Surfaces in Precision Engineering, Microengineering and Nanotechnology

L. De Chiffre (1), H. Kunzmann (1), G.N. Peggs (1), D. A. Lucca (1) 2 Technical University of Denmark, Denmark, Physikalisch-Technische Bundesanstalt, Germany, 3 4 National Physical Laboratory, United Kingdom, Oklahoma State University, USA

Abstract This paper addresses the role of surfaces at the micrometric and nanometric length scales. Applications, functional behaviour, and manufacturing issues are reviewed with respect to state-of-the-art and emerging products fabricated using high precision technologies. Examples of surfaces obtained with precision engineering, microengineering and nanotechnology are presented, encompassing surfaces in computers, MEMS, biomedical systems, light and X-ray optics, as well as in chemical systems. Surface properties at micro and nanoscale are considered, including geometry as well as physical and chemical properties. Different manufacturing processes are reviewed with respect to surface fabrication, encompassing conventional machining, microfabrication, and nanomanipulation. Surface metrology at micro and nanoscale is briefly addressed, and its fundamental importance strongly emphasized. Keywords: surface, precision engineering, microengineering, nanotechnology

The authors thank the following contributors: (* indicates CIRP member) P. Bariani, Denmark N.J. Bjerrum, Denmark K.D. Bouzakis*, Greece E. Brinksmeier*, Germany F. Christensen, Denmark J. Corbett*, UK H.N. Hansen*, Denmark N. Ikawa*, Japan T. Inamura*, Japan M.J. Klopfstein, USA L. Koenders, Germany R. Krger-Sehm, Germany J.K. Nrskov, Denmark M. Tricard, USA K.J. Weinmann*, USA 1. INTRODUCTION

at micro and nanoscale are considered, including geometry as well as physical and chemical properties. The paper contains a review of the different manufacturing processes, with respect to surface fabrication, encompassing conventional machining, microfabrication, and nanomanipulation. Surface metrology at micro and nanoscale is briefly addressed. Table 1 gives a schematic overview of applications, functional behaviour, and manufacturing technologies that are considered in this work with respect to surfaces. A number of keynote papers published by CIRP during the last few years [1-5] provide the baseline for the paper. Surface metrology has been the subject of the 2002 keynote paper [5] but is not extensively considered in this paper, though its fundamental importance is emphasized. Examples of applications Computer chips Data storage MEMS Biomedical systems Micro-optical systems X-ray optics Fuel cells Implants Other Functions Optical Fluid dynamic Tribological Biomedical Mechanical Chemical Aesthetic Other Fabrication technologies Machining Masking Replication Deposition Manipulation Other

Surfaces act as interfaces governing the functional behaviour of a product. Often, the behaviour controlling mechanisms involve surface details on a micrometre or nanometre scale. Many emerging products are based on achieving these small scales, as is the case in precision engineering, microengineering, and nanotechnology. This paper considers the role of surfaces at the micrometric and nanometric length scales. It contains a review of important applications involving surfaces, considering properties and functional behaviour, as well as manufacturing issues, with respect to state-of-the-art and emerging products fabricated using high precision technologies. A number of examples of surfaces obtained with precision engineering, microengineering and nanotechnology are presented, encompassing surfaces in computers, MEMS, biomedical systems, light and X-ray optics, as well as in chemical systems. Surface properties

Table 1: Examples of applications, functional behaviour, and high precision manufacturing technologies concerning surfaces.

2.

SURFACES IN PRECISION ENGINEERING, MICROENGINEERING AND NANOTECHNOLOGY

some issues regarding their manufacturability and wear resistance are not yet solved.

2.1 Surfaces in computers and peripherals The tremendous impact of computer technology has become possible because of the progressive downscaling of integrated circuits and storage devices. The smallest features of the most modern integrated circuits are already significantly smaller than 1 m, and the scale reductions in storage media are equally impressive. Commercial magnetic storage has now reached a density of 400 million bits per square centimetre. This corresponds to a square single-bit size of 500 nm side length [6]. Considering that the critical dimension for electronic devices needs to shrink down to 22 nm in the year 2016, the fabrication of nanostructures has become a technologically important research area [7]. The magnetic properties of a computer hard disk are influenced by a surface region several nanometres thick. In order to minimize head stiction to the disk surface, surface polishing is followed by a texturing process producing circumferential grooves or laser texturing, the overall roughness of the structured surface being Rq = 35 nm [5]. 2.2 Surfaces in microelectromechanical systems (MEMS) In MEMS devices free-standing micrometre and submicrometre sized structures are realized on the surface of a polished silicon wafer by bulk or surface micromachining. These structures are not just the projection of a two dimensional feature into the depth, but truly three dimensional [8]. Very often these structures have to be movable like the cantilever used to support the seismic mass of an accelerometer or microscale mechanisms realized by IC compatible processes. MEMS are characterized by small masses, tight functional tolerances, smooth surfaces and light loads. Surface mechanisms are then of tremendous importance in determining their reliability. A major issue in MEMS is stiction, as illustrated in Fig. 1. Removal of a silicon oxide sacrificial layer is accomplished by wet HF etching. During the subsequent drying operation some shrinking drops may, due to their surface tension, bend the free standing polysilicon structure down to the substrate. There, a permanent adhesion occurs and the device functionality is compromised, Fig. 1(a). Stiction may also occur at any time during normal operation, as a result of an overdrive or handling, Fig. 1 (b). Adhesion forces are indeed often stronger than ones obtained by actuation. Single mechanisms and their relative contribution in determining the total stiction force have been discussed in [8]. Reduction of adhesion and friction forces at interfaces may be achieved by modifying surface chemistry or topography. Tribological coatings, well known in the area of mechanical engineering have an interesting potential as tribologically optimized surfaces for micro parts. Important differences exist due to the small offset (0.12m) and the low forces. Current research is focusing on development of wear resistant surfaces which show minimized friction and, above all, low stick-slip behaviour. Nanocoatings of DLC (diamond like carbon), metal doped-DLC and CNx were demonstrated also to have excellent wear resistance against abrasive and adhesive treatments [9]. Self assembled organic coatings have been proved to eliminate release-related stiction and inuse stiction, as well as reduce friction in microengines, but Fig.1: Typical stiction problems in MEMS. (a) Micromachine stiction during release-etch process; (b) stiction between overdriven suspended mass accelerometer and limit stop [8]. Stiction in MEMS is the main problem from an industrial point of view, while wear debris due to tight clearances and contact fatigue can be of concern in dynamic devices such as micromotors. 2.3 Surfaces in biomedical systems Miniaturization of medical diagnostic tools promise cost reductions owing to the volume scaled reagents consumption, time saving (diffusion time dependence), improved reliability and ease of use. Concepts such as bio compatibility in implanted chips, bio-recognition, cross contamination and bio-fouling in analytical systems, wetting properties and electrophoresis in micro-channels often determine device success. Ultimately all these factors depend on interactions at the surface. Recently there has been a strong trend toward high aspect ratios structures because they are capable of achieving a higher active surface area per unit substrate surface area. This is particularly important for chemical and biomedical applications, which offer the possibility of higher packaging densities of microstructural elements and higher throughput in continuous flow systems. In biomedical devices, where cells are present, interactions at the surface involve biologic functional units ranging from water molecules and small proteins at sub-nanometre size to cells in the micrometre range. Protein adsorption mechanisms on a synthetic surface play a fundamental role in determining cell adhesion [10]. Many microfabricated diagnostic tools are under development. Several studies show the possibility of manufacturing three-dimensional microstructures both in silicon and polymeric materials to form microprobe arrays [11]. Aspect ratios up to 100:1 are obtained using the SU-8 photoresist [12]. In lab-on-chip applications, surface chemistry plays a double role. In certain areas protein adsorption is highly desirable, since it mediates cell adhesion and eventually bio-recognition, on the other hand cell cultures have to be restricted to some selected regions within the micro-array. Indeed other pre-selected device zones are sensed to provide a background signal, and therefore they have to resist protein adsorption. In other words surface chemistry is designed and realized to provide the tailored chemical reactions only where desired. With respect to protein resistance, a 20 nm thick plasma polymerized tetraglymer coating layer has been shown to perform satisfactorily as a control medium [13]. In biochip arrays for DNA analysis several different single strand DNA segments are attached

