Epitaxial diamond films were deposited on polished single crystal Ib type HPHT diamond plates of (100) orientation by microwave CVD. The epilayers were used for the fabrication of surface channel MESFET structures having sub-micrometer gate length in the range 200-800 nm. Realized devices show maximum drain current and trasconductance values of about 190 mA/mm and 80 mS/mm, respectively, for MESFETs having 200 nm gate length. RF performance evaluation gave cut off frequency of about 14 GHz and maximum oscillation frequency of more than 26 GHz for the same device geometry.

Polycrystalline and mono-crystalline CVD diamonds have been investigated in relation to radiation dosimetry applications. In this work we report results on the thermoluminescence (TL), afterglow (AG) and dosimetric performance on two mono-crystalline CVD diamonds containing boron and silicon as doping materials. The samples were exposed to beta (Sr90/Y90) in the dose range of 0.07-8.26 Gy and UV light in the range of 200-400 nm, followed in both cases, by TL and AG read-outs. The boron doped sample exhibited one main TL peak at 130 °C and some overlapped peaks around 250 °C and the silicon doped samples exhibited two TL peaks around 148 and 286 °C after the crystals were subjected to beta radiation. UV radiation exposed samples showed two main TL peaks around 139 oC for boron doped, with overlapped components in the high temperature side, and at 220 and 355 oC for silicon doped samples. The integrated TL and AG intensities reached saturation around to 3.0 and 1.0 Gy in boron and silicon doped samples, respectively. The AG signal from boron doped samples reached saturation for around 60 s of 230 nm UV light irradiation and the silicon doped sample showed a linear response up to 10 minutes of 300 nm UV exposure with no apparent saturation for higher irradiation times. The TL/AG behavior of the present CVD diamond indicates the promising applications of these materials as TL/AG dosimeter for ionizing and UV radiation.

Carbon nanomaterials especially ultrananocrystalline diamond and nanocrystalline diamond films have attracted more and more interest due to their unique electrical, optical and mechanical properties, which make them widely used for different applications (e.g. MEMS devices, lateral field emission diodes, biosensors and thermoelectrics). Nanocrystalline diamond can also offer novel advantages for drug delivery development. Recent studies have begun to use nanocrystalline diamond for in-vivo molecular imaging and bio-labeling. To enable grafting of complex bio-molecules (e.g. DNA) the surface of ND requires specific fictionalization (e.g. H, OH, COOH & NH2). Due to the surface dipoles of functionalised nanodiamond band bending at the surface can be easily induced and from the measured band bending we can deduce the type of the fictionalization on the surface. The surface potential of H-terminated and OH terminated nanodiamond layers was investigated by Kelvin probe microscope. From the change of the surface potential value (as the departure of the material surface from the state of electrical neutrality is reflected in the energy band bending) the work function of the H-terminated nanodiamond layer was established to be lower than OH-terminated nanodiamond layer. The surface potential difference can be explained by the surface dipole induced by the electro-negativity difference between the termination atoms.

Diamond superlattices were fabricated by producing multilayer structures of isotopically pure carbon-12 (12C) and carbon-13 (13C), which confine electrons by a difference in band-gap energy. Secondary ion mass spectrometry (SIMS) measurements were employed to characterize the isotopic composition of the diamond superlattices. Layers between 2 nm and 350 nm in thickness can be designed and fabricated using a microwave plasma-assisted chemical vapor deposition technique.

Nanocrystalline diamond films have generated much interested due to their diamond-like properties and low surface roughness. Several techniques have been used to obtain a high re-nucleation rate, such as hydrogen poor or high methane concentration plasmas. In this work, the properties of nano-diamond films grown on silicon substrates using a continuous DC bias voltage during the complete duration of growth are studied. Subsequently, the layers were characterised by several morphological, structural and optical techniques. Besides a thorough investigation of the surface structure, using SEM and AFM, special attention was paid to the bulk structure of the films. The application of FTIR, XRD, multi wavelength Raman spectroscopy, TEM and EELS yielded a detailed insight in important properties such as the amount of crystallinity, the hydrogen content and grain size. Although these films are smooth, they are under a considerable compressive stress. FTIR spectroscopy points to a high hydrogen content in the films, while Raman and EELS indicate a high concentration of sp2 carbon. TEM and EELS show that these films consist of diamond nano-grains mixed with an amorphous sp2 bonded carbon, these results are consistent with the XRD and UV Raman spectroscopy data.

