Characterization Tools of Nanomaterials 7.1. SCANNING PROBE MICROSCOPY (SP 7.1.1 Introduction The recent tremendous advancement of materials science in in particular is due co the discovery and development of modem characterization equipm most clegant and useful of these equipment is the scanning tunnelling microscope (STM) and atomic force microscope (AFM). in the early 1980s two IBM scientists, Binnig & Rohrer | developed 2 new technique for studying st Scauuing Tunnelling Microscopy favention was quickly followed by the development of a whole family of re neta} category of Ses Probe Microscopy (SPM) techniques. OF these later technigh ost important is: Atomuc Force Microscopy (AFM). The development of these techniques has without doubt been most important event in the Surface science field in recent times, and opened up-many of science and engineering at the atomic and molecular level. 718 Se Rin of STi All of the wehniques are based upom scaming-a probe (iypically called the rip in STM, since it literally is a sharp meaallic tip) just above 2 surface whilst monitoring some intentction betwe the probe and the surface (cf. Fig. 7.1). The interaction that is monitored in: + STM is the tunnelling current beoween a metallic tip and 2 conducting substeate which are in very close proximity but not actually in physical contact. + AFM is the van der Waals force between the tip and the surface; this m short range repulsive force (in contact-mode) or the longer cange attractive force (in mo contuet mode), bee either te wTRy Fig, 7.1. Tip-Substrate geometry of SPM. For the techniques to provide information on the surface structure at the atornic level (which is what they are capable of doing!): |. The position of the tip with respect to the surface must be very accurately controlled (to within about 0.1 A) by moving either the surface or the tip. 2. The tip must be very sharp—ideally terminating in just a single atom at its closest point of approach to the surface, ‘The attention paid to the first problem and the engineering solution to it is the difference between a good microscope and a not so good microscope—it need not worry us here, sufficient to say that itis possible to accurately control the relative positions of the tip and the surface by ensuring good vibrational isolation of the mictoscope and using sensitive piezoelectric positioning devices, Tip preparation is a science in itself—having said that, itis largely serendipity which ensures that one atom on the tip is closer to the surface than all others, Let us lock at the region where the tip approaches the surface in greater detail—the end of the tip will almost invariably ‘show § cectain amount of structure, with a variety of erystal facéts exposed —and if we now go down to the atomie scale, there is a reasonable probability of ending up witha truly atomic tip as explained in Figs, 7.2(a), (b) and (c) @ Fig. 7.2. (a) Schematic representation ofthe tip-campie geometry. (b) magnified versions of " ‘ © OF tip, and (0) at higher magnification, aatiChapter 7 Characterization Tools of Nanomateriats nig +: and wil he surface by the application of a voltage betyicen ncaa ere beeen the to, provided the separation of the tip and surge” i en nis pives wze to a tunnelling current, The direction of current toe sofficenty smal ay of the bias. Ifthe sample is biased -ve with respect tothe tip, es tere rom whe surface to the tip 2s shown in Fig. 73(2, whilst i the sample’) teeta vi sewon to the tp, then electzons will low from the tip to the surface as sy own, in Fig. 7.300). (by Fig. 72 Elactron tunnelling due to sample biasing under (a) negative bias, and (b) positive bias. ‘he name of the technigue arses from the quantum rzchanical tunnelling-lype mechanic by which the electrons can meve between the tip and substrate, Quantum mechantesd tunnelling perus particles to twanel through a potential bartier which they could aot surmount according ics—in this case electrons are able to waver tse the classically- forbidden region’ between the two solids as illustrated schematically on the energy diagram in Fig. 7.4, BS oc Vos ore T Por) This i an over-simplistic Starting point for understanding bow th Tunnelling is exponentially-dopendent 1 model of the n ipon the distance of seo —, & - oe A ig — 180 + Introduetion to Nanoscience and Nanotechnology surface: the tunnelling eurtent is therefore a very sensitive function Of this se of the surface topology may then be carried out in One OF the wo ways: 1. In constant height mode [in’ which the tunnelling current is monitored ax the tip is Sseanned paralle} to the surface, ef. Fig 7.5(a), 2 In constant current mode fin which the cunmelling earn is maintained constant 2s the Aip is scanned seross the surface, ef. Fig, 7.5(b)), aration, Imaging Movement of the tp at constant height mode: Movement of the tn at constant curert made ————— 2 ——“- @) © Fig. 7.5 (a) Constant height mode operation of the STA 4p. (b) constant current mode operation of the STM lip, HE the tp is scanned at what is nominally « constant height above Actually @ periodic variation in the separation distance between the tp Oh: Point the tip will be directly above a sutface atom and the twanc ‘whilst at other soints the tip will be above hollow siteson the eurlace will be much smaller (of. Fis, shows a per "Image" of the surface piewire of the surface!) Jn practice, however, the normal way of saan Constant whilst the tip is scammed across the surface. This ie Up's height above the surface so that the tunnelling cumont doce no Position. In this mode, the tip will move slightly upwardly ay it passes slightly in towards the surface as it passes over a hollow. ne shown in Fig. 7.5(h): ‘The image is then formed by plotting the tip height (strictly, the voltage applied to the piezo} vs. the lateral Up position. 