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SEM and its Applications for Polymer Science

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Physical Methods in Chemistry and Nano Science

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SEM and its Applications for Polymer Science

Module by : Stacy Prukop, Andrew R. Barron.

Introduction
The scanning electron microscope (SEM) is a v ery useful imaging technique that utilized a beam of electrons to acquire high magnification images of specimens. V ery similar to the transmission electron microscope (TEM), the SEM maps the reflected electrons and allows imaging of thick (~mm) samples, whereas the TEM requires ex tremely thin specimens for imaging; howev er, the SEM has lower magnifications. Although both SEM and TEM use an electron beam, the image is formed v ery differently and users should be aware of when each microscope is adv antageous.

Microscopy physics
Image formation
All microscopes serv e to enlarge the size of an object and allow people to v iew smaller regions within the sample. Microscopes form optical images and although instruments like the SEM hav e ex tremely high magnifications, the phy sics of the image formation are v ery basic. The simplest magnification lens can be seen in Figure 1 (#id1 1 6 8 9 6 5 6 1 7 0 5 7 ) . The formula for magnification is shown in Equation 1 (#eip-9 2 6 ) , where M is magnification, f is focal length, u is the distance between object and lens, and v is distance from lens to the image.
f M= uf = f vf
(1)

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Fi gu r e 1: Ba sic m icr oscope dia g r a m illu st r a t in g in v er t ed im a g e a n d dist a n ces u , f , a n d v .

Multistage microscopes can amplify the magnification of the original object ev en more as shown in Figure 2 (#id1 1 6 8 9 6 6 4 7 9 7 4 8 ) . Where magnification is now calculated from Equation 2 (#eip-2 9 9 ) , where f1 , f2 are focal distances with respect to the first and second lens and v1 , v2 are the distances from the lens to the magnified image of first and second lens, respectiv ely .
(v1 f 1 )(v 2 f 2 ) f1f2
(2)

M=

Fi gu r e 2: A sch em a t ic dia g r a m of t h e opt ics u sed in a m u lt ist a g e m icr oscope.

In reality , the objects we wish to magnify need to be illuminated. Whether or not the sample is thin enough to transmit light div ides the microscope into two arenas. SEM is used for samples that do not transmit light, whereas the TEM (transmission electron microscope) requires transparent samples. Due to the many frequencies of light from the introduced source, a condenser sy stem is added to control the brightness and narrow the range of v iewing to reduce aberrations, which distort the magnified image.

Electron microscopes
Microscope images can be formed instantaneous (as in the optical microscope or TEM) or by rastering (scanning) a beam across the sample and forming the image point-by -point. The latter is how SEM images are formed. It is important to understand the basic principles behind SEM that define properties and limitations of the image.

Resolution
The resolution of a microscope is defined as the smallest distance between two features that can be uniquely identified (also called resolv ing power). There are many limits to the max imum resolution of the SEM and other microscopes, such as imperfect lenses and diffraction effects. Each single beam of
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light, once passed through a lens, forms a series of cones called an airy ring (see Figure 3 (#id1 1 6 8 9 6 7 4 9 9 9 4 4 ) ). For a giv en wav elength of light, the central spot size is inv ersely proportional to the aperture size (i.e., large aperture y ields small spot size) and high resolution demands a small spot size.

Fi gu r e 3: A ir y r in g illu st r a t in g cen t er in t en sit y (left ) a n d in t en sit y a s a fu n ct ion of dist a n ce (r ig h t ).

Aberrations distort the image and we try to minimize the effect as much as possible. Chromatic aberrations are caused by the multiple wav elengths present in w hite light. Spherical aberrations are formed by focusing inside and outside the ideal focal length and caused by the imperfections within the objectiv e lenses. Astigmatism is because of further distortions in the lens. All aberrations decrease the ov erall resolution of the microscope.

Electrons
Electrons are charged particles and can interact with air molecules therefore the SEM and TEM instruments require ex tremely high v acuum to obtain images (1 0 -7 atm). High v acuum ensures that v ery few air molecules are in the electron beam column. If the electron beam interacts with an air molecule, the air will become ionized and damage the beam filament, which is v ery costly to repair. The charge of the electron allows scanning and also inherently has a v ery small deflection angle off the source of the beam. The electrons are generated with a thermionic filament. A tungsten (W) or LaB6 filament is chosen based on the needs of the user. LaB6 is much more ex pensiv e and tungsten filaments meet the needs of the av erage user. The microscope can be operated as field emission (tungsten filament).

Electron scattering
To accurately interpret electron microscopy images, the user must be familiar with how high energy electrons can interact with the sample and how these interactions affect the image. The probability that a particular electron will be scattered in a certain way is either described by the cross section, , or mean free path, , which is the av erage distance which an electron trav els before being scattered.