to the surface in differentiated locations. Biochemical response depends on matching the known DNA fragments with the ones under test. Detector DNA molecules immobilization must be accomplished in such a way that surface binding is gentle enough to preserve their bio-recognition function. Polarization forces at metal surfaces as well as ionic or covalent interactions on many metal oxides and semiconductor surfaces may determine unacceptable loss of specificity. CMOS surfaces are therefore modified by introduction of space layers and linker molecules with the aim of preserving specificity and localization in DNA biochip arrays [10]. At present there is an increasing trend toward the adoption of polymeric films and bulk materials in biomedical and chemical microdevices. This is due to properties such as, for example: transparency, corrosion resistance or biocompatibility and the possibility of designing the material itself as required by the specific application. The role of the surface is of major importance also with respect to signal detection in biosensors; reflectivity and adsorption properties are relevant issues in thin-film design of optical coatings. Electrophoretic separation of chemical species is currently achieved in microfabricated microfluidic devices. Polymer fabricated systems are under development that are relatively cheap. In these systems, the wetting properties are of major concern. A different approach has been followed in programmable biochips based on SAW actuation which have been recently presented [14]. Here, instead of trapping the liquid into microchannels, it is kept into micro-beakers and transported across the surface of a chip. The surface is chemically functionalized, see Figure 2, in such a way to lay down fluidic tracks on the surface, very much like printing circuits on electronic boards. In this way, specific regions of the chip can be made hydrophobic or hydrophilic. The tracks are shaped by lithography [14].

preventing leakage of strong drugs [15]. Retinal implants based on CMOS technology have recently been reported [16]. When adopting a subretinal principle, an electroactive array of micro-photo diodes convert light into analogue current which is transmitted to the tissue through a passivation silicon dioxide layer and electrodes patterned into a nanoporous TiN layer. This porous layer increases the contact area by a factor of up to 100. Bioresistance is a key for this kind of implant which is meant to have lifetime duration. SEM of in vivo implants showed failure of the passivation layer and pit corrosion of the silicon underneath. Therefore the use of other protective layers is under investigation. Micromachined nanoporous membranes can be used to create immunoisolation biocapsules to protect transplanted cells from immunological attack. A fabrication protocol based on a thin sacrificial oxide thermally grown and sandwiched between two silicon structural layers gives membrane structures with highly defined pore sizes, as small as 10 nm [17]. These were demonstrated to be suitable in xenotransplantation: the typical dimensions of insulin, glucose, oxygen and carbon dioxide molecules are below 3.5 nm, while the antibodies are demonstrated to be retained by a membrane with a pore diameter of 30 nm. The strict control of pore diameter is of great importance, since even a small amount of pore diameters over the nominal cutoff value would allow the passage of antibodies in sufficient amounts to initiate immunorejection pathways. An important area is that of implants for medical use, where the current R&D on surface modifications pointing toward complex and multifunctional surfaces identifies three classes: one aiming at optimizing the topography (pore distributions, roughness, etc.); the second one focusing on the biochemical properties of surface coatings and impregnations (ion release, multi-layer coatings, coatings with biomolecules, controlled drug release, etc.); and the third one dealing with the viscoelastic properties of surface materials [18]. The surface is recognized by the biological system through the combined chemical and topographic pattern of the surface, and the viscoelastic properties. In most cases, biorecognition is a central component. Any attempt to make a sophisticated functional surface for biointeractions must take into account the highly developed ability of biological systems to recognize specially designed features on the molecular scale [10]. Famous examples are antibodyantigen, enzyme substrate, and receptor transmitter recognition (e.g., in cell membranes). The recognition is programmed into the molecules through the combination of their 3D topographic architecture, the superimposed chemical architecture, and the dynamic properties. Consequently an optimally designed surface for specific biological function must take these aspects into account. Although the fundamental interactions occur on the molecular scale there is an interesting and unique synergistic connection between the nanometre and the micrometre length scales when cells are present, as e.g., in the cases of medical implants, tissue engineering and cell-based bioelectronics. Recent work in the area of surface modification by texturing, implantation, and coatings can be found in references [19-25]. 2.4 Surfaces in light and X-ray optics For general-purpose-research telescopes the description of the optical quality of the surfaces is normally based on a specified point spread function and a simple roughness criterion. There are two types of mathematical relationships relating surface roughness and other surface figuring errors to scattering. However, the two basic

Fig. 2: Sketch of BioMEMS with selective texture for the generation of droplets having a 20 pl volume. The diameter of circles on the surface is approximately 30 m [14]. Therapeutic tools such as implantable biocapsules and drug delivery systems are the object of extensive research. Microfabricated pumps for drug delivery applications are based on actuated silicon membranes. Fluid compression is achieved by overdriving a reciprocating membrane. The return motion is due to the membranes own elasticity. There, the squeeze effect is limited by texturing one of the contacting surfaces. In these devices, thermal mismatch due to the difference in thermal expansion between silicon and silicon dioxide, has been used to pretension the surface of valves

expressions are not normally used together. The rootmean-square (rms) wavefront aberration in terms of wavelengths is denoted by . For small aberrations, the fractional loss L of intensity in the central peak of an image that is close to the diffraction limit is simply related to the Strehl ratio, that is a measure of image quality [26], [16]: L = 1 exp(-(2) ) 4
2 2 2

