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Recent developments in the field of nano-structured materials for technological as well as scientific prospective are quite interesting. In this context carbon plays a dominant role. Few examples such as carbon nanotubes (CNTs), fullerene, nanostructured diamond, as well as, amorphous carbon film, particularly, diamond-like carbon (DLC) coating are the areas of today’s research. This thesis deals with ECR plasma deposition of carbon in two different forms, i.e., Diamond-like carbon (DLC) and carbon nanotubes (CNTs) In the case of DLC coatings the chemical vapor deposition (CVD) and sputtering CVD configuration has been used. The carbon nanotubes have been grown using CVD configuration. DLC films were deposited by ECR-rf CVD mode, as well as, ECR sputtering mode. In case of CVD films, about 0 — 100 Watts rf bias was employed in steps of 20 Watts, corresponding to effective negative self bias voltage of 15 — 440 V. CH4 and C2H2 have been used as source gas for CVD films. Microwave power was optimized at 300 Watts. In case of sputtering, a cylindrical graphite target (diameter 9 cm and length 6 cm) kept at the exit of the Ar plasma was biased with -200 V. Films were deposited on floating substrate (temperature ~100 oC). Films were deposited on Si, quartz, and steel substrates and characterized by FT-IR, Raman, UV-Visible, Photoluminescence spectroscopy (PL), spectroscopic ellipsometry. Nanoindentation was used to evaluate the film’s elastic property. Pin-on-disk measurement was used to study the tribological property of the films. Electrical properties of the films deposited on Si [p-(100), 10 Ω cm] were studied using picoammeter / source measuring instrument by two probe method. FT-IR analysis showed sp3C-H absorption peak at 2930 cm-1 for the CVD films, while sputtered films did not show any C-H absorption. Raman spectroscopy was used to evaluate bonding aspects as well as hydrogen content of the films. Comparison of sp3C : sp2C among the films was done based on I(D) / I(G) of the Raman peaks, while hydrogen content was estimated based on background slope of the Raman spectra. It was observed that increase in rf bias induces more sp2C while hydrogen content decreases. An optimum substrate bias of 40 Watts was predicted from the Raman spectra. For sputtered films Raman spectra indicated the formation of nanocrystal diamond in a-C matrix. UV-Visible-NIR optical transmission spectroscopy was used to determine the band gap (Tauc), E0, of the films. It showed that increase in rf bias increases the absorption coefficient α. The films deposited from CH4 with a substrate bias of 0 and 20 Watts (i.e., high hydrogen content in the film) followed (hνα)1/2 = const. (hν –E0), while other films hνα = const. (hν –E0) ( h is Plank constant ν is frequency of light). E0 varied from 1.1 — 2.5 eV. It was assumed that for π--π* transition follows root relation while π--σ * transition follows linear relation. Spectroscopic ellipsometry was used to determine optical constants, film thickness, and interface thickness. Deposition rate found out to be ~100 nm / mints for C2H2, ~10 nm / mints for CH4, and ~2.5 nm /mints for sputtered films. Formation of interface layer of thickness about 5 —30 nm due to high energy ion bombardment takes place for the films deposited at 40 Watts rf bias or higher. Band gap and related phenomena was revisited from the data that was obtained from this instrument which reasonably matches with the earlier results. PL experiments were carried out at room temperature using lamp excitation source as well as laser excitation source (457.9 nm wavelength). In case of lamp excitation source any wavelength from 200 —900 nm region can be selected. PL spectra showed that there are two sources of PL signal, one from nanocrystal diamond and other from sp2C phase. To obtain PL signal from diamond UV excitation wavelength was required. This diamond phase is highly efficient emitter as compared to sp2C phase. Based on the closeness of diamond’s optical centre labeling of the peaks was done. For CVD films N3 ( 457 nm), H4 (495 nm), H3 (520 nm), [N-V]0 (~590 nm) optical centers of diamond was observed. For sputtered films [N-V]0 (2.08 eV), H3 (2.38 eV), H4 (2.50 eV), N3 (2.81eV), N3 (2.96 eV), 3.3 eV ( undocumented peak), 5RL ( 4.14 eV) optical centers of diamond as well as band-edge emission (5.01 eV ) was observed. Nanoindentation technique was used to estimate the elastic property and related phenomena of the films. It shows that the films are having hardness of 5—17 GPa and reduced modulus of 20 —120 GPa depending on the deposition parameters. All the films show highly elastic response at lower load, i.e., at low indentation depth where elastic recovery is 85—95 %. At higher load substrate effect comes into the picture. Further morphology in and around the region was evaluated using scanning probe microscopy (SPM). It was shown that substrate effect comes into picture that is based on film’s thickness as well as its elastic property. Films were further characterized by pin-on-disk experiments. C2H2 based films were used because of high