7.1.3 The Detalle of'STM To understand the theory of how STM wi hhow it relates to all the experimental ob the surface, then there is and the surface atoms. Ar ling current will be large (and by the . imaging the surface is to maintain the tunnelling achieved by-adjusting the orks, it is vital to know what is tunnelling current, and servations,Chapter 7 Characterization Tools of Nanomatecinis + 181 7.1.3.1 Tining curent Tunnelling current is originated from the wavelike properties of purticies (electrons. in the case) in quantum mechanics. When an clectron is incident upon vacuum burier with potential energy larger than the Kinetic energy of the electron, there is still « non-zero probability that it may traverse the forbidden region and reappear on the other side of the barrier. It is shown by the leaks out electron wavefunction in Fig. 7.6. _ Vacuum loyal ' 1 L-Fomnitevat Fig. 7.6 Electron wavefunction as tunnelling eurent. The electron wavefunctions at the Fermi level haye a characteristic exponential inverse decay length K given by — et ay where, m is mass of electron, is the local tunnelling barrier height or the average Sark function Of the Gp and the sample. If two conductors are so close that their leak out electron wavefinctions overlap, as shown in Fig. 7.7. then a sinall voltage. V. applied between the cip and the sample will allow thé overlapped electron wavefunction to permit quantum mechatiics Vacuum level 075 Fig. 7.7 Qvoriagping of electron wavelunciion at small tip-sample distance, under bias,182 + introduction to Nanoscience and Nanotechnology funnelling and a current, ¢ will low seross the vacuum gep. At low voltage and temperature fe kd . (72) Where d is the distance between the tip and the sample. IF the distance increased by 1 A, the Rulrent flow decreased by an order of magnitude, so the sensitivity to vertical distance is terribly high. As the lip scans across the surface, it gives atomic resolution image as shown in Fig. 7.8, ‘This is the STM image of $i (11) = 7X7 surface, and:the white spots represent the position of the atoms. Fig. 7.8 STM image of a'Si (111) surface, the white spots rearesent the Position of the: atoms.185 + Introduction’ to Nanoscience and Nanotechnology 7.13.5 “ste Some opplcations Here are some examples of using STM in bo technological applications: ” i 2g ct on R The invention of STM have left 2 great imps ne a real SPACE which is the is bs Of STM to study metal and semiconductor surfaces cn prove ie information. Especially in studying semiconductors such #8 $i (100) su nn The STM echnologically important Si substrate material for microelectronics device fa iat on during image of $i (100) surface shown below giv direct confirmation of dimers on rewlation and surface reconstruction, although it has been previously suggested by theoretical calcu other experimental observations. Here are the bias-dependent STM images, shown 18 Fig, 7.12. postive bias to the tip whereas the right one is taken with nepsive bias W directly reflect the spatial distribution of the occupied’ bonding StaKe 8 i advanced th surface science studies and ad e surface Science. The left image is waken with to the tip. The images in berween the dimer WOT can Fig. 7.12. Bias-dependent STM images of a Si (100) surtace ntibonding states localize pom the dimer. Figure 7.13 erminated (1X 1) lattices into a (2% 1) ms on top layer, while small dots are Way fi atoms, while the unoccupied depicts the model of the reconst reconstmiction via dimerization, Uie |, represent atoms of second layer bake cy % e@ eo 0 Schemave tnovel of the recons . 5 '@ TECONSHUEtION of the Bulketei reconstruction va dimenzation terminated (1x1) lattices into a (2x1) ea (xeau —— & & & ‘Y-axis { micron — G0r a Bade~— Ls haw Cena eS ome ds Frod Toole of Nenamatore tp i dt manoiopography OF a surfay feutions:, The microtopography an ! stag na for high precision optical components and disk ga” Toad of ground surfaces in area where: such a finish is crucial hin indivi Kon @ diamond. surface roughriess of macl is the imoge of an individual rum mar ad-tum STM Fig. 7.14(a), is the image ition for a high capacity harg 4 STM image. shown in etic film deposition igh capacity hard qj for subsequent magn Al substrate to be used drive. The image obtained by scanning electron microscope (SEM) is shown in Fig. 7.14¢) The i btained bs ing el mit e (SEM) is sh ready comparison. The high spatial resolution of STM provides an important complement ih * SEM. gy Fig, 7-14 (a) STM image of an individual tum mark on-¢ diamond-tumed Al substrate, and (b) SEA image of the same, 3. Manipulation of atomis: One innovative applications of STM recently found is ‘manipulation of atoms, Figure 7.15 describes the example of the STM. manipulation of atoms, According