Elastic scatter
Elastic scatter, or Rutherford scattering, is defined as a process which deflects an electron but does not decrease its energy . The wav elength of the scattered electron can be detected and is proportional to the atomic number. Elastically scattered electrons hav e significantly more energy that other ty pes and prov ide mass contrast imaging. The mean free path, , is larger for smaller atoms meaning that the electron trav els farther.
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Inelastic scatter
Any process that causes the incoming electron to lose a detectable amount of energy is considered inelastic scattering. The two most common ty pes of inelastic scatter are phonon scattering and plasmon scattering. Phonon scattering occurs when a primary electron looses energy by ex citing a phonon, atomic v ibrations in a solid, and heats the sample a small amount. A Plasmon is an oscillation within the bulk electrons in the conduction band for metals. Plasmon scattering occurs when an electron interacts with the sample and produces plasmons, which ty pically hav e 5 - 30 eV energy loss and small .

Secondary effects
A secondary effect is a term describing any ev ent which may be detected outside the specimen and is essentially how images are formed. To form an image, the electron must interact with the sample in one of the aforementioned way s and escape from the sample and be detected. Secondary electrons (SE) are the most common electrons used for imaging due to high abundance and are defined, rather arbitrarily , as electrons with less than 50 eV energy after ex iting the sample. Backscattered electrons (BSE) leav e the sample quickly and retain a high amount of energy ; howev er there is a much lower y ield of BSE. Backscattered electrons are used in many different imaging modes. Refer to Figure 4 (#id1 1 6 8 9 6 3 7 9 7 9 6 5 ) for a diagram of interaction depths corresponding to v arious electron interactions.

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Fi gu r e 4: Dia g r a m illu st r a t in g t h e dept h s a t w h ich v a r iou s sa m ple in t er a ct ion s occu r .

SEM Construction
The SEM is made of sev eral main components: electron gun, condenser lens, scan coils, detectors, specimen, and lenses (see Figure 5 (#id1 1 6 8 9 7 2 4 7 2 6 0 0 ) ). Today , portable SEMs are av ailable but the ty pical size is about 6 feet tall and contains the microscope column and the control console.

Fi gu r e 5: Sch em a t ic dr a w in g of t h e SEM illu st r a t in g pla cem en t of elect r on g en er a t ion , collim a t ion pr ocess, sa m ple in t er a ct ion a n d elect r on det ect ion .

A special feature of the SEM and TEM is known as depth of focus , dv/du the range of positions (depths) at which the image can be v iewed with good focus, see Equation 3 (#eip-1 8 9 ) . This allows the user to see more than a singular plane of a specified height in focus and essentially allows a range of three dimensional imaging.
dv = du u v
2 2 2

= M

(3)

Electron detectors (image formation)

The secondary electron detector (SED) is the main source of SEM images since a large majority of the electrons emitted from the sample are less than 50 eV . These electrons form tex tural images but cannot determine composition. The SEM may also be equipped with a backscatter electron detector (BSED) which collects the higher energy BSEs. Backscattered electrons are v ery sensitiv e to atomic number and can determine qualitativ e information about nuclei present (i.e., how much Fe is in the sample). Topographic images are taken by tilting the specimen 20 - 40 toward the detector. With the sample tilted, electrons are more likely to scatter off the top of the sample rather than interact within it, thus y ielding information about the surface.

Sample preparation
The most effectiv e SEM sample will be at least as thick as the interaction v olume; depending on the image
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technique y ou are using (ty pically at least 2 m). For the best contrast, the sample must be conductiv e or the sample can be sputter-coated with a metal (such as Au, Pt, W, and Ti). Metals and other materials that are naturally conductiv e do not need to be coated and need v ery little sample preparation.

SEM of polymers
As prev iously discussed, to v iew features that are smaller than the wav elength of light, an electron microscope must be used. The electron beam requires ex tremely high v acuum to protect the filament and electrons must be able to adequately interact with the sample. Poly mers are ty pically long chains of repeating units composed primarily of lighter (low atomic number) elements such as carbon, hy drogen, nitrogen, and ox y gen. These lighter elements hav e fewer interactions with the electron beam which y ields poor contrast, so often times a stain or coating is required to v iew poly mer samples. SEM imaging requires a conductiv e surface, so a large majority of poly mer samples are sputter coated with metals, such as gold. The decision to v iew a poly mer sample with an SEM (v ersus a TEM for ex ample) should be ev aluated based on the feature size y ou ex pect the sample to hav e. Generally , if y ou ex pect the poly mer sample to hav e features, or ev en indiv idual molecules, ov er 1 00 nm in size y ou can safely choose SEM to v iew y our sample. For much smaller features, the TEM may y ield better results, but requires much different sample preparation than will be described here.

