Roland Sachser

Focused electron beam induced deposition: A perspective

Summary Background: Focused electron beam induced deposition (FEBID) is a direct-writing technique with nanometer resolution, which has received strongly increasing attention within the last decade. In FEBID a precursor previously adsorbed on a substrate surface is dissociated in the focus of an electron beam. After 20 years of continuous development FEBID has reached a stage at which this technique is now particularly attractive for several areas in both, basic and applied research. The present topical review addresses selected examples that highlight this development in the areas of charge-transport regimes in nanogranular metals close to an insulator-to-metal transition, the use of these materials for strain- and magnetic-field sensing, and the prospect of extending FEBID to multicomponent systems, such as binary alloys and intermetallic compounds with cooperative ground states. Results: After a brief introduction to the technique, recent work concerning FEBID of Pt–Si alloys and (hard-magnetic) Co–Pt intermetallic compounds on the nanometer scale is reviewed. The growth process in the presence of two precursors, whose flux is independently controlled, is analyzed within a continuum model of FEBID that employs rate equations. Predictions are made for the tunability of the composition of the Co–Pt system by simply changing the dwell time of the electron beam during the writing process. The charge-transport regimes of nanogranular metals are reviewed next with a focus on recent theoretical advancements in the field. As a case study the transport properties of Pt–C nanogranular FEBID structures are discussed. It is shown that by means of a post-growth electron-irradiation treatment the electronic intergrain-coupling strength can be continuously tuned over a wide range. This provides unique access to the transport properties of this material close to the insulator-to-metal transition. In the last part of the review, recent developments in mechanical strain-sensing and the detection of small, inhomogeneous magnetic fields by employing nanogranular FEBID structures are highlighted. Conclusion: FEBID has now reached a state of maturity that allows a shift of the focus towards the development of new application fields, be it in basic research or applied. This is shown for selected examples in the present review. At the same time, when seen from a broader perspective, FEBID still has to live up to the original idea of providing a tool for electron-controlled chemistry on the nanometer scale. This has to be understood in the sense that, by providing a suitable environment during the FEBID process, the outcome of the electron-induced reactions can be steered in a controlled way towards yielding the desired composition of the products. The development of a FEBID-specialized surface chemistry is mostly still in its infancy. Next to application development, it is this aspect that will likely be a guiding light for the future development of the field of focused electron beam induced deposition.

A Tunable Strain Sensor Using Nanogranular Metals

This paper introduces a new methodology for the fabrication of strain-sensor elements for MEMS and NEMS applications based on the tunneling effect in nano-granular metals. The strain-sensor elements are prepared by the maskless lithography technique of focused electron-beam-induced deposition (FEBID) employing the precursor trimethylmethylcyclopentadienyl platinum [MeCpPt(Me)3]. We use a cantilever-based deflection technique to determine the sensitivity (gauge factor) of the sensor element. We find that its sensitivity depends on the electrical conductivity and can be continuously tuned, either by the thickness of the deposit or by electron-beam irradiation leading to a distinct maximum in the sensitivity. This maximum finds a theoretical rationale in recent advances in the understanding of electronic charge transport in nano-granular metals.

Tuning the electrical conductivity of Pt-containing granular metals by postgrowth electron irradiation

We fabricated Pt-containing granular metals by focused electron beam–induced deposition from the (CH3)3CH3C5H4Pt precursor gas. The granular metals are made of platinum nanocrystallites embedded in a carbonaceous matrix. We exposed the as-grown nanocomposites to low-energy electron beam irradiation and measured the electrical conductivity as a function of irradiation dose. Postgrowth electron beam irradiation transforms the matrix microstructure and thus the strength of the tunneling coupling between Pt nanocrystallites. For as-grown samples (weak tunnel coupling regime) we find that the temperature dependence of the electrical conductivity follows the stretched exponential behavior characteristic of the correlated variable-range hopping transport regime. For briefly irradiated samples (strong tunnel coupling regime) the electrical conductivity is tuned across the metal-insulator transition. For long-time irradiated samples the electrical conductivity behaves like that of a metal. In order to further anal...

The transient electrical conductivity of W-based electron-beam-induced deposits during growth, irradiation and exposure to air

W-based granular metals have been prepared by electron-beam-induced deposition from the tungsten hexacarbonyl W(CO)(6) precursor. In situ electrical conductivity measurements have been performed to monitor the growth process and to investigate the behavior of the deposit under electron beam post-irradiation and by exposure to air. During the first part of the growth process, the electrical conductivity grows nonlinearly, independent of the electron beam parameters. This behavior is interpreted as the result of the increase of the W-particles diameter. Once the growth process is terminated, the electrical conductivity decreases with the logarithm of time, sigma approximately ln(t). Temperature-dependent conductivity measurements of the deposits reveal that the electrical transport takes place by means of electron tunneling either between W-metal grains or between grains and trap sites in the matrix. After venting the electron microscope the electrical conductivity of the deposits shows a degradation behavior, which depends on the composition. Electron post-irradiation increases the electrical conductivity of the deposits.