(1)

As pointed out by Born and Wolf [26], the formula is derived for low-order (smooth) aberrations. In contrast, the Total Integrated Scattering S, at normal incidence for random roughness is given by: S = 1 exp(-(4) ) 16
2 2 2

(2)

where is the rms surface roughness as deviation from a mean plane [27]. Expression (1) applies to an optical wavefront generating an image that is close to the diffraction limit of resolution. Expression (2) in the form shown applies to any beam of light in reflectance at normal incidence. However, in case (2), rms wavefront errors at normal incidence are equal to 2. We therefore have = /2. The two expressions give similar results despite having different origins. With the advent of advanced design telescopes and recent developments in polishing technologies, it may be possible to tailor the characteristics of mirror surfaces to improve the optical characteristics of an optical element. The major advantage is that stray light could be managed in a much more efficient way than currently possible [28] by engineering the surface. It would be possible, for example, to direct stray light away from key regions of the field where maximum contrast is needed to meet the science requirement. Surface roughness plays a major role in reflective x-ray optics. X-rays incident at very shallow angles can be reflected with high efficiency off smooth metallic or metalcoated surfaces, for example gold. Such mirrors, with designs of varying degrees of complexity, are widely used in x-ray telescopes and other x-ray imaging applications. In typical applications, an x-ray telescope mirror is made from glass ceramic material that is highly polished and coated with metal, or it can be made from nickel electrodeposited on a mandrel. In practice, such a telescope receives x-rays from sources in space and they first strike an annular parabolic surface and are then reflected on to an annular hyperbolic surface (an optical configuration developed by Wolter [29]). Frequently, such surfaces are nested to improve the collecting efficiency of the telescope. In telescopes with the best angular resolution the geometry of the individual mirrors is as close to perfection as possible but this implies a rigid surface that has a thickness of some millimetres. For applications where less angular resolution is needed foils can be used. In both cases the surface texture of the surface strongly affects the performance of the mirror because it gives rise to x-ray scatter and therefore minimizing the surface texture is a vital aspect of the manufacture of such components. Fortunately, the improvement between an optical component and an x-ray component is not the ratio of the optical to x-ray wavelengths because the x-ray optical component is operating at grazing incident. It can be shown that a surface texture improvement of about 25 is needed for the x-ray case that has been demonstrated to be possible [30]. A number of researchers have demonstrated manufacturing and measuring substrates with surface

textures in the region of 0.4 nm Ra was possible in the 1980s [31] and figure accuracies of 0.2 nm are published today. The very demanding metrology requirements spawned a significant number of instruments designed to measure exceptionally smooth surfaces and they were both of the contacting [32] and the non-contacting [33] types, such as ellipsometry, where a light beam of known polarization is incident on the sample. In general the light reflected from the surface is elliptically polarized and, for very thin coatings, the light will reach the lower interface and the ellipsicity of the light will be thickness dependent. The axial angular slope is another key parameter that must be controlled during manufacture [30] and slopes in the range of 2 to 5 microradians are required for optics with good performance. Attempts at making x-ray microscopes were based on reflective optics [34-35] but in recent years more success was achieved using zone plates, noteably amplitude zone plates [36] but more recently by phase zone plates [37-39]. There is much interest in x-ray microscopes because their resolution is determined by the width of the outer ring of the zone plate which can be of the order of 35 nm which is therefore at least 10 times better than an optical microscope. Moreover, the x-ray microscope can be used to image intact cells to a depth of a few micrometres [40-41].The normal type of x-ray microscope takes an image of the whole specimen at once but there are scanning variants where the object to be measured is rastered whilst a picture is built up [42]. Multi-layer based x-ray optical systems represent an important area. Multi-layer coatings are being used successfully as beam-forming elements for soft x-ray applications such as hard x-ray micro-probes [43]. Such coatings that can be 100 layers thick are arranged in such a way that reflections add in phase. However, the thickness of such layers is of the order of 1 to 10 nm thick and the surface texture must be carefully controlled to the order of 0.1 nm Ra [44]. Windt et al. [45] point out that it is very important to specify, and measure within, the surface wavelength which influences the x-ray reflectivity, in this -1 case from 1 to 100 m . Examples of micro-optical systems are the OLED (organic light emitting diodes), which are illumination sources based on electrophosphorescent organic thin film layers (less than 500 nm). Their light extraction efficiency is limited to 20% due to total internal reflection. This limitation is partially removed when an ordered array of microlenses is attached to the substrate surface opposite to that of the OLEDs. Ten micrometre diameter PDMS microlense arrays fabricated using transfer moulding were demonstrated to improve external quantum efficiency of an OLED by 50%. No alignment is required for these arrays since the microlense diameter is about ten times smaller than a display pixel [46]. 2.5 Surfaces in chemical systems The surface plays an important role in chemical systems such as heterogeneous catalysis, fuel cells, etc., since chemical reactions depend on the amount of active surface, predominantly on the micrometre to nanometre scale. Actually, catalysts are today the most important group of commercial nanomaterials [47-48]. The majority of industrial catalysts are high-surface-area solids onto which an active component is dispersed in the form of very small particles. These have dimensions of 1 to 20 nm and are often referred to as nanoparticles. Catalysis will continue to be an important area of nanotechnology since solutions to many important resource, energy and

environmental problems require new catalysts with tailormade nanostructures. An area involving catalysis which is receiving particular attention is represented by fuel cells [49]. In a fuel cell, basically consisting of two electrodes sandwiched around an electrolyte, oxygen passes over one electrode and hydrogen over the other, generating electricity, water and heat. Several kinds of fuel cells have been developed, for example [49]: Phosphoric Acid (PAFC), Proton Exchange Membrane (PEM), Molten Carbonate (MCFC), Solid Oxide (SOFC), Alkaline, Direct Methanol Fuel Cells (DMFC), Regenerative Fuel Cells, Zinc-Air Fuel Cells (ZAFC), Protonic Ceramic Fuel Cells (PCFC). As an example, in PEM fuel cells, the proton exchange membrane is a thin plastic sheet that allows hydrogen ions to pass through it. The membrane is coated on both sides with highly dispersed metal alloy particles (mostly platinum) that are active catalysts. In PCFC cells, gaseous molecules of the hydrocarbon fuel are absorbed on the surface of the anode in the presence of water vapor, and hydrogen atoms are efficiently stripped off to be absorbed into the electrolyte, with carbon dioxide as the primary reaction product. Figure 3 gives an impression of the role played by the active surface area in a MCFC cell cathode which is considerably expanded by a high porosity. Another important area is that of microchemical sensors, which has been partially illustrated in connection with micromedical applications in section 2.3.