deposition rate. Since 40 Watts, 60 Watts, and 100 Watts films adhere well with steel only on these films tribological test was possible. A hardened bearing-steel was used as substrate and a 2 mm diameter cylindrical pin made of tool steel was use as pin. Studies were carried out with three different loads of 20, 40, and 60 N. Friction coefficient varied from 0.02 — 0.04 and wear rate was found to be 10-6 — 10-9 mm3 / N m. A sputtered film of 0.1 μ m on the top of the CVD film, in many respects, enhances the tribological properties. It was shown that certain amount of wear is required for low friction of DLC. Electrical characterization of the films deposited from CH4 showed that they are highly insulating with resistivity of 1013 —1011 Ω-cm, and current conduction mechanism has been found to be predominantly space charge limited conduction (SCLC). Similar to the observations of Tauc’s relation, the film deposited with 0 and 20 Watts bias behave differently and followed the relation , where as, all other films exhibited the relation ( α, n are constants). It signifies that for 0 and 20 Watts rf biased films traps are uniformly distributed across the band gap while for others it decreases from the conduction band. For 0 and 20 Watts rf biased films no Ohmic current was observed at a detection level of 10-11 A. 40 Watts and higher rf biased films showed that three distinct regions in the I-V curves; initially Ohmic region, next to it SPLC region, and finally breakdown region. Increase in rf bias causes increase in Ohmic current. Film deposited from C2H2 showed diode-like behavior with higher conduction current limited by resistive control, and the resistivity of the films was ~ 109 — 105 Ω-cm. Difference in resistivity between the films deposited from CH4 and C2H2 was explained by considering the impurities in the source gas resulting in nitrogen doping concentration. Increase in Ohmic current for the CH4 films was explained by assuming the widening of the σ--σ * gap. Similar diode-like behavior was observed with the sputtered film. The last part of the work deals with the growth mechanism of aligned CNTs and their field emission (FE) properties. Nanotubes were grown at 700 0C on Ni coated (thickness 40 nm, 70 nm, and 150 nm) Si substrate using a mixture of CH4 and H2 gas. Microwave power of 500 Watts was optimized for nanotube growth. Nickel nanoparticle formation mechanism from a continuous Ni film was explained by considering the stress that is generated due to the difference in thermal expansion coefficients of Si and Ni at 700 oC. Though the thicker film such as 150 nm does not form nanoparticle due to stress, hydrogen induced fragmentation of the film due the brittleness of the film even causes formation of finer nanoparticles. A substrate bias in the range 0— 250 V was used to align the nanotubes. Perfectly aligned CNTs were obtained at -250 V substrate bias. The density of the tubes varied from 108 —109 / cm2 while its length was 0.5 — 2 μ m. Due to hydrogen induced fragmentation of the films, 150 nm Ni thick film showed smallest diameter 2 — 5 nm CNTs. 40 nm films showed nanotube diameter of 10 — 30 nm and 150 — 300 nm while 70 nm showed 10 — 30 nm diameter nanotubes. Diameter of the nanotubes was estimated using transmission electron microscopy (TEM). Field emission analysis of these CNTs was done using Fowler-Nordheim (F-N) plot and the investigation revealed that the field emission properties strongly depend on density and aspect ratios. The non-linearity in the F-N plot or current saturation phenomena was explained in terms of change in work function due to heating effect during FE which was pronounced in case of longer nanotube. Suitable efficient cold-cathode emitters for a particular usage (assuming that the variables are applied field and emission current) could be designed from the obtained results. An ammonia gas sensor using thick nonaligned CNTs was realized. For this purpose a thick film of CNTs (~ 0.5 μm) was deposited. This sensor can detect 100 ppm level of ammonia. About 1.5 — 4.5 % change of resistance depending on ammonia concentration (100 —1000 ppm) was observed.

Electrodeposition of diamond-like carbon (DLC) films was studied on different substrates using two different electrochemical methods. The first electrochemical method using a three-electrode system was studied to successfully deposit hydrogenated DLC films on Nickel, Copper and Brass substrates. The as-deposited films were characterized by scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopy (FTIR) and cyclic voltammetry (CV). A variety of experimental parameters were shown to affect the deposition process. The second electrochemical method was developed for the first time to deposit hydrogen free DLC films on Ni substrates through a two-electrode system. The as-deposited films were characterized by Raman spectroscopy and FTIR. According to Raman spectra, a high fraction of diamond nanocrystals were found to form in the films. Several possible mechanisms were discussed for each deposition method. An electrochemical method was proposed to deposit boron-doped diamond films for future work.

