Four-point Probe Measurements Research Articles

Tracking Charge Carrier Paths in Freestanding GaN/AlN Nanowires on Si(111).

Functional and abundant substrate materials are relevant for applying all sophisticated semiconductor-based device components such as nanowire arrays. In the case of GaN nanowires grown by metalorganic vapor phase epitaxy, Si(111) substrates are widely used, together with an AlN interlayer to suppress the well-known Ga-based melt-back-etching. However, the AlN interlayer can degrade the interfacial conductivity of the Si(111) substrate. To reveal the possible impact of this interlayer on the overall electrical performance, an advanced analysis of the electrical behavior with suitable spatial resolution is essential. For the electrical investigation of the nanowire-to-substrate junction, we used a four-point probe measurement setup with sufficiently high spatial resolution. The charge separation behavior of the junction is also demonstrated by an electron beam-induced current mode, while the n-GaN nanowire (NW) core exhibits good electrical conductivity. The charge carrier-selective transport at the NW-to-substrate junction can be attributed to different, local material compositions by two main effects: the reduction of Ga adatoms by shadowing of the lower part of the NW structure by the top part during growth, i.e. the protection of the pedestal footprint from Ga adsorption. Our combination of investigation methods provides direct insight into the nanowire-to-substrate junction and leads to a model of the conductivity channels at the nanowire base. This knowledge is crucial for all future GaN bottom-up grown nanowire structure devices on conductive Si(111) substrates.

Development of microstructure-rheological and electrical properties relationship in PS/POE/HNTs blend nanocomposites using machine learning

Halloysite nanotubes (HNTs) and polypropylene-grafted maleic anhydride (PP-g-MA) were studied for their effects in blends of polystyrene (PS) and polyolefin elastomer (POE). The method used to prepare PS/POE blends (90/10 and 80/20 wt/wt) containing 1, 3, and 5 phr HNTs with or without PP-g-MA (a compatibilizer) was melt blending. Structural and morphological studies using X-ray diffraction analysis (XRD), scanning electron microscopy assisted energy dispersive X-ray spectroscopy (SEM-EDS), and transmission electron microscopy (TEM) confirmed a matrix-droplet morphology and the sample containing compatibilizer has better microstructure than the other formulations. The presence of both PP-g-MA and HNTs together has been discovered to improve the viscoelastic properties of the solid, as evidenced by increased storage modulus and complex viscosity. A notable change occurred in the rheological behavior of the PS/POE blends containing 5 phr of PP-g-MA and HNTs. The dependence of zero-shear viscosity on HNTs loading (0–5 phr) was approximated as a polynomial curve by fitting the experimental data with the Carreau-Yasuda model. Computational fluid dynamics (CFD) simulations were also used to study the effects of HNTs loading on changes in fluid flow patterns and shear rates. The calculated effective viscosities at a given shear rate (0.05 1/s) were in qualitative agreement with the experimental results. Moreover, we utilized various machine-learning techniques to predict the complex viscosity of PS/POE blends and their nanocomposites. The results showed that Extreme Gradient Boosting (XGBoost) outperformed other predictive models based on evaluation metrics. Four-point probe measurements found that the samples containing 5 phr HNT had the lowest conductivities due to the presence of aggregated structures. However, the homogeneous distribution of HNT led to a sudden rise in conductivity in the samples containing 5 phr of PP-g-MA. Computer modeling results of samples with uniform and non-uniform HNT distributions showed that the conductivity decreased with HNT loading and decreased considerably compared to the uniform distribution.

Wide-range resistivity characterization of semiconductors with terahertz time-domain spectroscopy

Resistivity is one of the most important characteristics in the semiconductor industry. The most common way to measure resistivity is the four-point probe method, which requires physical contact with the material under test. Terahertz time domain spectroscopy, a fast and non-destructive measurement method, is already well established in the characterization of dielectrics. In this work, we demonstrate the potential of two Drude model-based approaches to extract resistivity values from terahertz time-domain spectroscopy measurements of silicon in a wide range from about 10−3 Ωcm to 102 Ωcm. One method is an analytical approach and the other is an optimization approach. Four-point probe measurements are used as a reference. In addition, the spatial resistivity distribution is imaged by X-Y scanning of the samples to detect inhomogeneities in the doping distribution.