Complex patterns 3D nature with re-entrances Miniaturised components

Figures 4 and 5 show examples of surfaces on modern products, where micrometre details govern the functional behaviour of the surface through the so-called lotus effect [51]. Figure 6 illustrates the typical dimensions of structures obtained with different manufacturing processes, which are, in general, interrelated. Going down from millimetre to nanometre length scales is not only a scaling of the size of the material, the nature of the material itself changes. At distances of some nanometres it is not only less material which is observed, the material becomes atomic and discrete in character, i.e., the atoms of the surface determine the physical and chemical properties of the surface. On the other side we have to take into account the atomic steps on surface crystals. Steps at this scale depend on the treatment of the sample and represent the surface heights becoming discrete. Calculations of the roughness of such atomic surfaces have been produced recently, [52-53].These calculations take into account the available data of crystals and knowledge acquired using the bulk values, although the atoms on the surface show different structures, as observed by Low Energy Electron Diffraction (LEED) and Scanning Tunneling Microscopy (STM). The surface atoms are arranged in such a way that the surface energy is minimized. Accordingly, on a clean silicon surface of (111) orientation we see a 7x7 unit cell, whereas on a (100) surface a 2x1 structure is observed, Figs. 7 and 8. The meaning of 7x7 is that the surface unit cell is 7 times larger in the x direction than assumed from the bulk values, see [54-56].

Fig. 3: SEM micrograph of modified NiO cathode for MCFC [50]. SURFACE PROPERTIES AT MICRO AND NANOSCALE The issue of defining the surface itself has been reviewed in the 2002 keynote paper [5] emphasizing the fact that a surface also depends on the measurement technique used to characterize it, and measurements at different depths are needed for complete characterization. It is moreover clear that interactions between geometrical, physical, and chemical properties take place, and that the influence from mesoscopic conditions, reaction velocities, quantum effects, etc. becomes of paramount importance. 3.1 Geometry A number of aspects among those listed below differentiate the geometry of high precision surfaces from the geometry of surfaces of conventional products: Very fine topographical scales High aspect ratios 3.

Fig. 4: A regular surface structure from which the Lotus effect can be obtained (University of Bonn/Courtesy of the PTB)

Fig. 5: Lotus effect of paint on glass (Courtesy of the PTB)

min. height of micro structures in m 3000 2000 1000 min. height of micro structures in m 3000 2000 1000

hot molding injection molding

min. lateral dimensions in m

X-ray lithography optical lithography

min. height of micro structures in m 3000 2000 1000 5 50 100 150 200

electrodeposition micro laser beam cutting

Fig. 6: Height versus lateral dimension of micro-structures produced using different fabrication processes (Courtesy of A. Weckenmann, University Erlangen-Nurenberg)

physical state has been extensively treated in two recent keynote papers [5][57], and the critical importance of surface and subsurface integrity of ultraprecision surfaces has been documented [57]. As a result of the increasing need to characterize the mechanical response of surface regions in the nanometre range, significant efforts in the development of indentation instruments that measure load versus depth have been made. Nanoindentation has been shown to be able to successfully characterise the elastic modulus and hardness of the very near surface of solids and thin films, and nanoscratching has been employed to characterise thin film adhesion. The use of nanoindentation for the characterisation of the near surface residual stress state has also recently been discussed [5]. In addition to these measurements, nanoindentation has been used to study pop-in [58] - an abrupt increase in penetration at a given load - which has been observed in a large variety of materials including metals [59] and semiconductors [60-61]. Pop-in is a near surface behaviour which has been most commonly associated with the sudden nucleation of dislocations and the onset of plasticity [58], [62], although in some cases it has been attributed to oxide layer breakthrough [59]. Nanoindentation coupled with FEM modeling has been used to determine the constitutive behaviour of the near surface [63]. The fundamental nature of near surface plasticity is also being investigated by nanoindentation and relates to the fact that for many different crystalline materials, hardness of the near surface is seen to decrease with increasing depth. This indentation size effect is thought to have a physical basis described by strain gradient plasticity [64], [67] although rate effects are also thought to play an important role [68]. Unique surface behaviour has also been investigated using nanoindentation. For example, the near surface photoplastic effect (PPE) in II-VI semiconductors [69 - 71], has been reported. Whereas the PPE has been observed in bulk single crystal II-VI semiconductors [72] for many years, only recently has it been observed at the near surface. Wolf et al. [69] examined the effect of white light illumination on the hardness of (111)ZnSe. Nanoindentation was performed using a Berkovich indenter in darkness and under illumination by a tungsten 2 halogen lamp that produced 50 mW/cm on the surface. Over the entire depth range (50 nm to 450 nm) an increase in hardness of approximately 10% was observed. In further studies by the same group, the spectral sensitivity of the change in hardness was investigated, again on (111)ZnSe [70]. The wavelength of the incident light was varied from 470 nm to 585 nm. The largest increase in hardness was obtained with light of a wavelength of 510 nm, slightly greater than that representing the band gap of the material, 480 nm. Recently, Klopfstein et al. [71] studied the effects of white light illumination on the nanoindentation response of (0001) etched ZnO for a depth from the surface of 25 nm to 275 nm. Illumination resulted in a 40% increase of the load at which pop-in or the onset of plasticity occurred. Figure 9 shows the measured hardness as a function of contact depth with sample illumination and in darkness. In both cases the indentation size effect, an increase in hardness with decreased indentation depth, was observed. To a depth of 100 nm the hardness of the illuminated sample was found to be 7% to 20% greater than that measured in darkness. Beyond this depth no observable difference in hardness was found. The increase in near surface hardness with illumination was attributed to the charging of dislocations by surface states of the material. The lack of an observed PPE for indentations with a contact depth greater than 100

Fig 7: STM image of a clean Si (111)- 7x7 surface. Horizontal range: 20 nm; Vertical range: 15 nm; Z-range (out of paper): 0.4 nm. The rhombus shows the 7x7 surface unit cell. (Courtesy of the PTB)

Fig. 8: STM image of a 20 nm x 20 nm large part of a silicon (100) 2x1 surface with an atomic step. The step height is 0.13 nm. (Courtesy of the PTB) 3.2 Physical properties The mechanical properties of the surface and near surface region can play an important role in the functional behaviour of precision surfaces, e.g., frictional effects in tribological systems. Characterisation of the near surface

nm was attributed to a reduced effect of the surface states on dislocation charging in this region and insufficient bulk charging resultant from short dislocation travel distances.