Significant drops in adhesion have been measured for copper and diamond like carbon (DLC) films with the introduction of water at the film/substrate interface. A 1 thick tungsten superlayer with high compressive residual stress was deposited on the films of interest to help induce interfacial debonding by indentation. Modifications were made to the superlayer indentation technique to introduce water at the interface while performing indents. Film adhesion dropped by a factor of 10 to 20 for the copper films and 50 to 60 for the DLC films. The reduction in adhesion is believed to be caused by a combination of lowering surface energy and a chemical reaction at the crack tip. When the film compressive residual stress is at least 4 times the critical buckling stress of a debonded film, telephone cord delaminations morphology can be observed. Delamination propagation has been induced in the past by applying a mechanical force to the film and similar results have been observed with the introduction of water. Crack propagation rates of 2 to 3 microns per second were measured for the DLC films with the introduction of water at the film/substrate interface. Telephone cord delaminations show potential for future use as microchannels in microfluidic devices and have shown excellent stability when manipulated with a microprobe to control fluid transport.

The deformation mechanisms operating in diamond-like carbon (DLC) coatings on (100) and (111) Si, has been investigated. The effect of coating thickness, indenter geometry, substrate orientation and deposition technique on the deformation of DLC coatings and the underlying substrate was studied by undertaking nanoindentation followed by subsurface microstructural characterization. Uncoated (111) Si was also investigated for comparison. The observed microstructural features were correlated to the indentation response of the coatings and compared with simulation studies, as well as observations on uncoated Si. In uncoated (111) Si, phase transformation was found to be responsible for the discontinuities in the load-displacement curves, similar to (100) Si. However, slip was activated on {311} planes instead of on {111} planes. Moreover, the density of defects was also significantly lower and their distribution asymmetric. The coatings were adherent, uniformly thick and completely amorphous. The load-displacement curves displayed several pop-ins and a pop-out, the indentation loads for the first pop-in and the pop-out depending primarily on the thickness of the coating. The coatings exhibited localized compressive deformation in the direction of loading without any through-thickness cracks. The extent of this localized deformation increased with indentation load. Hardness and thickness of the coatings and the geometry of the indenter influenced the magnitude of compressive strains. Harder and thinner coatings and a blunt indenter exhibited the minimum degree of deformation. Densification by rearrangement of molecules has been suggested as the mechanism responsible for plastic compression. At indentation loads corresponding to the first pop-in, (100) and (111) silicon substrates initially deformed by <111> and <311> slip respectively. Higher indentation loads caused phase transformation. Therefore, unlike in uncoated Si, dislocation nucleation in the Si substrate has been proposed as the mode responsible for the first pop-in. Subsequent pop-ins were attributed to further deformation by slip and twinning, phase transformation and extensive cracking (median and secondary cracks) of the substrate. The pop-out, however, was ascribed to phase transformation. Extensive deformation in the substrate, parallel to the interface, is attributed to the wider distribution of the stress brought about by the DLC coating. Good correlation was obtained between the nanoindentation response, microstructural features and simulation studies.

In this work, the friction and wear behavior of three DLC coatings was evaluated in various conventional and alternative fuels as well as in commercially available formulated engine oils and additive-free synthetic oil. The first DLC has a thin top-coating of hydrogenated amorphous carbon (a-C:H), the second consists of Si-doped DLC (a-C:H:Si) and the third is a W-doped multilayered structure of a-C:H and a-C:H:W. The tribological tests were performed using a ball-on-flat reciprocating rig at low contact pressures. Methods such as white light interferometry (VSI), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), Raman spectroscopy, transmission electron spectroscopy (TEM) and electron spectroscopy for chemical analysis (ESCA/XPS) were used for analyzing and characterizing the coatings and counter surfaces in an effort to gain an understanding of the tribological mechanisms involved.