It has been reported that physico-chemical properties of diamond surfaces are closely related to the surface chemisorbed species on the surface. Hydrogen chemisorption on a chemical vapor deposition grown diamond surface is well-known to be important for stabilizing diamond surface structures with sp3 hybridization. It has been suggested that an H-chemisorbed structure is necessary to provide a negative electron affinity condition on the diamond surfaces. Negative electron affinity condition could change to a positive electron affinity by oxidation of the H-chemisorbed diamond surfaces. Oxidized diamond surfaces usually show characteristics completely different from those of the H-chemisorbed diamond surfaces. The unique electron affinity condition, or the surface potential, is strongly related to the chemisorbed species on diamond surfaces. The relationship between the surface chemisorption structure and the surface electrical properties, such as the surface potential of the diamond, has been modelled using DFT based calculations.

The oxygen redox couple in adsorbed water films acts as an “electrochemical ground” that tends to pin the Fermi level in solids at the electrochemical potential of the redox couple. We discuss this effect on the conductivity of diamond; the conductivity type of sp2-based carbons including single-walled, semiconducting carbon nanotubes and graphene; the photoluminescence of GaN and ZnO; and the contact charging of metals.

The unique material characteristics of silicon carbide (SiC) and nanocrystalline diamond (NCD) present solutions to many problems in conventional MEMS applications and especially for biologically compatible devices. Both materials have a wide bandgap along with excellent optical, thermal and mechanical properties. Initial experiments were performed for NCD films grown on 3C-SiC using a microwave plasma chemical vapor deposition (MPCVD) reactor. It was observed from the atomic force microscopy (AFM) analysis that the NCD films on 3C-SiC possess a more uniform grain structure, with sizes ranging from approximately 5 – 10 nm, whereas on the Si surface, the NCD has large, non-unioform inclusions of grains ≈1 μm in size. The in vitro biocompatibility performance of NCD/3C-SiC was measured utilizing 2 immortalized neural cell lines: H4 human neuroglioma (ATCC #HTB-148) and PC12 rat pheochromocytoma (ATCC #CRL-1721). MTT (3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay was used to measure viability of the cells for 96 hours and live/ fixed cell. AFM was performed to determine the general cell morphology. The H4 cell line shows a good biocompatibility level with hydrogen treated NCD as compared with the cell treated polystyrene control well, while the PC12 cells show decreased viability on the NCD surfaces.

Previously, the nanocrystalline grain boundaries were often contaminated by the “non-diamond phase” with the photo-ionization threshold at 0.8 eV. Here, we present the optical spectra of the NCD films grown on transparent substrates by the microwave plasma enhanced chemical vapor deposition (CVD) at a relatively low temperature below 600°C. The transmittance and reflectance spectra are useful to evaluate the film thickness, the surface roughness and the index of refraction. The direct measurement of the optical absorptance by the laser calorimetry and photothermal deflection spectroscopy (PDS) provides high sensitive methods to measure the weak optical absorption of thin films with rough surface. The optical measurements indicate the high optical transparency of our standard, nominally undoped 0.2-0.3 μm thick NCD film with low non-diamond content. However, the optical scattering is rather high in UV and needs to be reduced.

In this paper an overview is given on recent results obtained in the framework of an Italian/Croatian collaboration aimed to explore the potential of techniques based on focused MeV ion beams to locally modify the structural, electrical and optical features of diamond.

Experiments were carried out using light (H, He, C) ion beams with energies of the order of MeV, focused to micrometer-size spot and raster scanned onto the surface of monocrystalline (IIa or Ib) diamond samples. Different energies, ion species and fluences were used, in conjunction with variable thickness masks and post annealing processes, to define three-dimensional structures in diamond, whose electrical/optical/structural properties have been suitably characterized. Finite element numerical methods have been employed in the modeling of the material modification and in device design.