to the picture, iron atoms are placed on Cu (111) sutface at ‘very low temperature (4K). Tron atoms are first physisorbed on the Su surface, then the tip is placed directly overs Fig. 7,= 4188 + introcuetion to Nanoscience and Nanotechnology, physisorbed atom and towered to inorease the aumetive: force by increasing the tunnelling aoa the atom was dragued by the Up and moves aurosy the Surluce 10 a desired position. ma. the tip was witherawn by loweriag the tunnelling current, These STM images show the The steps of queuum corral formation 7.14 Summa STM In summary, the development. of the Various scanning, probe microscopy techniques has revolutionized the study of surface structure—stomie resolution images have been obtained not cly on single crystal substrates in UM but also on samples at atmospheric pressure and even ‘ander solution. Many problems still remain, liowever, and the interpretation of SPM. data is not alovays as stightforward as it might at fist soem. There is sill very much @ place forthe more ditional surface structural techniques sucfi as LEED. This introduction to STM fias concentrated on the non-invasive imaging applications of the vechnigue, yet there is increasing interest in using such iochniques as a tool for the actual ‘modification of surfaces. At the momnent this is still at the “gimmicky” stage, but the longer term implications of being able to manipulate surface structure and molecules atte atomic level have get to be fully appreciated: we can but await the future with interest! Fig. 7.16 Image of 2 quantum corral. Figure 7.16 shows @ STM image showing iron atoms adsorbed on s copper (111) surface fosming 2 “quantum corral" in «very low tempersture (4K), Actually, the image shows the contour of the local density of cloctron states. The corral is about 14.3 nm in dianteter 7.2 GENERAL CONCEPT AND’ DEFINING: CHARACTERISTICS, OF AFI _ Skane Proiiy robe: Wizoscopes 7.21 ‘The atomic force microscope ‘sone of about two dozen types of scunned-proximity probe injoroscopes. All of these microscopes work by: meusuting @ tors! propesty—such as height, optical absorption, or magnetism—with a probe or “tj " placed very olose to the sample. ‘The ca180 Introduction to Nanoselence and Nanotechnology + High-resolution tip-sample positioning, + Force feedback ‘The refinements are described below: 7.2.2 Laser Beam Deflection . , a convenient and sensitive method of measuring cantil lever deflection. AFMs can generally measure the vertical deflection of the cantilever with picometee efolution, To dehieve this, most AFMs today use the optical lever, a device that ac es resolution comparable to an interferometer while remaining inexpensive and easy-to-use [5-7]. The optical lever [Fig. 7,17()} operates by reflecting 2 laser beam off the cantilever [Angular deflection ofthe cantilever causes a two-fold larger angular deflection of the laser beam. “The reflected laser beam strikes a position-sénsitive photodetector consisting of two side-by-side photodiodes. The difference between the two photodiode signals indicates the position of the laser spot on the detector and thus the angular deflection of the cantilever. Because the cantilever-to-detector distance generally measures thousands of timés the length of the cantilever, \ the optical lever greatly magnifies motions of the tip. Because of this ~2000-fold magnification optical lever detection can theoretically obtain 2 noise level of 10 m/Hz'# (8). For measuring cantilever deflection, to date, only the relatively cumbersome techniques of interferometry and tunnelling detection have approached this value. Laser beam deflection offers Detectorand ‘ Teedtack eteetronias Phoiodiods Sampfe surta i ° Cantilever and tip PZT scanner - oy [b) Schematic diagram.of the opetat ing principle of an AEM. 7.2.3 AFM Contilevers “erally, AFM cantilevers have high caxibility. A high fexibitity yl we General x ig! ibili ig il j ibility stylus exerts lower downward forces on th sample. tesulting in loss disgort reason, AFM cantilever '8 in less distortion and dama; ile scanni: snilevers generally have spring constants of about ot Mim en Peete . "Fig. 7.18), AsChapter 7_Characterization Tools of Fig. 7.18 Schematic illustration of the meaning of “spring constant’ as applied to it Canes i tai i Visualizing the cantilever as a coil spring, its spring constant directly ate downward force exerted on the sample. Paul Hansma points out (9,10), a Slinky is about ten times stiffer G Nfm). Ie would aie) long time to image a surface. by dragging a Slinky over it (in the configuration of Fig: it because a Slinky cannot respond quickly as it passes over features. That is, a Slinky bas gj Tesonant frequency, but an AFM cantilever should have a high resonant frequency. The cag for the resoriant frequericy of a spring: nd to be very small. Commercial veal manufacture almost all AFM cantilevers by microlithography processes similar 10 those usd make computer chips, The Park Scientific Insteuments [11] cantilevers shown in Fig 7} measure 100 jum-in length and consist of sili i reflectivity. Fig. 7.19. Etectron mire : if Te aeh Ot 10100 jum fon = ele i, cant 9 V-shaper -Paul + Catech; cantiavors trom Park Scientific instr meni. Suna, ae °Higure 7.27 shows an image of bovine serum albumen (BSA) On Sillcon. A nuluoEr OF wpoear in the topography image, each presuinably corresponding to a single BSA bumps aj r { B moleute, "The elasticity image reveals that each of the bumps is soft relative to the silicon substrate, a reasonable result for protein molecules, Fig. 7.27 1x1 um simuttaneous topography (left) and elasticity (righ!) images of bovine serum albumen on silicon (sample prepared by Sie-Ting Wong of Abbott Laboratories). 