Conjugated Polymers with Self-Immolative Sidechain Linkers for Carbon Nanotube Dispersion.

Single-walled carbon nanotubes (SWNTs) are promising materials for generating high-performance electronic devices. However, these applications are greatly restricted by their lack of purity and solubility. Commercially available SWNTs are a mixture of semi-conducting (sc-) and metallic (m-) SWNTs and are insoluble in common solvents. Conjugated polymers can selectively disperse either sc- or m-SWNTs and increase their solubility; however, the conductivity of conjugated polymer-wrapped SWNTs is largely affected by the polymer side chains. Here, a poly(fluorene-co-phenylene) polymer that contains a self-immolative linker as part of its sidechains is reported. The self-immolative linker is stabilized with a tert-butyldimethylsilyl ether group that, upon treatment with tetra-n-butylammonium fluoride (TBAF), undergoes a 1,6-elimination reaction to release the sidechain. Sonication of this polymer with SWNTs in tetrahydrofuran (THF) results in concentrated dispersions that are used to prepare polymer-SWNT thin films. Treatment with TBAF caused side-chain cleavage into carbon dioxide and the corresponding diol, which can be easily removed by washing with solvent. This process is characterized by a combination of absorption and Raman spectroscopy, as well as four-point probe measurements. The conductance of the SWNT thin films increased ≈60-fold upon simple TBAF treatment, opening new possibilities for producing high-conductivity SWNT materials for numerous applications.

Etching and Compositional Ratio Effect on the Surface Properties of Bismuth Telluride Thin Films

Bismuth telluride has garnered considerable attention owing to its versatile properties applicable in thermoelectric and antibacterial domains, as well as its intriguing topological insulating properties. In this work, our group fabricated bismuth telluride thin films with various ratios using radio frequency magnetron sputtering. The surface properties of these thin films were thoroughly analyzed by employing a diverse array of analytical techniques, including X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), four-point probe and contact angle (CA) measurements. Specifically, our XPS findings indicated that Bi is more susceptible to oxidation than Te following Ar+-ion etching. Pure Te thin films exhibited the highest Rq value of 31.2 nm based on AFM and SEM results due to their larger grain sizes. The XRD patterns revealed a peak at 27.75° for thin films with 20% Te, attributed to its rhombohedral structure. Moreover, thin films with 30% Te yielded the highest weighted average work function with a value of 4.95 eV after etching. Additionally, pristine Bi and Te thin films demonstrated the most robust hydrophobic properties compared to intermediate-composition thin films, as determined by CA measurements.

Aerosol-Assisted Chemical Vapor Deposition of 2H-WS2 From Single-Source Tungsten Dithiolene Precursors.

The tungsten carbonyl dimethyldithiolene (dmdt) complexes W(CO)4(dmdt), W(CO)2(dmdt)2, and W(dmdt)3 were evaluated as potential single-source precursors for the chemical vapor deposition of WS2. The results of TGA-MS, DIP-MS, and pyrolysis with NMR analysis were consistent with a thermal decomposition pathway in which loss of 2-butyne through a retro[3+2]cycloaddition of the dithiolene ligand generated terminal sulfido ligands. Aerosol-assisted chemical vapor deposition onto silicon substrates was performed using all three complexes, yielding 2H-WS2 thin films as characterized by Raman spectroscopy and GI-XRD. Film morphology and elemental composition of the films were determined using SEM, EDS, and XPS. Four-point probe measurements afforded a film resistivity of 8.37 Ωcm for a sample deposited from W(dmdt)3 in toluene at 600 °C.