and N2. In another study by the same research group, the mechanical properties of TiCxN1-x thin films deposited on cemented carbide substrates were measured as a function of the intrinsic stress on the film as measured by X-ray diffraction [84]. Investigation into the effects of multilayer structures of compositionally modulated Ti/TiN films on their hardness where the modulation periods examined were 10, 15, 20, and 40 nm has also been reported [85]. Fracture toughness of thin films has been calculated based on the analysis of the energy release rate from the loaddisplacement curve during nanoindentation. For indentation techniques, radial cracks are produced during the unloading cycle when brittle materials are indented by a sharp indenter. The length of radial cracks is known to correlate with the fracture toughness and is used to calculate fracture toughness based on various equations which have been reported [86], [87]. The fracture process has been shown to progress in three stages [86]: (1) first ring-like through-thickness cracks from around the indenter result from high stresses in the contact area; (2) delamination and buckling occur around the contact area at the film/substrate interface by high lateral pressure; and (3) second ring-like through-thickness cracks and spalling are generated by high bending stresses at the edges of the buckled film. The same model has been used to study the fracture toughness of multilayer hard coatings deposited on cemented carbide [88]. In this study, the changes in slope of plots of load-penetration depth squared were shown to reveal the changes of the coating/substrate system. Two other methods based on correlating crack lengths emanating from the corners of the indentation when the indenter and load are removed, and correlating fracture toughness have been reported [89]. A new mechanical test, the cross-sectional nanoindentation test, has recently been developed for measuring fracture toughness [89]. In this test, indentations are made normal to the wafer cross-section within the substrate and close to the interface of interest. From the results of this test a model based on elastic plate theory was developed to numerically calculate the interfacial critical energy release rate [90]. Inputs to the model are the thin film elastic properties, thin film thickness, interfacial crack area and maximum thin film deflection during the test. The interfacial delamination area (crack area) was measured by optical and scanning electron microscopy. The maximum thin film deflection during the test can be obtained from the load versus displacement curves and the Berkovich diamond-tip geometry assuming that the indenter shaft does not tilt during the test. The wear resistance of brittle materials has been shown to be principally determined by its fracture toughness as well as elastic modulus and hardness [88]. 3.3 Chemical properties Heterogeneous catalysts are typically multiphase systems and the structural and chemical states of the active species depend intimately on process conditions. Particles ranging in size from roughly 1 to 50 nm exhibit physical and chemical properties that are intermediate between those of the smallest element from which they can be composed (such as a metal atom, the stoichiometric unit of a metal oxide) and those of the bulk material [48]. Catalyst performance can be sensitive to particle size because the surface structure and electronic properties can change greatly in this size range. Theoretical calculations have been successfully attempted of adsorption properties, reaction pathways, and activation energies for surface chemical reactions [91]. The approach taken in surface science has been to study elementary reactions on well

Figure 9: Hardness as a function of contact depth for etched (0001)ZnO with sample illumination (circles) and in darkness (squares). Error bars denote maximum and minimum of the data [71]. In addition to the surfaces of bulk materials, the physical behaviour of thin films is also of significant interest. Although there are several techniques used to characterize the mechanical properties of thin layers on the order of 100 nm in thickness including for example, ultra short surface waves [73], nanoindentation has been successfully used to characterize the mechanical properties (elastic modulus and hardness) of thin films as a function of film thickness, growth condition, chemical composition and residual stress state. For example, the elastic modulus and constitutive behaviour of electron beam PVD deposited zirconia have recently been reported [74]. In another study, the mechanical properties of sol-gel zirconia deposited on polished disks of 316 stainless steel were measured as a function of film thickness from 0 nm (as polished) to 900 nm, for different values of load [75]. Similar work has been done on solgel-deposited titania (TiO2) on glass and copper with thicknesses from 50 nm to over 200 nm [76], on aluminum deposited on glass with thicknesses between 240-1700 nm [77], and on sol-gel-derived hard coatings on polyester [78]. In this last study, the influence of UV irradiation and low temperature heating on the thickness and the hardness of the film was reported. The hardness of the films was evaluated not only as a function of film thickness but also as a function of the deposition temperature of the film, since deposition temperature was shown to be related to the thickness of the TiN and TiCN coatings [79]. A correlation between the resulting hardness of silicon oxinitride (SiOxNy) films and processing temperature has also been reported [80]. The effects on measured elastic modulus and hardness of the substrate bias voltage and nitrogen partial pressure in the deposition of titanium nitride (TiNx) thin films [81], and vacuum annealing time in the deposition of Mo-Si-N/SiC [82] have also been studied. The influence of the carbonto-nitrogen composition ratio, x, in TiCxN1-x thin films deposited on cemented carbide substrates on the mechanical properties including hardness and elastic modulus has also been reported [83]. In this study, TiCxN1-x thin films were grown with x=0 (TiN) to x=1 (TiC) by varying the flow ratio between the reaction gases CH4

defined single crystal surfaces. Single crystal surfaces are only crude models of the high surface area catalysts used industrially. Catalysts need to have a high surface area, and they often consist of a mixture of phases, some of which have the catalytically active surface, while others support the small particles of active phases or keep them from sintering. Recently, it has become possible to produce and study models of supported catalysts and to study them under realistic high pressure and temperature conditions. It was shown that catalysis is decisively affected by atomic steps on the surface. Fig. 10 illustrates the fact that chemical activity is tremendously reduced when surface steps are covered with gold using PVD [92].

Ea = 36 5 kJ/mol
-10 log s0 -11 -12 -13

Electron Microscope (TEM) with in situ capabilities [92], [95]. The electrons passing through the sample in the TEM provide information not only about particle size and shape but also about the lattice structure and the chemical composition of individual particles. Also STM and AFM have been used to examine the nanostructure of model catalyst systems. Using STM, for example, it has been possible to explain why the addition of small amounts of Au to Ni catalysts used for the steam reforming of methane reduces the tendency of such catalysts to deactivate because of C deposition [96]. The STM image in Fig. 11 shows Au atoms located on a Ni surface. The presence of the Au atoms near a Ni atom reduces the tendency of C to bond to the Ni, and hence to initiate the formation of carbonaceous deposits that deactivate the catalyst. SURFACE FABRICATION IN PRECISION ENGINEERING, MICROSYSTEMS AND NANOTECHNOLOGY In this section, different manufacturing processes are reviewed with respect to surface fabrication. The processes are grouped according to the following three main areas: Conventional machining (encompassing precision engineering material removal operations as well as EDM and laser machining) Microfabrication (encompassing silicon micromachining as well as polymer replication processes) Nanomanipulation (encompassing positioning and manipulation as well as modification and patterning on micrometre and nanometre scales using localized tools). 4.1 Machining A number of processes are particularly relevant for the manufacture of ultra-precise microstructures: diamond turning, diamond milling, contour boring (Figure 12), micro grinding and ultrasonic assisted processes such as diamond cutting as well as ultrasonic lapping. For the ultraprecision manufacturing of complex surfaces and microstructures diamond turning and fly-cutting are commonly employed. However, for certain tasks these processes have geometric and kinematic limitations. Diamond contour boring and ball-end milling extend the types of surfaces which can be generated to almost arbitrarily shaped mirror arrays and profiles with high aspect ratio, being suitable machining methods for the fabricating of microstructures [57], [97-102]. 4.