With respect to Silicon-on-Diamond approaches as an alternative to SOI where diamond is used as the buried dielectric, we have in recent works demonstrated the feasibility of a novel approaches where the CVD diamond layer is grown on silicon using Bias Enhanced Nucleation (BEN) over large area substrates, then smoothed and assembled to successfully enable the fabrication of first prototypes of silicon-on-diamond substrates. The key novelty to those SOD substrates were that only a very thin box dielectric diamond layer is used (typically from 150 to 500nm thick), as required by the current SOI technology. However we had also observed that the silicon-diamond interface quality to be sensitive to the nature of the nucleation interface. Thus the current contribution here studies the chemical nature of various capping materials used to solve the issue of electrical defects in case of direct silicon-diamond interface and at the same time to enable the whole system to benefit from the high thermal conductivity of diamond when compared to other standard electrical insulating materials.

Nucleation is the rate-determining step in the initial stages of most chemical vapour deposition processes. In order to achieve uniform deposition of diamond thin films it is necessary to seed non-diamond substrates. Here we discuss a simple electrospray deposition technique for application of 5 nm diamond seed particles onto substrates of various sizes. The influence of selected parameters, such as experimental spatial arrangement and colloidal properties, are analysed in optimizing the method by optical and electron microscopy, both before and after nanocrystalline diamond deposition on the seed layer. The advantages and limitations of the electrospray method are highlighted in relation to other commonly exploited nucleation techniques.

Large-signal radiofrequency performances of surface channel diamond MESFET fabricated on hydrogenated polycrystalline diamond are investigated. The adopted device structure is a typical coplanar two-finger gate layout, characterized in DC by an accumulation-like behavior with threshold voltage Vt ∼ 0-0.5 V and maximum DC drain current of 120 mA/mm. The best radiofrequency performances (in terms of fT and fmax) were obtained close to the threshold voltage. Realized devices are analyzed in standard class A operation, at an operating frequency of 2 GHz. The MESFET devices show a linear power gain of 8 dB and approximately 0.2 Wmm RF output power with 22% power added efficiency. An output power density of about 0.8 W/mm can be then extrapolated at 1 GHz, showing the potential of surface channel MESFET technology on polycrystalline diamond for microwave power devices.

The electrical characteristics of high quality single crystal boron-doped diamond are studied. Samples are synthesized in a high power-density microwave plasma-assisted chemical vapor deposition (CVD) reactor at pressures of 130-160 Torr. The boron-doped diamond films are grown using diborane in the feedgas at concentrations of 1 to 50 ppm. The boron acceptor concentration is investigated using infrared absorption and a four point probe is used to study the conductivity. The temperature dependent conductivity is analyzed to determine the boron dopant activation energy.

We successfully observed electron emission from hydrogenated diamond (111) p+-i-n+ junction diodes. Here, p+- and n+-layers mean that the boron and phosphorous impurity concentrations in these layers are around 1020 cm-3. Then the p+-layer on top of the diode suppresses electron emission from the top-surface area. The heavily doped layers also play an important role to obtain high diode and emission currents. The emission started when the applying bias voltage was equal to the built-in potential, and the emission current reached to over 1 μA at room temperature operation. With taking into account our previous photoemission yield spectroscopy results and with the very high binding energy of free excitons of 80 meV in diamond, we suggested that the electron emission was derived from free excitons generated in the i-layer of the diodes.

We employ UV photolithographic and electron beam lithographic patterning of diamond seeding layer on SiO2/Si substrates for the selective growth of micrometer and sub-micrometer diamond patterns. Using bottom-up strategy, thin diamond channels (470 nm in width) are directly grown. Differences between wet chemical and plasma treatment on the patterned diamond growth are studied. We find that the density of parasitic diamond crystals (outside predefined patterns) is lowered for gas mixture CF4/O2 plasma than for rich O2 plasma. After CF4/O2 plasma treatment, the density of parasitic crystals is 106 cm-2 which is comparable to the wet chemical treatment. Introducing sandwich-like structure, i.e. photoresist-seeding layer-photoresist, and its treatment (lift-off and CF4/O2 plasma) further reduces the density of parasitic crystals down to 105 cm-2. The advantage of this novel treatment is short processing time, simplicity, and minimal damage of the substrate surface.