Polycarbynes ( poly(hydridocarbyne), poly(methylcarbyne) and poly(phenylcarbyne) ) are a class of network polymers which are primarily composed of tetrahedrally hybridizated carbon atoms which have hydrogen, methyl or phenyl pendant group linked via three carbon-carbon single bonds to form a three dimensional network of fixed rings. This backbone oers unusual properties on the polymer including thermal decomposition to form diamond and diamondlike carbon. In this thesis, polycarbynes were synthesized by electrolytical reduction of trihaloorganocompounds, namely chloroform, hexachloroethane, 1,1,1-trichloroethane and 1,1,1-trichlorotoluene. Poly(hydridocarbyne) was synthesized using chloroform and hexachloroethane. Poly(methylcarbyne) was synthesized from 1,1,1-trichloroethane. Poly(phenylcarbyne) was synthesized from 1,1,1-trichlorotoluene. Polycarbynes were characterized by UV/Vis spectroscopy, 1H and 13C NMR spectroscopy, FTIR and GPC. All results are found to be consistent with literature / and thus a single step cheap, safe and easy method was introduced to scientists and manufacturers in diamond science. The resulting polymers were heated upon 1000oC under nitrogen atmosphere for 24 hours yielding in the formation of diamond and diamond-like carbon. Results indicated that both diamond films and powders were successfully produced from polycarbynes. Diamonds formed from the polymers were characterized via optical microscope, SEM, X-ray and Raman spectroscopy. All results shown in thesis are completely consistent with studies previously done for polycarbynes and diamond.

With the continuing trend towards miniaturization, micro milling plays an increasingly important role in fabrication of freeform and high-accuracy micro parts or components directly and cost-effectively. The technology is in kinematics scaled down from the conventional milling, however, existing knowledge and experiences are limited and comprehensive studies on the micro tooling performance are essential and much needed particularly for the process planning and optimization. The cutting performance of micro tools is largely dependent on the dynamic performance of machine tools, tooling characteristics, work material properties and process conditions, and the latter three aspects will be focused in the study. The state of the art of micro milling technology with respect to the tooling performance has been critically reviewed, together with modelling work for performance prediction as well as metrology and instrumentation for the performance characterization. A novel 3D finite element method taking into account the geometry of a micro tool, including the tool diameter, rake angle, relief angle, cutting edge radius and helix angle, has been proposed for modelling and simulation of the micro milling process. Validation through well-designed micro milling trials demonstrates that the approach is capable of characterizing the milling process effectively. With the support of FEM simulation developed, the tooling geometrical effects, including those from helix angle, rake angle and cutting edge radius with influences on cutting forces, tool stresses, tool temperatures, milling chip formation and temperatures have been comprehensively studied and compared for potential micro tool design and optimization purposes. In an effort to prolong the tool life and enhance the tooling efficiency, DLC and NCD coatings have been deposited on micro end mills by PE-CVD and HF-CVD processes respectively. Corresponding cutting performance of these coated tools have been assessed and compared with those of WC micro tools in both dry and wet cutting conditions so as for better understanding of the coating influence on micro tools. Furthermore, the cutting characteristics of the DLC coated and uncoated tools have been analysed through verified plane-strain simulations. The effects of coating friction coefficient, coating thickness and UCT have been determined and evaluated by design of simulation method. Mechanical, chemical and physical properties of a work material have a direct influence on its micro-machinability. Five most common engineering materials including Al 6061-T6, C101, AISI 1045, 304 and P20, have been experimentally investigated and their micro milling behaviours in terms of the cutting forces, tool wear, surface roughness, and micro-burr formation have been compared and characterized. Feed rate, cutting speed and axial depth of cut constitute the complete set of process variables and they have significant effects on the tooling performance. Fundamental understanding of their influences is essential for production engineers to determine optimum cutting parameters so as to achieve the maximum extension of the tool life. 3D FE-based simulations have been carried out to predict the process variable effects on the cutting forces, tool stresses, tool temperatures as well as micro milling chip formation and temperatures. Furthermore, experimental approach has been adopted for the surface roughness characterization. Suggestions on selecting practical cutting variables have been provided in light of the results obtained. Conclusions with respect to the holistic investigation on the tooling performance in micro milling have been drawn based on the research objectives achieved. Recommendations for future work have been pointed out particularly for further future research in the research area.