Role of Divalent Co-Dopant as Structure Stabilizer in Scandia-Stabilized Zirconia Electrolyte for SOFC

The present investigation reports the role of divalent binary co-dopant (Ca2+) in 11 mol% scandia stabilized zirconia (11SSZ) electrolytes to resolve its severe long-term aging issue for application in solid oxide fuel cells (SOFC). Dense electrolytes were formulated via the solid-state reaction method and their crystal structure was identified by X-ray diffractometer (XRD). To examine total electrical conductivity and its stability in oxidizing and reducing atmosphere DC four-point probe measurement was used. Among all the compositions, 0.2Ca11SSZ demonstrates the highest conductivity of 0.075 S cm−1 at 800 °C, with excellent stability of 6.7%/100 h in a reducing (97 vol% H2/3 vol% H2O) atmosphere. However, the presence of 0.5 mol% calcium in 11SSZ results in more than threefold suppression of aging rate compared to undoped11SSZ i.e. 2.19%/200 h in air atmosphere at 800 °C. Additionally, the doping of divalent Ca2+ widens the electrolytic domain up to pO2 ∼ 10−26 atm at 1000 °C compared to state-of-art 8YSZ (pO2 ∼ 10−22 atm), with 0.024% linear expansion on phase transition and 172 MPa flexural strength. Convincingly, the excellent structure stability and ionic conductivity of calcium co-doped 11SSZ compared to state-of-the-art electrolytes make them potential candidates to be used as an electrolyte for SOFC application.

Superior Conductivity of Transparent ZnO/MoS2 Composite Films for Optoelectronic and Solar Cell Applications.

The use of transparent conductive oxides in optoelectronics created a revolution where new-generation materials with high transmittance, low sheet resistance values, durability, and portability can be achieved without decreasing efficiency or increasing costs. Transparent ZnO/MoS2 sandwich-structured conductive composite films were produced in this study via the sol-gel method, which is considered the most efficient method due to its simple process and low cost. The crystal structure properties of ZnO/MoS2 were characterized via X-ray diffraction (XRD) patterns. The crystal sizes of ZnO films doped with different amounts of MoS2 were determined. A UV-visible absorption spectrometer was used to perform the spectroscopic analysis of the film. The area under the absorption curve and the full width of the half-maxima of absorbance data were calculated. Using these values, the optimum amount of MoS2 was determined for the best additive distribution. In addition, in order to determine the best transparent conductive material, resistance values measured via the four-point probe method were compared for different MoS2 additive amounts. The optical and electrical characterizations of transparent ZnO/MoS2 conductive oxide films were investigated. According to the parameters obtained via UV-vis spectroscopy, XRD, and four-point probe measurements, the most effective dispersion that exhibits a low width ratio and high resonance ratio was found for ZnO/MoS2 with a doping amount of 4 mg, the crystallite size of the films was found to be within the range of 21.5 and 24.6 nm, and these observations demonstrated a figure-of-merit value of more than 4.8 × 10-2 with respect to these sandwich-structured films. Compared to the values of previous studies on various transparent ZnO-doped conductive oxide materials, it is possible to claim that these new films have a structure that is very similar to the transparent conductivity characteristics of other films, and they may even be superior relative to some MoS2 amounts.

Deconvolution of heat sources for application in thermoelectric micro four-point probe measurements

Joule heating is a primary phenomenon responsible for increasing temperature in electronic devices, and consequently, decreasing the lifetime and performance of electronic devices. However, this unwanted Joule heating can itself be used as a local source of heat to map the temperature-dependent material properties. Recently, micro four-point probe (M4PP) showed a promising potential for characterizing the temperature coefficient of resistance (TCR) and the Seebeck coefficient using Joule heating resulting from the measurement current. Here, we use M4PP to estimate the micrometer scale, relative temperature profile resulting from a single heat source. We introduce a triplet of four-point voltages measured at the second harmonic frequency, to deconvolute the thermoelectric voltage from the three individual heat sources involved. This paper tests and documents the validity of the proposed scheme in the 1–40 μm range on highly doped single crystal Si at 300 K, supporting predominantly Fourier heat transport at these scales. The method of deconvolution of heat sources reduces the complexity in evaluation of length- and time-dependent measurements, specifically used in the characterization of thermoelectric properties. The proposed method may also facilitate a more profound understanding of heat transport on the mesoscopic scale.