7.2.7 oAFMwand Biology ‘The ability of AFM to image. at atomic resolution, combined with its ability to image a wide ety of samples under a wide variety of conditions, has created a great deal of interest in applying it to the study of biological structures, Images have appeared in the literature showing DNA, single proteins, structures such as gap junctions,sand living cells (9). Unfortunately, AFM cannot image all samples at atomic resolution. For biological samples, dull tips and tip-sample interaction forces prevent high-resolution imaging. The end radii of available tips confine atomic resolution to flat, periodic samples such as graphite. In addition, because biological structures are soit, the fip-sample interaction tends to diston or destroy them. Figures 7.28(a), (b) and (c), for example, shows how forces exerted on small collagen fibrils tend @) (e) () Fig. 7.26 Images 1-{a}, 50-{b), and 100-(c) of small collagen fibrils [rom a sequence of 100 images. Repetitive scanning of the same area progressively detaches the ‘ibnis trom the glass Substrate, causing distortion in the direction of scanning, left-to-right and top-to-bottom.resolution ™. eerie 3 _ a uh \ een RET : Increase resolution magnification | Fig. 7.20 Schematic illustration of the differénce between resolution and magnitcat, thi ii \d-very Small obje light diffraction and interference mre when ets STTegss oe the aa a “ i a . 5 8, ae fare 1B wavelength (due to wave particle duality). A 100% 7 peer ee a f i nm. Therefore electron microscopes are capajy,j j electron have an associated wavelength o} f rose i 5 producing high-resolution images. In fact, Electron Microscopes gee 4 ae oped to ove the limitations of Light Microscopes which are limited by the physics of light to 500x 0: ff) magnification and a resolution of 0.2 micrometers. In the early 1930) 's this theoretical init been reached and there was a scientific desire to see the finer details of the interior of organic cells (nucleus, mitochondria, etc.). This required 10,000x plus magnification vi was just not possible using Light Microscopes. The Transmission Electron Microscope was the first type of Electron Microscope to be developed and is pattemed exactly. on theLi Transmission Microscope except that a focused beam of electrons is used instead of light through” the specimen. It was developed by Max Knoll and Emst Ruska in Germany in I The first Scanning Electron Microscope (SEM) debuted in 1942 with the first commen instruments around 1965. Its late development was due to the electronics involved in “scant the beam of electrons across the sample. ‘ie Scanning electron microscope (SEM) is @ type of electron microscope capable of prod ighveesolution images of a sample surface\{16-17], Di in which the ime L, 4 credited, |SEN. images have a characteri lamidoal cpenen ea aeaeall indbing he sures sree crtcteistc thee-dimensional appearance and. are use scanning electron microscope, iw w sample] Figure 7.31 shows the schematic diag lt the electrons by stray aic ore Ole system must be vacaum protected to prevent scatitél an to be prepared carefully to eee teva Se ere enOe Sen ees Casta Md the vacuum inside the microsco Silieraed monochromatic eleorons, The staan sob represents the Soe ge progucité§ usual i erg : me iy ot by the “coarse probe current non Ee tt Snount of curent inthe beara, It works in confuse eee oe Form "KS in conjunction with the condenser ape"200 = introduction te Nanoscience and Nanotechnology serene fl Condenser lenses Objective tens Xeray detectore« + Secondary electzon Hetector ‘Specimen siub-~ Fig. 7.37 Schematic diagram of SEM, to climinatz the hiyhvangle ‘electrons from the beam. The belt is then constricted by the condenser aperture (usually not user selectable), eliminating some high-angle electrons. (The second condenser lens forms the electrons into a thin, tight, coherent aad is usually controlled by the “fine ptobe current Iso A user selectable objective aperture further elitninates high-angle electrons from the beam] |A set of goils then “Scan” or “sweep” the beam in.a grid fashion (like a television), dwelling on points for « peviod of time determined by the sean speed (asually in the microsecond cange)!|rhe final lens, the objective, focuses the seanning team onto the part of the specimen desired) When the beam strikes the sample (and dwells for a few microseconds) intersctions écour inside the sample and are detected with various jostraments Before the béam moves to its next dwell point, these instruments count the number of interactions anid display @ pixel on a CRT whose intensity is determined by this number! (the more reactions, the brighter the pixel). This process is repeated until the grid scan is finished and then repeated, the entire pattem can be seanned 30 times per sécond. 