Chromium thin film on glass substrate is the backbone of lithographic mask production as well as in the manufacturing of precision scale gratings and reticles. The lithographic masks, precision scale gratings and reticles, which are widely used in metrology instruments, motion systems and high precision machining tools ranging from digital calipers to coordinate measuring machines, typically consist of the patterned chromium film on the top of the glass substrate. In proportion to the development of such systems and devices, as a rule, high quality is requested altering the requirements for chromium thin films. This work aims to develop thin films with low surface roughness and improved scratch/wear resistance as compared to conventional chromium thin films. It covers – the systematic study of substrate surface preparation methods for improved chromium thin film adhesion to substrate; properties of chromium thin films deposited on glass using different physical vapor deposition techniques; investigation of diamond-like carbon (DLC) films and DLC-polymer composites on chromium thin films; and development of novel chromium composite films. The systematic study showed that soda–lime–silica float glass substrate surface activation and contamination removal by O2 plasma treatment process and wet chemical processing with NH4OH and H2O2 in H2O solution can effectively improve chromium thin film adhesive bonding to the substrate. It was determined that two-step thermal deposition... [to full text] / Plona chromo plėvelė ant stiklo pagrindo yra pagrindinis litografinių kaukių, precizinių optinių liniuočių ir limbų gamybos komponentas, nes plėvelėje formuojami didelės skiriamosios gebos topografiniai piešiniai. Šie piešiniai yra plačiai naudojami moderniausiuose mikro- ir nanotechnologijų procesuose, įvairiuose metrologiniuose instrumentuose, judesio sistemose, precizinio tikslumo medžiagų apdirbimo staklėse, fotoelektriniuose linijinių ir kampinių poslinkių matavimo keitikliuose. Tokių sistemų ir įrenginių technologinis progresas kelia naujus aukštos kokybės reikalavimus plonoms chromo plėvelėms. Šiame darbe buvo siekiama sumažinti chromo plėvelių paviršiaus šiurkštumą bei pagerinti jų mechanines savybes (atsparumą įbrėžimams/dilimui). Disertacija apima stiklo (naudojamo litografinių kaukių, precizinių optinių liniuočių ir limbų gamyboje) paviršiaus paruošimo metodų efektyvumo sisteminę studiją, skirtingais fizikiniais metodais nusodintų plonų chromo plėvelių bei apsauginių deimanto tipo anglies (DLC) ir DLC-polimero kompozicinių plėvelių savybių tyrimą, o taip pat naujų chromo kompozicinių plėvelių sukūrimą. Sisteminiai tyrimai parodė, kad plonos chromo plėvelės adheziją su silikatiniu plukdytuoju stiklu labiausiai pagerina apdorojimas deguonies jonų plazmoje ir cheminis paviršiaus paruošimas amonio hidroksido ir vandenilio peroksido vandeniniame tirpale. Nustatyta, kad dviem žingsniais termiškai garintos plonos chromo plėvelės, po pirmo garinimo jas apdorojant... [toliau žr. visą tekstą]

The deformation mechanisms operating in diamond-like carbon (DLC) coatings on (100) and (111) Si, has been investigated. The effect of coating thickness, indenter geometry, substrate orientation and deposition technique on the deformation of DLC coatings and the underlying substrate was studied by undertaking nanoindentation followed by subsurface microstructural characterization. Uncoated (111) Si was also investigated for comparison. The observed microstructural features were correlated to the indentation response of the coatings and compared with simulation studies, as well as observations on uncoated Si. In uncoated (111) Si, phase transformation was found to be responsible for the discontinuities in the load-displacement curves, similar to (100) Si. However, slip was activated on {311} planes instead of on {111} planes. Moreover, the density of defects was also significantly lower and their distribution asymmetric. The coatings were adherent, uniformly thick and completely amorphous. The load-displacement curves displayed several pop-ins and a pop-out, the indentation loads for the first pop-in and the pop-out depending primarily on the thickness of the coating. The coatings exhibited localized compressive deformation in the direction of loading without any through-thickness cracks. The extent of this localized deformation increased with indentation load. Hardness and thickness of the coatings and the geometry of the indenter influenced the magnitude of compressive strains. Harder and thinner coatings and a blunt indenter exhibited the minimum degree of deformation. Densification by rearrangement of molecules has been suggested as the mechanism responsible for plastic compression. At indentation loads corresponding to the first pop-in, (100) and (111) silicon substrates initially deformed by <111> and <311> slip respectively. Higher indentation loads caused phase transformation. Therefore, unlike in uncoated Si, dislocation nucleation in the Si substrate has been proposed as the mode responsible for the first pop-in. Subsequent pop-ins were attributed to further deformation by slip and twinning, phase transformation and extensive cracking (median and secondary cracks) of the substrate. The pop-out, however, was ascribed to phase transformation. Extensive deformation in the substrate, parallel to the interface, is attributed to the wider distribution of the stress brought about by the DLC coating. Good correlation was obtained between the nanoindentation response, microstructural features and simulation studies.