Ea = 126 21 kJ/mol
-14 0.0015 0.0020 0.0025 0.0030 0.0035 1/T (K-1) Fig. 10: Dissociative N2 Adsorption on Ru(0001). The energy Ea required for dissociation increases from 36 kJ/mol to 126 kJ/mol, if surface steps are covered with Au atoms [92].

Fig. 11: STM image of a Ni(111) surface with 2% of a monolayer of Au. The Au atoms appear black in the images. The Ni atoms next to the Au atoms appear brighter because of a change in geometry and electronic structure, indicating that the chemical activity of the Ni atoms may be modified by nearest-neighbor Au atoms [96]. Through in situ studies, it is possible to obtain a detailed atomic-scale description of the nanostructures and the sites where the catalysis takes place, i.e., the active sites under reaction conditions. In situ methods have been successfully applied to elucidate the properties of a large number of heterogeneous catalysts, recently with the development of a novel high resolution Transmission

Fig. 12: Contour boring with half-arc monocrystalline diamond tool. Left: Details of machining a mould for lenses; Right: tool details [102].

A number of ultra-precision machine tools has been developed over the last twenty years in order to meet the ever growing demand for reduced dimensional tolerances, together with high surface and subsurface integrity Error! Reference source not found.. For many industries the above requirements, coupled with the advent of new advanced materials, including glasses and ceramics, is leading to the capabilities of conventional machining methods and machine tools being eclipsed by new processes and machine systems currently at the research stage. The design of these machines is fundamental in improving machining performance by, for example, designing for high loop stiffness, the minimalisation of thermal effects [103] and friction, and the incorporation of advanced measurement and control systems. In addition, for highest accuracy, automatic control and software compensation methods are becoming increasingly important. Past examples of ultra precision machine tools include the Large Optics Diamond Turning Machine, developed at Lawrence Livermore National Laboratory in the USA [105], and the Cranfield Nanocentre diamond turning and grinding machine [106] developed in the UK. More recently, an ultra precision double disk grinding machine aimed at 'ductile' grinding of 400 mm diameter silicon wafers, within a flatness of 100 nm has been developed in Japan [107]. The machine has achieved extremely high quality ductile mode grinding of the silicon wafers with very low (sub micron) dislocation damage. A further recent development has been the realisation, in the UK, of another ultra precision grinding machine tool Tetraform 'C'. Tetraform includes a combination of novel concepts for the design of machine tool structures, which have been developed to provide a very high dynamic stiffness, which is required to machine, directly, brittle materials with extremely low levels of subsurface damage. The machine utilises a passively damped space frame, with all loads being carried in closed loops. The resulting structural design, coupled with the use of hydrostatic leadscrews and guideways for each axis, provides very high static and dynamic stiffnesses [108].

demonstrate a measured Ra value of 2.3 nm and 5.4 nm for each surface [109]. Important research work has been carried out by CIRP members concerning computer simulation of the mechanisms involved in chip formation and surface generation in single crystal nanoscale cutting [110-119]. Manufacturing of lenses by an alternative precision polishing method called magnetorheological finishing (MRF) has demonstrated ability to produce optical surfaces with an accuracy better than 30 nm peak to valley and surface roughness less than 1 nm on optical glasses, single crystals (calcium fluoride, silicon), and glass ceramics [120]. In MRF, see Figure 14, material removal is accomplished through hydrodynamical forces resulting from the flow of magnetorheological fluid. In contrast to conventional polishing, a quasi-solid boundary in the magnetorheological fluid produces a high shear stress, but no normal load, resulting in material removal with a minimum of material damage.

Fig. 14: Polishing mechanism in MRF [120]. Another example of precision finishing, Zeeko's Precessions polishing process uses a spinning, inflated membrane tool, which is pushed against the part to create a variable-sized polishing spot [121-124]. The tool rotationaxis is precessed to create a near-Gaussian removalprofile, and the spot traverses the part under control of a 7axis CNC machine-tool. A numerical optimiser interprets measured metrology data and computes the optimum spot-sizes and dwell-times across the part to minimise form-errors. Nanometric surface textures are possible using such a technique with good control of waviness. Laser micromachining has established itself as a means for manufacturing of microsystems for various applications during the past years. These new applications demand for the quality of micromachined devices combined with more functionality. The short pulse duration, high pulse energy and extremely small penetration depth of excimer laser radiation into irradiated surfaces facilitate the machining of brittle-rigid materials as ceramics and glass. Another special characteristic is the large beam profile of this kind of laser. Thus, it is possible to modify large surface areas at one time or, by the use of a mask, it is possible to create many differently shaped structures [116], [125-127]. 4.2 Microfabrication Microfabrication encompasses operations such as lithography, oxidation, etching, wafer bonding, electroplating, deposition of silicon wafers, etc. involved in the micromachining of silicon as well as polymer replication processing by hot embossing or imprinting, injection molding, laser ablation, soft lithography, x-ray photolithography, etc. Much importance is currently given to solving the stiction problem during micromachining of silicon for the fabrication of microsystems. Release related stiction in MEMS can be

Fig.13: Optical quality machining of M50 bearing steel There is a growing interest in the production of optical quality surfaces on metallic components, particularly to control tribological properties. The ability to machine metallic surfaces to optical quality (< 10 nm Ra) has a significant impact on both the time and economics of manufacture, particularly when slow polishing and lapping processes can be eliminated. However, to achieve realistic material removal rates the machine tool must have a high dynamic stiffness. As an example, Tetraform C has been used to grind M50 bearing steel. Figure 13 illustrates a stepped workpiece where the upper surface was ground using a 200 m wheel depth of cut and the lower region a 500 m wheel depth of cut. A 76 m CBN cup wheel was used in association with electrolytic inprocess dressing (ELID). Wyko plots for both surfaces