7.3.4 SEA Techniques ‘The various steps involved for SEM imaging are now qualitatively described in detail. Firstly, the sample is pluced inside the microscope's vacuum column through an air-tight door, After the air is pumped out of the column, an electron gun (ut the top) emits 2 beam of high energy electrons. This beam travels downward through a series of magnetic tenses designed ta focus the electrons to a very fine spot. Near the bottom. «'set of scanning goils moves the focused beam buck and forth across the specimen, row by row. As the electron beam hits each spot on the sample, secondary electrons are knocked loose from its surface. A detector counts these electrons and sends the signals to an amplifier. The final image is built up from the number of electrons mitted from each spot on the sample, The steps are described sequentially in Figs 732G@)<(0) and: 7.33 show al} of the above-mentioned processes logether inside an SEM.ee = bee ll wer transmitted unscattercd electrons and $0 Will appear 4. Wey eran aa have niore Ec pa and thus ae 4 5 -d electrons: These are the incident electrons that ares ‘f Et cal) by atoms in the specimen an-lastic fashion (a9 | pssap scatiered electrons are then transmitted through the remaining portions of the » ‘a Jlectrons follow Bragg's Law and thus are scattered according to Wavelengts ity fevenn the atoms in the’ specimen sin(angle of. seul = dd sing, ok electrons have the same energy (thus wavelength) and enter the specimen nora) ye is . All incidents that are scattered by the same atomic spacing: will be Scattered by th sia These “similar angle” scattered electrons can be collated using magnetic lenges io ¢ 4 of spots; each spot corresponding t0 2 specific atomic spacing (a plane). This Patent yield information about the orientation, atomic arrangements and phases present in then examined. Inelastically scattered electrons: These are the incident electrons that interact with ‘atoms in an inelastic fashion, loosing energy. during the interaction. These electron a transmitted through the rest of the specimen. Inelastically scattered electrons can be ut two ways: * Electron energy loss spectroscopy: The inelastic loss of energy by the ig electrons is characteristic of the elements that were interacted with. These ene: unique 10 each’ bonding state of cach element and thus can be used to extay compositional and bonding (i.e: oxidation state) information on the specimes p being examined. ° Kakuchi bands: Bands of alternating light and. dark lines that are formed by'in scattering interactions that are related to atomic spacings in the specimen. Thest ly can be either measured (their width is inversely proportional to atomic: spac “followed” like a roadmap to the “real’” elasticity scattered electron pattern, 7.3.7 Environmental SEM: Environmental SEM (ESEM) allows samples to be observed in low-pressure ps ervitonmenis (1 0 50 Tor) and high relative humility (up to 100%). ‘This is made post the development of a secondary-clectron detector capable of operating in the presence a ‘Vapour and by the use of pressure-limiting apertures with differential pumping in the te | es) electron beam to separate the vacuum tegions around the gun and lenses from the’a 208 + Introduction ta Nanoscience and Nanotechnology reactions and solid-air-2as systems in general comld not be abserved by conventional SEM, but can be done by ESEM, The first commercial ESEMs were produced by the ElectroScan Corpotation in USA in 1988, ESEM is especially useful for non-metallic and biological materials because couting with carbon or gold is unnecessary. Plastics and Elastomers can now be routinely examined, as can biological samples. Coating is irreversible. and may reduce the value of the results obtained. Thus very small details on the surface of the sample may be concealed by the coating, Ict alone that coating is done under vacuum, which drastically alters hydrated specimens. oo ifcansmission clectron microscopy (TEM) involves a high energy electron beam, emitted from an electron gun, to transmit through 2 specimen that is in part trnsparent to electrons and carries the information about the inner structure of the specimen. This transmitted electron beam is then feaches the imaging system of the microscope and the spatial vanation in this information (the Sjouge") is then magnified by a series of electromagnetic lenses until it is recorded by hitting a fluorescent screen, photographic plate, or light sensitive sensor such as a charge-coupled, device (CCD) camera, The image detected by the CCD may be displayed in real-time on a monitor or compute’) (Ems work the same way as SEMS except that the transmitted part of the electrons is projected onto a phosphor soreen far the user to se Various steps of the working of TEM are as follows’ (cf. Fig. 7.39): firsily, the electron gun produces 2 stream ‘of monochromatic elections. which is hen focused toa small, thin, coherent beam by the use of secon scion aid Candensarlences -— ‘Spogimon grid --—4 Objective tens Project lens -. Fig. 7.39 Schematic diagram of « TEM._ Chapter 7 Characterization Tools of Nanomateriais + 209 condenser lenses. The beam is restricted by the condéaser aperture (usually user selectable), knocking out high angle electrons (those far from the optic axis, we dotted line doin the centres “Thereafter. the beam strikes the specimen