Conductance regimes of W-based granular metals prepared by electron beam induced deposition

We prepared a series of W-based granular metals by means of electron beam induced deposition from the carbonyl percursor W(CO)6. For samples with W-contents of 31.8(±1.4), 34.0(±1.7) and 36.9(±1.8) at%, we observed a modified power law dependence σ=σ0+bTβ of the electrical conductivity with β=0.47–0.58, which we found to be approximately fulfilled over the temperature range from about 2 to 265 K. Deviations from this modified power law are discussed. Existing theoretical approaches that can, in principle, account for power-law dependencies in σ(T) for homogeneously disordered or granular metals are reviewed and their relevance for explaining our data is critically examined. Firstly, if a percolating path is formed by touching metallic particles, the formation of a pseudo-gap at the Fermi level that follows a T1/2 temperature dependence according to Altshuler and Aronov may explain our data. However, the Altshuler–Aronov result is valid for weak Coulomb coupling and represents a small, low-temperature correction. Its applicability close to a metal–insulator transition is questionable. Secondly, we analyze whether an alternative transport mechanism may be at work that is based on the onset of large-scale coherent electron motion along a tunnel-percolation path in the limit of large inter-grain tunneling. Again, this approach cannot be unambiguously applied to explain our experimental findings.

Universal Conductance Correction in a Tunable Strongly Coupled Nanogranular Metal

We present temperature-dependent conductivity data obtained on a sample set of nanogranular Pt-C with finely tuned intergrain tunnel coupling strength g. For samples in the strong-coupling regime g > g(C), characterized by a finite conductivity for T→0, we find a logarithmic behavior at elevated temperatures and a crossover to a √T behavior at low temperatures over a wide range of coupling strengths g(C) ≈ 0.25 < g ≤ 3. The experimental observation for g > 1 is in very good agreement with recent theoretical findings on ordered granular metals in three spatial dimensions. The results indicate a validity of the predicted universal conductivity behavior that goes beyond the immediate range of the approach used in the theoretical derivation.

Binary Pt–Si Nanostructures Prepared by Focused Electron-Beam-Induced Deposition

Binary systems of Pt-Si are prepared by electron-beam-induced deposition using the two precursors, trimethyl(methylcyclopentadienyl)platinum(IV) (MeCpPt(Me)(3)) and neopentasilane (Si(SiH(3))(4)), simultaneously. By varying the relative flux of the two precursors during deposition, we are able to study composites containing platinum and silicon in different ratios by means of energy-dispersive X-ray spectroscopy, atomic force microscopy, electrical transport measurements, and transmission electron microscopy. The results show strong evidence for the formation of a binary, metastable Pt(2)Si(3) phase, leading to a maximum in the conductivity for a Si/Pt ratio of 3:2.

Room temperature L10 phase transformation in binary CoPt nanostructures prepared by focused-electron-beam-induced deposition

CoPt-C binary alloys have been fabricated by focused-electron-beam-induced deposition by the simultaneous use of Co₂(CO)₈ and (CH₃)₃CH₃C₅H₄Pt as precursor gases. The alloys are made of CoPt nanoparticles embedded in a carbonaceous matrix. TEM investigations show that as-grown samples are in an amorphous phase. By means of a room temperature low-energy electron irradiation treatment the CoPt nanoparticles transform into face-centered tetragonal L1₀ nanocrystallites. In parallel, the system undergoes a transition from a superparamagnetic to a ferromagnetic state at room temperature. By variation of the post-growth irradiation dose the electrical and magneto-transport properties of the alloy can be continuously tuned.

Catalytic purification of directly written nanostructured Pt microelectrodes.

In the majority of cases, nanostructures prepared by focused electron beam induced deposition employing an organometallic precursor contain predominantly carbon-based ligand dissociation products. This is unfortunate with regard to using this high-resolution direct-write approach for the preparation of nanostructures for various fields, such as mesoscopic physics, micromagnetism, metaoptical phenomena in the visible spectral range, or others. Following early attempts of postprocessing Pt-based structures prepared by focused electron beam induced deposition at several hundred degrees Celsius in a reactive gas atmosphere, recent work has focused on developing in situ purification processes by using a stationary O2 flux in combination with electron irradiation to oxidize the carbonaceous component of the deposits. Here we show that this purification process is driven by the catalytic activity of Pt and in fact does not rely on the parallel electron irradiation process to function, if the O2 exposure is done in a pulsed fashion. We suggest a multistep cleaning mechanism which results in pure, nanoporous Pt. By suitably chosen beam parameters, high-resolution Pt dot and line structures with dimensions below 10 nm can thus be conveniently obtained. In temperature-dependent resistance measurements, we find the typical metallic behavior of Pt. In low-temperature magnetoresistance measurements, we see clear evidence for weak antilocalization effects and deduce a dephasing length of 234 nm at 1.2 K. We consider this to be a promising starting point for developing this approach into a versatile preparation technique for Pt-based mesoscopic structures, in particular since the purification process can be run in parallel on different deposits. We furthermore anticipate that our results will spur further research on purification approaches for nanostructures prepared by focused electron beam induced deposition containing a catalytically active metal species such as Pd-, Fe-, or Co-based deposits.

Magnetotransport properties of iron microwires fabricated by focused electron beam induced autocatalytic growth

We have prepared iron microwires in a combination of focused electron beam induced deposition and autocatalytic growth from the iron pentacarbonyl, Fe(CO)5, precursor gas under ultra-high vacuum conditions. The electrical transport properties of the microwires were investigated and it was found that the temperature dependence of the longitudinal resistivity (?xx) shows a typical metallic behaviour with a room temperature value of about 88????cm. In order to investigate the magnetotransport properties we have measured the isothermal Hall-resistivities in the range between 4.2 and 260?K. From these measurements, positive values for the ordinary and the anomalous Hall coefficients were derived. The relation between anomalous Hall resistivity (?AN) and longitudinal resistivity is quadratic, , revealing an intrinsic origin of the anomalous Hall effect. Finally, at low temperature in the transversal geometry a negative magnetoresistance of about 0.2% was measured.