minimized by several engineering approaches: sublimation-drying and supercritical CO2 drying and vapor HF etching preventing meniscus formation were successfully applied. Another approach is to perform a partial undercutting of the surface microstructure and fill the voids with a polymer layer. Physical surface modification: the surfaces are roughened to reduce the effective contact areas, selective etching is typically employed to change the surface topography [128], [129]. Chemical surface modification methods have been attempted, including low surface energy plasma polymerized fluorocarbon film deposited in the field-free zone of plasma reactors. A more effective chemical surface modification involves the formation of a selfassembled monolayer (SAM). Several classes of organic films have been explored, including alkyl- and perfluoroalkyl-trichlorosylane SAMs, dichlorosilane- and alkene-based molecular films. Among these classes of films, the most widely used is the octadecyltrichlorosilanebased SAM. Despite the progress made so far, some crucial issues concerning their manufacturability have not been addressed yet such as: reproducibility, scale up from single dies to whole wafers and eventually multiwafer cassettes are currently engineering challenges. Durability of monolayer coatings is still a concern. Non organic coatings as DLC and Me-DLC films were fabricated via PECDV methods. The deposition temperature below 200C has allowed the use of polymers (SU-8 for instance) as substrate. Adhesion to the substrate was also proved to be acceptable. Extensive research work is going on to develop polymer microdevices, particularly for microfluidic and biomedical applications. Process conditions using replica techniques such as hot embossing, microinjection moulding and soft lithography of elastomeric polymers should be chosen to take account of the design of the microstructures to be manufactured. The critical dimensions that can be replicated by injection moulding with an acceptable quality are mainly determined by the aspect ratio of the microstructures [130]. For aspect ratios lower than unity, these minimal dimensions reach values in the submicrometre scale, for example in the manufacturing of CDs. In the case of higher aspect ratios, the conventional injection moulding process no longer achieves a sufficient replication quality mainly because the resin hardens before complete filling of the mould. By using special microinjection moulding techniques, polymeric microstructures with minimum wall thicknesses of 10 m, structural details in the range of 0.2 m and surface roughness of about Rz<50 nm can be manufactured. The greatest advantage of this approach consists in the aspect ratios that can reach values up to 20. Hot embossing [131] of high aspect ratio microstructures requires control over properties such as sidewall roughness of the embossing master and the chemical interface between the tool and the polymer. With respect to friction minimization during the de-embossing phase, 80 nm rms is an empirical limit for the fabrication of structures with an aspect ratio larger than 0.5. The LIGA process and ASE silicon etching allow sidewall rms values in the order of 10 and 8 nm respectively. Therefore, they are perfectly suited to high aspect ratio replication. Addition of release agents to the polymer allows replication of aspect ratios up to 50. Replica techniques allow fabrication of polymer independent components such as fluidic conduits. These elements are then aligned and assembled with CMOS electronics into sensors and actuators. Approaches based on parallel fabrication of aligned electronics and polymer

microstructures have been attempted as well. Lithographic patterning of polymides and SU-8 are employed to produce polymer microstructures on a wafer substrate, using x-ray lithography aspect ratios of 100:1 can be obtained [12]. Other approaches reported in the literature are liquid crystal polymers [132], and etching techniques. Fluoropolymers are inert to most solvents and chemicals, hence micromachining of these polymers offer great potential for use in microdevices containing corrosive fluids or gases. The low surface energy makes the fabrication of microstructures from these substrates most difficult when using conventional micromachining techniques. Low energy ion beam treatments on fluoropolymer surfaces have been demonstrated to enhance the wetting characteristics of photoresists with a minimal surface modification (Rsq 40 nm) [11]. An alternative method using direct plasma etching has recently been proposed. This approach is known as deep reactive ion silicon etching (DRIE). It allows the fabrication of high aspect ratio structures with a smaller minimum feature size than replica techniques and the ability to integrate devices with associated CMOS electronics [133]. MEMS membranes patterned with polymer lines have been fabricated, with potential application in microfluidics. Localized stiffening is achieved due to the polymer lines, making possible the selective actuation of separate regions of the membrane. Unfortunately, roughness and footing in the bottom edge of the polymer microstructure were evident. Thin parylene films are suitable for manufacturing elastic membranes owing to its low Youngs modulus and can be used for the fabrication of check valves in microfluidics. In this application, gas phase BrF3 is used to roughen the valve seat surface. This process reduces stiction and surface tension in the valve by minimizing contact area between the mating surfaces. The roughened valve seat surface also leads to enhancement of the adhesion of the parylene anchors. Surface modification techniques to improve wetting properties in microchannels are currently being addressed. As an example sulfunation of PCA microchannel surfaces was demonstrated to influence the electro-osmotic flow as well as surface topography, the effects of sulfunation lead to a smoother PCA surface and a significantly higher electro-osmotic flow for pH values below 8 [134]. Replication has been used for the mass production of CDs, optical components, as well as roughness calibration standards [135], to mention some examples. As the semiconductor industry progresses towards extreme ultraviolet (EUV) lithography there is an increased demand for ultraprecision surfaces with surface roughness values less than 1 nm. Mirrors for x-ray optics and synchrotron radiation sources also require nanometre level peak-to-valley roughness. In addition to surface roughness, the crystallinity of the near surface may also be important, e.g., Bragg diffraction optics. A few examples of the many different physical and chemical processes used to generate ultraprecision surfaces are discussed below. In a series of papers Mori et al. [136-138] demonstrated the use of plasma chemical vaporization machining (CVM) to achieve nanometre level surface roughness. In plasma CVM, a plasma is generated between an electrode and the sample in the presence of a gas, typically helium with SF6, or CF4 at nearly atmospheric pressure. The shape of electrodes which have been used include a hollow cylinder [139], a rotating disk [138], a rotating cylinder [137] and an inner-diameter saw [136]. Mori et al. [137] claimed that the removal of material is by the chemical interaction of the plasma and the sample resulting in no mechanical damage to the sample. Plasma CVM using a rotating cylinder for

