synthesis of the glucose-regulated protein GRP78. No special response to stress on crystallin synthesis was noticed.

Creating pure nanostructures from electron-beam-induced deposition using purification techniques: a technology perspective.

The creation of functional nanostructures by electron-beam-induced deposition (EBID) is becoming more widespread. The benefits of the technology include fast 'point-and-shoot' creation of three-dimensional nanostructures at predefined locations directly within a scanning electron microscope. One significant drawback to date has been the low purity level of the deposition. This has two independent causes: (1) partial or incomplete decomposition of the precursor molecule and (2) contamination from the residual chamber gas. This frequently limits the functionality of the structure, hence it is desirable to improve the decomposition and prevent the inclusion of contaminants. In this contribution we review and compare for the first time all the techniques specifically aimed at purifying the as-deposited impure EBID structures. Despite incomplete and scattered data, we observe some general trends: application of heat (during or after deposition) is usually beneficial to some extent; working in a favorable residual gas (ultra-high vacuum set-ups or plasma cleaning the chamber) is highly recommended; gas mixing approaches are extremely variable and not always reproducible between research groups; and carbon-free precursors are promising but tend to result in oxygen being the contaminant species rather than carbon. Finally we highlight a few novel approaches.

Evolution of eye lens crystallins: the stress connection.

Crystallins, the structural proteins of the eye lens, ensure the transparency and integrity of the lens throughout life. Recent sequence comparisons have shown that evolution has recruited crystallins among already existing heat-shock proteins and stress-inducible enzymes.

Si amorphization by focused ion beam milling: Point defect model with dynamic BCA simulation and experimental validation.

A Ga focused ion beam (FIB) is often used in transmission electron microscopy (TEM) analysis sample preparation. In case of a crystalline Si sample, an amorphous near-surface layer is formed by the FIB process. In order to optimize the FIB recipe by minimizing the amorphization, it is important to predict the amorphous layer thickness from simulation. Molecular Dynamics (MD) simulation has been used to describe the amorphization, however, it is limited by computational power for a realistic FIB process simulation. On the other hand, Binary Collision Approximation (BCA) simulation is able and has been used to simulate ion-solid interaction process at a realistic scale. In this study, a Point Defect Density approach is introduced to a dynamic BCA simulation, considering dynamic ion-solid interactions. We used this method to predict the c-Si amorphization caused by FIB milling on Si. To validate the method, dedicated TEM studies are performed. It shows that the amorphous layer thickness predicted by the numerical simulation is consistent with the experimental data. In summary, the thickness of the near-surface Si amorphization layer caused by FIB milling can be well predicted using the Point Defect Density approach within the dynamic BCA model.

Structure-based design and protein engineering of intersubunit disulfide bonds in gonadotropins.

Pairs of cystine residues were introduced in the alpha- and beta-subunits of human choriogonadotropin at positions with optimal geometries for the formation of disulfide bonds. Using the homology with luteinizing hormone and follicle stimulating hormone, similar mutations were carried out in these glycoprotein hormones. In nearly all mutants the corresponding disulfide bonds were formed leading to a non-natural, covalent linkage between the alpha- and beta-subunits. The mutants typically display wild-type receptor binding and bioactivity. The mutants with non-natural intersubunit disulfide bonds display enhanced thermostabilities relative to the corresponding heterodimeric glycoprotein hormones, rendering them candidates for long acting gonadotropins with enhanced shelf lives.

Crystallization and preliminary crystallographic analysis of antistasin, a leech-derived inhibitor of blood coagulation factor Xa.

The salivary gland of the Mexican leech Haementeria officinalis contains a 15 kDa protein which is a potent and selective inhibitor of factor Xa. It inhibits not only blood coagulation, but also metastasis. A gene, coding for a sequence similar to published antistasin sequences, has been synthesized and expressed in Chinese hamster ovary (CHO) cells. The recombinant protein was purified and crystallized at pH 6.0, using 31% ammonium sulfate as a precipitant. The crystals diffract at least to 2.8 A. The spacegroup is I422 with a = b = 77.7 A and c = 88.4 A. The crystals contain 42% solvent and one protein molecule in the asymmetric unit. A search for heavy atom derivatives is in progress.

Crystallization and preliminary X-ray analysis of human antithrombin III.

Human antithrombin III has been crystallized from 18 to 21% (w/v) polyethylene glycol 4000 at pH 7.15. The spacegroup is P2(1) with cell parameters a = 89.8 A, b = 100.8 A, c = 70.0 A and beta = 106 degrees. The diffraction limit is 3.2 A. The asymmetric unit contains two protein molecules. Analysis of dissolved crystals for biological activity and by gel electrophoresis suggests that one protein molecule in the asymmetric unit is intact, while the other is cleaved.