Studying the Effects of Annealing and Surface Roughness on Both the Magnetic Property and Surface Energy of Co60Fe20Sm20 Thin Films on Si(100) Substrate

In this study, Co60Fe20Sm20 alloy was employed for sputter deposition onto Si(100) substrate within a high vacuum environment, and subsequent thermal treatment was conducted using a vacuum annealing furnace. Thorough measurements and analyses were carried out to evaluate how various film thicknesses and annealing temperatures affect the material. The investigations encompassed observations of structural and physical properties, magnetic traits, mechanical behavior, and material adhesion. The results from the four-point probe measurements clearly demonstrate a trend of decreasing resistivity and sheet resistance with increasing film thickness and higher annealing temperature. Analysis through atomic force microscopy (AFM) shows that heightened annealing temperature corresponds to decreased surface roughness. Furthermore, when analyzing low-frequency alternating current magnetic susceptibility (χac), it became evident that the maximum magnetic susceptibility value consistently rises with increased film thickness, regardless of the annealing temperature. Through magnetic force microscopy (MFM) observations of magnetic domain images in the films, it became apparent that there was a noticeable reduction in the brightness contrast of the magnetic domains. Furthermore, nanoindentation analysis reveals a clear trend. Elevating the film thickness leads to a reduction in both hardness and Young’s modulus. Contact angles range between 67.7° and 83.3°, consistently under 90°, highlighting the hydrophilic aspect. Analysis of surface energy demonstrates an escalation with increasing film thickness, and notably, annealed films exhibit a substantial surge in surface energy. This signifies a connection between the reduction in contact angle and the observed elevation in surface energy. Raising the annealing temperature causes a decline in surface roughness. To summarize, the surface roughness of CoFeSm films at different annealing temperatures significantly impacts their magnetic, electrical, and adhesive properties. A smoother surface reduces the pinning effect on domain walls, thus enhancing the χac value. Furthermore, diminished surface roughness leads to a decline in the contact angle and a rise in surface energy. Conversely, rougher surfaces exhibit higher carrier conductivity, contributing to a reduction in electrical resistance.

Influence of Deposition Parameters of ITO Films on the Performance of HJT Solar Cells

TCO (transparent conductive oxide) films are widely used in solar cells due to the characteristics of transparency and conductivity. In this paper, ITO (indium tin oxide) transparent conductive films are prepared on common slides by DC magnetron sputtering, and the preparation process and characteristics of ITO films are studied. The target for sputtering is ITO, with the mass ratio of In203 and Sn02 was 90% : 10%. The sheet resistance, carrier concentration, and carrier mobility of ITO films are measured and analyzed by a UV-Vis spectrophotometer, four-point probe, and Hall effect measurement system. By changing the oxygen content, deposition temperature, and sputtering power to studied the effects on the light transmittance and electrical conductivity of the ITO films, further studied the effects on the HJT (heterojunction with intrinsic thin film) solar cells, and finally determined the appropriate preparation parameters. Results show that the resistance is 6 . 4 ∗ 10 − 4 Ω • cm , the light transmittance is beyond 90.6%, efficiency is 23.78%, and bifacial ratio is 84% when oxygen content is 2.2%, sputtering power is 3 kw, and deposition temperature is 190°C.

Improving charge transport in integrated MoO3/C electrode materials for water-in-salt energy storage systems by incorporating oxygen vacancies