and pans of it are transmitted. This transmitted portion is focused by the objective lens’ into an image. Optional Objective and Selected Are metal apertures can restriet the beam; the objective aperture cnbances ihe contrast by blocking om high-angle diffracted electrons, whereas the selected area aperture enables the user to examine the periodic diffriction of electrons by ordered arrangements of atoms in the sample. The image is then passed down the column through the intermediate and projector lenses, being enlarged all the way. ‘Then the image strikes the phosphor image screen unc light is generated, allowing the user to see the image, The darker areas of the image represent those areas of the sample that fewer electrons were transmitted through (they are thicker or denser). The lighter areas of the mage represcnt those aréas of the sample that more electrons were transmitted through (they are thinner or less dense). A simplified representation of the principles of the image formation is given in Fig. 7.40. Optic axis ‘Object piane Coject tors: Back focal plane idiftection patter) mage plane - Fig. 7.40 Simplified representation of the ray path leading to the rst intermediate umage in ine image plane cf 1ne abject lens. Electrons, which come trom the condenser systam of the TEM, ate scattered by Iho sample, situated in the odject plane of the odject lens. Electrons scattered in the same direction are focused in the back local plane, and, as a resull, a diffraction pattern is formed there. Electrons coming ftom the same pain! of the object afe focused in the image plane. In the TEM, the first intermadiate image is magnified by further lenses (projective system), Ja general, there are two image modes of TEM: * Bright field image: In the bright field (BR) mode of the TEM, an aperture is placed in the back focal plane of the objective lens which allows only the direct beam to pass [of Fig. 7.41(a)). In this case, the image results from a weakening of the direct beam by its interaction with the sample, Therefore, mass-thickness and diffraction contrast contribute to image formation: thick areas, arcas in which heavy atoms are enriched, and crystalline areas appear with dark contrast. It should be mentioned that the iategpretalion of imtages is offen impeded by the simultaneous occurrence of the conirast-forming phenomess,210 + Introduetion to Nanoscience and Nanotechnology Optic sie Object apature Ditirection pattem Bright Held image Fig. 7.41(a) Schematic illustration of bright fied image mode. , . . * Dark field image mode: In dark field (DF) images, the direct bes i pal onthe eerie whe one or more diffracted beams are alowed to pass Be aie inl (et Fig. 7.4100). Since difftacted beams have sttonsly inert wh tp ina ‘ery useful information is present in DF images, ¢.g, about planar defects, stacking or particle sizes itional stages and detectors, ‘An netimes i same ay es Slectron cryomicresco, is a TEM with a piitimen holder capable of maintaining the Zerihea at Toad nitogen ar taste femperatures This allows ining epecinicis prepared in Sireoos ice, he prefered mene “TEhIGIE for imagine individual molecules ox_macromblecular assemblies ee assembliemsA TEM can be modified into a scanning transmission electron microsca, (STEM) by the a {dition of a system that rasters the beam across the sample to for ied rm the image, combined with Suitable detectors, An* Seis a ate RTE inet oe eS research and Evelopmiem, There ate a number of drawbacks to the TEM technique. Many materials requite Chapter 7 Charactorization Tools of Nanomaterials = 211 analytical TEM is one equipped with derectors shat can determine the elemental composition of its X-ray spectrum or the energy-loss spectrum of the transmitted electrons. Modem research TEMS may include aberration corectors, to reduce the amount of distortion in the image, allowing information on features on the,scale of 0.) nm to be obtained (regalutions dowa to 0.05 nm have chieved, so far) a magnifications of SO million times. jnochromators may also be used which reduce the energy spread of the incident electron beam T Tess than 0.15 eV. | | Resolution of the TEM is limited primarily by spherical aberration, butanew generation of aberration cortectors have been able to ally overcome spherical aberration to increase fesolution, Softwaré-corection of spherical aberration for the is fy Resolution TEM (HR’ EM) = Kas-allowed the production of images with sufficient_resolution to show Carbon atoms ik a “GianmomI separated byl 0.89 189 pm) and atoms in silicon at 078 A (78 pri) at “magnifications of 50 million times (The ability to determine the positions of atoms within the specimen by analysin “Extensive Sample preparation to produce a sample thin enough to be electron transparent, which makes TEM analysis a relatively time consuming process with a low throughput of samples. The structure of the sample may also be changed during the preparation process, Also the field of view is relatively small, raising the possibility that the region analysed may not be characteristic of the whole sample: There is porential that the sample may be damaged by the electron beam, particularly in the case of biological materials. py oye Derek sa fees by oP ashen! MERIT High Resolution Transmission Electron Microscopy (HRTEM) allows the imaging of, the crystallographic structure of 2 sample at an atomic scale. Because of its hiigh resolution, it is an invaluable tool to study nanocrystalline materials. At present, the highest regolution realised is 0.8 A. Ongoing research and development, such as efforts in the framework of Transmission Electron Aberration-corrected Microscope (TEAM) [22] will soon push the resolution of HRTEM to 0,5 A. At these small scales, individual atoms and crystalline defects can be imaged. The basic pringiple of HRTEM is as follows: let us consider a very thin slice of crystal that has been tilted'so that a low-index direction is exactly perpendicular to the électron beam. All lattice planes parallel to the electron beam will be close enough to the Bragg position and will diffract the primary beam. The diffraction pattern is ‘the Fourier transform of the periodic potential for the electrons in two dimensions (ef. Fig, 7.42), In the objective lens, all diffracted beams and the primary beam are brought together again; their interference provides a back-transformation and leads to an enlarged picture of the periodic potential. This picture is then magnified by the clectron-optical system and finally seen on the screen at magnifications of typically 106. This imaging process called phase-contrast imaging or high resolution imaging. This process involves electron diffraction through the matetial atoms during transmission through ther (the relative phases of the electrons change upon transmission through the sample). Due to our inability to. record the phase of these waves, we generally measure the amplitude resulting from this imerference, however, the phase of the electron wave: still carries the information about the sample and generates contrast in the image, thus the name phase-contrast imaging. This\) 212 + inoduetion to Nonoscicnee and Nanotechnology pte aans Odject exit newer transfom WW Diffraction pattern —_—_—_<~S XIX ge i Inverse Fourier ee rae Fig. 7.42 Objective lens performs a Fourier transform that creates the diffraction patter of the ) object inthe back focal plane and an inverse Fourier transform that makes: ihe ~ interference of the diffracted beams back to.a real space image in the image plana (lattice image). diffraction contrast in addition to the already present contrast in the transmitted beam form the . required image. This, however, is true only if the sample is thin enough so that amplitude variations only slightly affect the image (the so-valled weak phase object approximation, , WPOA). But the interpretation of phase-contrast images ig not a straightforward task. Deconvofuting the contrast soon in a,high resolution image to determine which features are due to which atoms in the material can rarely, if ever, be dotie with the naked eye. Instead, because the combination of contrasts due to multiple diffracting elements and planes and the transmitted beam is. complex, computer simulations are used to determine what sort of contrast different structures may produce in a phase-conurast image, Thus, a reasonablé amount of information | about the sample needs to be understood belore x phase contrast image can be prop interpreted, such 46 u conjecture as to what crystal structure the material hits. Practically, hase contrast imaging is the highest resolution imaging technique ever developed, and can allow for resolutions of less than one A (less than 0.1 nanomenes), 1¢ thus enables the direct viewing of Columns of atoms in « crystalline material, But the difficulties in phase-contrast imaging is that the coutrist is not intuitively imerprexable as the image is influenced by strong aberrations of the ! imaging leases in the microscope. ‘Technically. phase-contrast images are formed by removing the object aperture entirely or by using 3 very large objective aperture (cf. Fig. 7.43), This ensures that not only the transmitted beam. but also the diffracied ones are ellowed to contribute to the image. The difference between HRTEM and conventional TEM is the use of this phase contrast imaging. Conventional TEM employs additional detectors attached to the electron beam column for spectroscopic measurements, wheres HRTEM has little or no additional attachments $0 as to ensure a uniform electromagnetic environment all the way down the column for each beam leaving the sample (wansmitied and diffracted). Because phase-contrast imaging relies on differences in phase between the electrons leaving the sample, any additionall phase shifts that occur between theCharacterization Tools. of Nanomateriats + 213 Optic aie, Ditfraction pattern Latice image Fig. 7.43. Schematic ‘diagram of the electron beam column in HATEM. To otain lattice images, 2 larger object aperture has to be selected thet allows many beams including the direct beam to pass. The image ic formed by (he interference of the difracted beams wilh tne direst beam (pheso-contrasl). # the point resolution of the mieresaope is Suticanty ign and a Suitable sample oriented along 3 zone axis; then highsresolution TEM (HRTEM) images are obtained, in many cases, the atomic sinicture of 3 specimen can cirectly be investigated by HATEM, sample and the viewing screen will make the image impossible to interpret, ‘Thus, very Low degree of lens aberration is also a