the electrode reduced the surface roughness of a Si wafer from 2.2 nm P-V to 1.4 nm P-V over a length of 250 m [137]. The technique has also been used with fused silica, polycrystalline molybdenum, polycrystalline tungsten and polycrystalline silicon carbide. Okamoto et al. [140] demostrated the use of plasma CVM in the production of amorphous silicon solar cells. They used a multi-wire electrode to create a series of grooves in the solar cells which were approximately 30 cm x 40 cm in size. Solar cells produced with plasma CVM had similar performance as ones produced by laser patterning. Elastic emission machining (EEM) is another technique in which the material is thought to be removed by a chemical mechanism [141], [142]. The technique has been revised since first introduced [143]. The elastic sphere previously used has been replaced by a nozzle that directs ultrapure water mixed with powder onto the surface. The powder, SiO2, Al2O3, or ZrO2, reacts with the sample and then is washed away by the fluid. The technique is very sensitive to organic impurities and dissolved oxygen in the ultrapure water which can oxidize the surface of the sample. EEM was used to reduce the roughness of a silicon workpiece from 3.2 nm P-V value to 0.98 nm P-V value for a 21 mm x 25 mm measurement area [142]. The technique has also been used on germanium [141] and quartz [142]. In contrast to the chemical action of plasma CVM and EEM, ion beam machining and figuring use the kinetic energy of ions to remove material. The technique has been used for the planarization of samples [144] as well as for the production of an off-axis ellipsoidal mirror [145]. Fechner et al. [144] optimized an ion planarization technique introduced by Johnson and Ingersoll [146] for many different materials. In this planarization technique photoresist was spun onto the workpiece surface with a spin coater. The photoresist coated workpiece was then ion milled with the angle of the ion source at the planarization angle, the angle at which the material removal rate for the photoresist and the workpiece was the same. This technique was used to reduce the roughness of OFHC copper from 24.7 nm rms to 2.95 nm rms for a 40 m x 40 m measurement area [144]. The technique was also used to planarize fused silica, CaF2, silicon, garnet, and electroless nickel. In addition, the technique was applied to smooth the surface of a 103 mm diameter CaF2 convex lens with a 248.4 mm curvature. The roughness at the center of the lens was reduced from 3.38 nm rms to 0.5 nm rms for a 1 mm measurement length [144]. Because of the curvature of the lens, the centre was smoother than the outer portions of the lens. Schindler et al. [147] used ion beam milling without a planarization film to reduce the roughness of a 200 mm diameter SiC mirror from 208 nm P-V to 41 nm P-V measured over the entire mirror surface. The technique can also be used to machine a specific shape into the workpiece. Often this is accomplished by inserting a mask in the path of the ion beam which is then raster scanned across the part. Mercier et al. [145] used this technique with a specially designed mask to create an offaxis ellipsoidal shape from a cube of silica. Further examples of recent developments in the science and technology used for the creation of perfect surfaces can be found in the proceedings of a recent international conference on production engineering [148].

4.3 Nanomanipulation Since the invention of scanning tunneling microscopy (STM) and atomic force microscopy (AFM) nearly two decades ago, these instruments have been used to fabricate surface structures ranging from ~100 nm down to atomic dimensions. Examples of atomic and molecular manipulation include the positioning of individual atoms on a surface using low temperature STM, as well as the removal/deposition of atoms at room temperature due to electric field or mechanical processes. Experiments that use such processes to carry out larger-scale material transfer and/or surface modification include fieldevaporation of hundreds of atoms from Au tips, electronstimulated processes in STM chemical vapor deposition, and miscellaneous mechanical and thermal processes. An extensive review with more than 200 references on this area can be found in [151]. STM/AFM nanolithography ranges from manipulation of single atoms using low temperature STM (Figure 15) to memory storage using AFM thermoindentation. The forces between an STM tip and an adsorbed atom can be used to move the atom to a new location on the surface. Usually, metal surfaces are used as substrates because the surface corrugations are small and, therefore, smaller forces are necessary to move adsorbed atoms. Unfortunately, the atoms can also more easily diffuse on such metal surfaces, so STM manipulation of such atoms is usually done at low temperatures where thermal diffusion is minimized. STM can then be used to either laterally move an atom on the surface, or vertically relocate it by transferring the atom to the tip and then redepositing it in another location. Another system where low temperatures are not required for STM manipulation is the restructuring of atoms on a semiconductor surface. These experiments are typically carried out at room temperature and under ultra-high vacuum conditions to maintain surface cleanliness. Individual surface atoms can be removed and/or deposited by direct tip-sample contact, high tunneling currents, or voltage pulses. Field evaporation occurs when surface atoms are ionized and extracted by a high electric field.

Fig. 15:Sequence of low-temperature STM images (49 nm 49 nm) showing the construction of a triangular corral composed of Ag atoms on a Ag(111) substrate [152].

Historically, this process was initially performed using the single-electrode tip geometry of a field ion microscope (FIM). More recently, however, evaporation has been observed at lower field values using the double-electrode tip/sample geometry of STM. Because evaporation usually occurs from the tip (vs. the sample) due to the higher field there, the choice of tip material is important. The fabrication of nanoscale structures using STM and AFM has been a field of relatively active research since the inception of these techniques. A unique advantage of these scanning probe techniques is the ability to manipulate matter down to the atomic level and to form structures not possible by other means. More recently, attempts have been made to develop more technologically interesting structures for use in device production. Unfortunately, the serial nature of the writing process makes it time consuming and not economical for commercial applications. One solution to this problem has been the introduction of multiple tip arrays. Techniques such as dip-pen lithography or thermomechanical indentation are adaptable to such an array geometry and may eventually yield viable device applications. For example, in current magnetic data storage the superparamagnetic effect will ultimately limit room 2 temperature magnetic data density near 100 Gb/in [149]. Thermomechanical data storage using AFM tip arrays has already demonstrated data densities higher than this limit [150]. At present, however, it is still an open question as to whether these specialized lithography techniques will eventually mature into technologies of widespread application. SURFACE METROLOGY AT MICRO AND NANOSCALE Surface metrology has been the object of the 2002 keynote paper [5] and is not specifically considered in this paper, but its fundamental importance is emphasized. Metrology is a prerequisite for the success of any modern production technology, including precision engineering, micro engineering and nanotechnology. The present situation concerning surface metrology can be illustrated with respect to the traceability of surface topography measurements: Fig. 16 shows the range of different measuring instruments while Fig. 17 a similar diagram regarding calibration standards. Comparing the present possibilities with requirements from production mentioned in other sections of this paper, the need for developments in the nanometre range appears clear. Another clear challenge is the true 3-dimensional characterization of surface details involving re-entrances, as discussed in [4] and [5]. In general, the need for measurement and testing in nanotechnology has been considered by a position paper compiled by the High Level Expert Group on Measurement and Testing under the European Framework Programme for Research and Development [153]. The report addresses nanometrology from the following perspectives: Written standards Scientific instrumentation Validated measurement procedures Measurement standards Chemical analysis Biology 5.

new fields of observation but also offered hitherto unknown possibilities to locally influence and transform matter at the level of large atoms, single molecules, and atomic clusters [6].

Wavelength

Fig. 16: Diagram of wavelength vs. amplitude for different surface roughness instruments (courtesy of the PTB).

Wavelength

Fig. 17: Diagram of wavelength vs. amplitude for different surface roughness calibration standards (courtesy of the PTB). 6. CONCLUSIONS

In this context, it is also worth remembering that it was actually the invention of the scanning probing microscopes during the 1980s, which not only opened up

Surfaces act as interfaces governing the functional behaviour of a product, the controlling mechanisms often involving surface details on a micrometre or nanometre scale. Many emerging products are based on achieving these small scales, as is the case in precision engineering, microengineering, and nanotechnology. This paper, providing a schematic overview of applications, functional behaviour, and manufacturing technologies, clearly shows that the surface properties are of decisive importance for an increasing number of modern products. Advances have been made in tailoring surfaces for different high-end applications. Advances have been made towards better characterization of surfaces at sub-micrometre levels and understanding of the mechanisms that involve surface geometry, together with physical and chemical material

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