Improvements in the charge storage properties of ⍺-MoO3 used as an electrode with a 30 m ZnCl2 water-in-salt electrolyte have been achieved by enhancements in electron and ion transport enabled by an inventive synthesis route. Electron transport was improved through the integration of MoO3 with dopamine-derived carbon via a chemical preintercalation route, and enhanced ion transport was achieved by incorporating oxygen vacancies in MoO3 structure through ethanol reduction under hydrothermal conditions. The presence of carbon was confirmed by corresponding D and G bands observed in Raman spectroscopy measurements. The presence of oxygen vacancies was proven through correlated XPS, TGA, Raman spectroscopy and XRD analyses, with the introduction of oxygen vacancies leading to an expanded interlayer region. Four-point probe measurements provided evidence of increased electronic conductivity due to the incorporation of carbon, and cyclic voltammetry-based charge storage mechanism analyses revealed increases in ion transport kinetics due to oxygen vacancy formation. Tuning the oxygen vacancy concentration is critical, as excessive concentrations of these point defects leads to structural instability and poor capacity retention. This work demonstrates the combined potential of carbon and oxygen vacancies in moderate concentrations to enhance the charge storage properties of transition metal oxides. The strategies developed in this study offer a path to the development of promising materials for high-rate, high-capacity, and long-duration electrochemical energy storage technologies.

Design of PGM-Free Cathode Catalyst Layers for PEMFC Applications: The Impact of Electronic Conductivity

The impact of the electronic resistance of platinum-group-metal-free cathode catalyst layers (PGM-free CCLs) for proton-exchange-membrane fuel cells (PEMFCs) was systematically investigated. Here we selected two different PGM-free catalysts (having high and low electronic conductivity) and integrated them into CCLs without and with conductive carbon fiber additives. To investigate the impact of the electronic resistivity () of PGM-free catalysts and CCLs, their through-plane values were quantified by an in situ electrochemical impedance spectroscopy (EIS) approach based on a one-dimensional transmission line model. The results indicate that the electronic conductivity of PGM-free CCLs can be increased by adding carbon additive, resulting in a significant improvement of the fuel cell performance (by ∼60 mV at 1 A cm−2 in H2/O2 configuration). Ex situ four-point probe measurements of the in-plane values of some of the CCLs were found to differ vastly from the through-plane values. This difference is attributed to the anisotropic morphology of the CCLs, caused by preferential fiber orientation and/or cracks in the CCLs. In the end, we suggest guidelines for the design and evaluation of PGM-free CCLs and for assessing and improving their electronic resistance.

Investigation of the microstructure, hardness and electrical conductivity properties of Fe/Graphene compacts

ABSTRACT The effects of graphene nanoplatelets added to pure Fe powders at different rates on microstructure, hardness and electrical conductivity were investigated. Prepared mixed powders were compressed at 700 MPa pressure and sintered at 1250°C. Densities of samples were measured Archimedes technique. Scanning electron microscope was used for microstructure investigations. The hardness was measured according to ASTM E384. Phase types, average crystallite size and dislocation density calculations in sintered samples were made. Electrical resistance measurements were made with the four-point probe measurement technique. Powder mixtures containing ≤5 wt-% graphene nanoplatelets were sintered into compact samples. The smallest grain size, highest dislocation density, highest hardness and electrical conductivity values were obtained in samples containing 2 wt-% of graphene nanoplatelets.

Direct 3D microprinting of highly conductive gold structures via localized electrodeposition

Directly 3D-printed metal microstructures could enable hybrid micromanufacturing, combining conventional micromanufacturing with additive micromanufacturing (µAM). The microstructure’s material properties, including the electrical resistivity, are of decisive importance for a wide range of applications in microelectronics, high-frequency communication, and biomedical engineering. In this work, we present a room-temperature process for µAM of gold structures based on local electrodeposition. We demonstrate control of the electrodeposition process by regulating the precursor species supply rate through air pressure and by regulating the reaction rate through the electrodeposition potential. We 3D printed complex gold microscale structures and characterized the resistivity of the printed gold by developing hybrid devices with integrated four-point probe measurement capability. Additionally, we printed copper microwires, building on a previously shown copper µAM process, and characterized the copper resistivity. We demonstrate near-bulk resistivity values of 65 nΩ·m (about 2.5 times higher than bulk) and 19 nΩ·m (only 10% higher than bulk) for the gold and copper wires, respectively, without post-treatment. Microstructural analysis of the gold wires revealed a dense metal deposit free of voids. Finally, we printed gold structures on a pre-patterned substrate, paving the way to hybrid devices in which additive micromanufacturing is combined with existing micromanufacturing techniques.