requirement for HRTEM, und awanves in spherical aberratia corrections have caabled a new generation of HRTEM w +6 solutions, once thought impossible. Some typical TEM and HRTEM images are 8 Although’ the inerction of the electron wave with the crystallographic: siructure of the sample ig not-entirely understood yet, bur a qualitunve is interaction ean readily be obwined. Physically; cack imaging electron interacts independently with the sample and. above I the sample, the wave of an election cai: be approximated as a plane wave incident on the sample i surface, As it penetsates the sample. i is auracted by the positewe atomic potentials of the anim Cores, and channels ulong the stom columns of the crystallographic Hattie. At the sume time, the interaction between the eleclion wave in differet atom volumns leads ( Bragg Uifimeton. As afesult of this interaction with the sample, the election exit Wave (the electron wave right Belov the sample), represented by &(x,¥9, becomes. superposition UF plane wi i Function of the spatial coordinate x) and a multitude of diffracted beams with different ineplane spatial frequencies v Quigh spatial frequencies correspond to large distances from the caput! axis cf. Fig. 7.43). The phase change-of 4,(x.1), compared tothe incident wave, peas s the location of the atom columns, The exit wave now passes through the imaging system of the mico™e 7" where it undergoes further phase change and interferes as the image Wave ine angi oe = {photo plate or CCD), Ie is important (0 realize, that the recorded iiss A ots y representation of the sample's crystallographic structure. For instance. hight Intensity BN i 7 se owhieh ae214 + Introduction to Nanoscience ang Nanotechnology. Fig. 7.44 (a) TEM image of CuAlO, nanopanicies (23), Dark regions are the representative hanopartites. Inset: shows the difction pattern, obtained by the TEM showing Hancoystaline nature of the panicles, and (b) HRTEM image of a Si nanoparticle ‘showing well-aligned atomic planes (21). Inset shows the firstlourier transform of the cleciron diffracted image. Bright spols indicate single-crystalline mature of the nanoparticle. fnight not indicate the presence of an atom column in that precise location. The relationship between the exit wave and the image wave is a highly noolinear one:and is a function of the ‘aberrations of the microscope. It is deseribed by the contrast transfer function. 7.4.2 Coniot)Teansfér Function’ Contrast Transfer Function (CTE), frequently refen EM imaging, allows to evaluate and compare the performances of different microscopes. CTF is the functicn whi modulates pe amoltudes and phases of the ciecuon diffraction pattem formed in the back focal plane of ie Objecuve ysically, it depicts the"phase changes of diffracted beams with respect to “The direct Beam. It can be represented as Toh) ==si . wit, ) 7.22) * map yaa® (723) witere Co is the spherical aberration coefficient which defines the quality of the microseo objective lens, 4 isthe slestion wavelength dependent on the atbettiath i : ; he accelerating voltage, Af i efocus.valve ard kis the spatial Frequency ing voltage, AF is the le CTF is very complicated, i tis Zero at the origin and oseiltatcry (vanies between —| (ef. Fig 7.45(@)]. Non-zeco values of this (or very close to zer0) values indicate no 'sno'contrast, which means no information and +1 passing through 0).for higher values of Function indicate good transmiuanee whereas zero transminance, Therefore, a 260 Values oF CTF thersChapter 7 Characterization Tools ot Nanomateriats + 275 es place for those spatial frequencies. For negative values of CTE, positive phase | baie te ane that atoms will appear dark on a bright background. On the other hang, for positive values of CTF, negative phase-contrast occurs, meaning that atoms will appear bright on a dark background. CTF can continue forever but, in reality, it is modified by envelope functions and eventually dies off due to the temporal coherency (caused by chromatic aberrations, focal and energy spread, and instabilities in the high tension and objective eng current), and spatial coherency (caused by the finite incident Seam convergence) [cf. Fig, 7.45(b)]. It is to be noted that the first crossing of the K-axis at extended! Scherzer defocus corresponds to point-to-point resolution of the microscope and the point where envelope functions damp the CTF to zero corresponds to the information limit of the microscope. X Point resolution, + tnformation fimit 3 5 o , wl 2 3 4 s . 6 (ormy* k (omy @) ©) Fig. 7.45 CTF for a 200 keV microscope at “extended” Scherzer defocus with envelope function: (@) applied and (b) not applied. EXERCISES 1. Why is spatial resolution of STM better than AFM? . Describe the basic working principle of an STM and explain thé charge transfer in terms of LDOS. 3. Explain how Z-piezo works for imaging the ‘sample surface in constant tunnelling current mode, we 4. Show that in STM the tunnelling current varies exportentially as the tip-sample distance. 5. Describe in brief some nanotechnological applications of STM. 6. “In principle, AFM resembles the record play oo Explain, Prayer as well as the stylus profilometer’ 7. Explain how AFM can be used in biological applications, 8. What is the difference between resolution and magnification?