Study of Single and Multipass f-rGO Inkjet-Printed Structures with Various Concentrations: Electrical and Thermal Evaluation.

Reduced graphene oxide (rGO) is a derivative of graphene, which has been widely used as the conductive pigment of many water-based inks and is recognized as one of the most promising graphene-based materials for large-scale and low-cost production processes. In this work, we evaluate a custom functionalised reduced graphene oxide ink (f-rGO) via inkjet-printing technology. Test line structures were designed and fabricated by the inkjet printing process using the f-rGO ink on a pretreated polyimide substrate. For the electrical characterisation of these devices, two-point (2P) and four-point (4P) probe measurements were implemented. The results showed a major effect of the number of printed passes on the resulting resistance for all ink concentrations in both 2P and 4P cases. Interesting results can be extracted by comparing the obtained multipass resistance values that results to similar effective concentration with less passes. These measurements can provide the ground to grasp the variation in resistance values due to the different ink concentrations, and printing passes and can provide a useful guide in achieving specific resistance values with adequate precision. Accompanying topography measurements have been conducted with white-light interferometry. Furthermore, thermal characterisation was carried out to evaluate the operation of the devices as temperature sensors and heaters. It has been found that ink concentration and printing passes directly influence the performance of both the temperature sensors and heaters.

Ultrashort laser sintering of printed silver nanoparticles on thin, flexible, and porous substrates

The fabrication of low-cost and mechanically robust flexible electronic patterns has increasingly gained attention due to their growing applications in flexible displays, touch screen panels, medical devices, and solar cells. Such applications require cost-effective deposition of metals in a well-controlled manner potentially using nanoparticles (NPs). The presence of solvent and precursors in NP based inks impacts the electrical conductivity of the printed pattern and a post-processing heating step is typically performed to restore the electrical properties and structure of the material. We report printing with picolitre droplet volumes of silver (Ag) NPs on flexible substrates using an acoustic microdroplet dispenser. The low-cost, controlled deposition of Ag ink is performed at room temperature on photopaper, polyimide and clear polyimide substrates. A localized, ultrashort pulsed laser with minimal heat affected zone is employed to sinter printed Ag patterns. For comparison, oven sintering is performed, and the results are analysed with scanning electron microscopy, four-point probe and Hall measurements. The femtosecond laser sintering revealed highly organized, connected nanostructure that is not achievable with oven heating. A significant decrease in sheet resistance, up to 93% in Ag NPs on clear polyimide confirms the laser sintering improves the connectivity of the printed film and as a result, the electrical properties are enhanced. The surface morphology attained by the laser sintering process is interpreted to be due to a joining of NPs as a result of a solid-state diffusion process in the near surface region of NPs.

On the influence of Ni(Pt)Si thin film formation on agglomeration threshold temperature and its impact on 3D imaging technology integration

Ni(10 at.% Pt) monosilicide is used as contact in microelectronics but suffers from degradation at relatively low temperatures due to agglomeration. Recent results obtained on 28 nm-FDSOI (Fully Depleted Silicon On Isolator) microelectronics devices have demonstrated severe yield loss after an anneal at 550 °C/2 h linked to Ni(Pt)Si film dewetting. Such agglomeration thermal budget is 100 °C lower than the ones measured on blanket wafers with in-situ or ex-situ four-point probe measurements. In this context, the aim of this paper is to investigate the effect Ni(Pt)Si formation process on the Ni(Pt)Si agglomeration using different approaches as (i) the classical one in which one anneal is applied to form silicide and leads also to agglomeration, (ii) the silicide formation through the standard SALICIDE process, “Self-Aligned Silicide”, and a subsequent anneal to induce agglomeration, and (iii) the standard SALICIDE process for silicide formation followed by an encapsulation of the top silicide surface by a SiN layer as applied in devices, and submitted finally to the agglomeration anneal. Our work demonstrated that the film thermal stability is influenced by the sequencing of the Selective Etch (SE) in the formation process and whether it is formed by a single or a double anneal. For single anneal, the thermal budget needed to agglomerate Ni(Pt)Si film is higher i.e., agglomeration occurs at around 700 °C/30 s in single anneal as compared to double anneal at around 550 °C/30 s. Another conclusion of this work is that four-point probe measurements are not sensitive enough to well estimate the real starting point of agglomeration phenomenon which is detrimental for devices (holes formation at the triple junctions). Some additional characterizations such as tilted Scanning Electron Microscopy (tilted SEM) are deeply needed for an accurate determination of agglomeration thermal budget. This study allows clarifying the main parameters leading to agglomeration: the film thickness and the grain size appear to be the more important ones.

Electron-Enhanced Atomic Layer Deposition of Titanium Nitride Films Using an Ammonia Reactive Background Gas

Electron-enhanced atomic layer deposition (EE-ALD) of titanium nitride (TiN) films was achieved using sequential exposures of tetrakis(dimethylamido)titanium (TDMAT) and low energy electrons in the presence of a continuous NH3 reactive background gas (RBG). Performing EE-ALD concurrently with a RBG is a new ALD film growth technique. The TiN EE-ALD was performed utilizing a hollow cathode plasma electron source (HC-PES). The HC-PES can deliver a high electron flux into background gases at pressures up to several mTorr. The TiN EE-ALD was conducted at temperatures of 30–70 °C using an electron acceleration voltage of 100 V and a NH3 pressure of ∼1 mTorr. The incident electron flux promotes electron stimulated desorption (ESD) and facilitates rapid nucleation and low temperature film growth. The TiN EE-ALD film growth was achieved on a variety of substrates including a native oxide on silicon, a SiO2 thermal oxide, and in situ silicon nitride films grown using electron-enhanced chemical vapor deposition (EE-CVD). Growth rates of 0.75 to 1.8 Å per cycle were measured using in situ four-wavelength ellipsometry for different TDMAT precursor exposures. Ex situ X-ray photoelectron spectroscopy (XPS) studies indicated that the TiN films were high purity and slightly nitrogen-rich. The in situ ellipsometry also measured low resistivities of ∼120 μΩ cm for the TiN films with thicknesses of ≥60 Å. These low resistivities were confirmed by ex situ four-point probe measurements and ex situ spectroscopic ellipsometry. X-ray diffraction investigations determined that the TiN EE-ALD films were crystalline. X-ray reflectivity studies also indicated that the thin TiN films had densities similar to bulk films. The high quality of the TiN EE-ALD films is attributed to the NH3 RBG. Interaction between the low energy electrons and the NH3 RBG is believed to form •NH2 and •H radical species that react with the surface during EE-ALD and improve film purity. The reactive •NH2 and •H species likely lead to nitridation and carbon removal from the films. RBGs greatly expand the possibilities for tuning film composition and properties during EE-ALD. In addition, TiN EE-ALD was accomplished on insulating substrates such as an SiO2 thermal oxide. The TiN EE-ALD is believed to be possible on insulating substrates because the secondary electron yield for electron energies of ∼100 eV is greater than unity.

Determination of thermoelectric properties from micro four-point probe measurements

Micro four-point probing is a branch of electrical metrology where electrical (and electromagnetic) properties of charge carriers such as conductance, mobility, and tunneling magnetoresistance can be accurately and precisely determined at the μm scale and below. Here, we propose and demonstrate a novel application of micro four-point probe (M4PP) aimed at quantifying the thermoelectric properties of a sample. Specifically, we show that for an AC current passing through a bulk material at a low angular frequency ω, the voltage drop across the sensing electrodes at 2ω is to first order proportional to the ratio (α/κ) of its Seebeck coefficient (α) to its thermal conductivity (κ). Verified by numerical simulations, our analytic theory is then put into practice on a suite of p- and n-type bulk semiconductors (Si, Ge, and BiTe). The M4PP estimates of the Seebeck coefficient in these materials are characterized both by high accuracy and precision, suggesting a novel in-situ metrology of thermoelectric properties at the µm scale.