Polymer sample preparation techniques Sputter coating

A sputter coater may be purchased that deposits single lay ers of gold, gold-palladium, tungsten, chromium, platinum, titanium, or other metals in a v ery controlled thickness pattern. It is possible, and desirable, to coat only a few nms of metal onto the sample surface.

Spin coating
Many poly mer films are depositing v ia a spin coater which spins a substrate (often ITO glass) and drops of poly mer liquid are dispersed an ev en thickness on top of the substrate.

Staining
Another option for poly mer sample preparation is staining the sample. Stains act in different way s, but ty pical stains for poly mers are osmium tetrox ide (OsO4 ), ruthenium tetrox ide (RuO4 ) phosphotungstic acid (H3 PW1 2 O4 0 ), hy drazine (N2 H4 ), and silv er sulfide (Ag2 S).

Examples
Comb-block copolymer (microstructure of cast film)
Cast poly mer film (see Figure 6 (#id1 1 6 8 9 6 7 8 0 0 9 6 3 ) ). To v iew interior structure, the film was cut with a microtome or razor blade after the film was frozen in liquid N2 and fractured. Stained with RuO4 v apor (after cutting). Structure measurements were av eraged ov er a minimum of 25 measurements.

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Fi gu r e 6: SEM m icr og r a ph of com b block copoly m er sh ow in g sph er ica l m or ph olog y a n d lon g r a n g e or der . A da pt ed fr om M. B. Ru n g e a n d N. B. Bow den , J. Am . Chem . Soc. , 2 0 0 7 , 129, 1 0 5 5 1 . Copy r ig h t : A m er ica n Ch em ica l Societ y (2 0 0 7 ).

Polystyrene-polylactide bottlebrush copolymers (lamellar spacing)

Pressed poly mer samples into disks and annealed for 1 6 h at 1 7 0 C. To determine ordered morphologies, the disk was fractured (see Figure 7 (#id1 1 6 8 9 6 9 4 8 6 3 4 2 ) ). Used SEM to v erify lamellar spacing from USAXS.

Fi gu r e 7: SEM im a g e of a fr a ct u r ed piece of poly m er SL-1 . A da pt ed fr om J. Rza y ev , Macrom olecules , 2 0 0 9 , 42, 2 1 3 5 . Copy r ig h t : A m er ica n Ch em ica l Societ y (2 0 0 9 ).

SWNTs in ultrahigh molecular weight polyethylene

Dispersed SWNTs in interactiv e poly mer. Samples were sputter-coated in gold to enhance contrast. The films were solution-cry stallized and the cross-section was imaged. Env ironmental SEM (ESEM) was used to show morphologies of composite materials. WD = 7 mm. Study was conducted to image sample before and after drawing of film. Images confirmed the uniform distribution of SWNT in PE (Figure 8
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(#id1 1 6 8 9 5 7 8 4 8 8 0 7 ) ).

MW = 1 0,000 Dalton. Study performed to compare transparency before and after UV irradiation.

Fi gu r e 8: SEM im a g es of cr y st a llized SW NT -UHMW PE film s befor e (left ) a n d a ft er (r ig h t ) dr a w in g a t 1 2 0 C. A da pt ed fr om Q. Zh a n g , D. R. Lippit s, a n d S. Ra st og i, Macrom olecules , 2 0 0 6 , 39, 6 5 8 . Copy r ig h t : A m er ica n Ch em ica l Societ y (2 0 0 6 ).

Nanostructures in conjugated polymers (nanoporous films)

Poly mer and NP were processed into thin films and heated to crosslink. SEM was used to characterize morphology and cry stalline structure (Figure 9 (#id1 1 6 8 9 6 2 7 8 4 8 6 1 ) ). SEM was used to determine porosity and pore size. Magnified orders of 200 nm - 1 m. WD = 8 mm. MW = 23,000 Daltons Sample prep: spin coating a solution of poly -(thiophene ester) with copper NPs suspended on to ITO coated glass slides. Ziess, Supra 35

Fi gu r e 9: SEM im a g es of t h er m oclea v ed film loa ded w it h n a n opa r t icles w it h sca le ba r 1 m . A da pt ed fr om J. W . A n dr ea sen , M. Jor g en sen , a n d F. C. Kr ebs, Macrom olecules , 2 0 0 7 , 40, 7 7 5 8 . Copy r ig h t : A m er ica n Ch em ica l Societ y (2 0 0 7 ).

Cryo-SEM colloid polystyrene latex particles (fracture patterns)

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Used cry ogenic SEM (cry o-SEM) to v isualize the microstructure of particles (Figure 10 (#id1 1 6 8 9 6 6 2 7 2 7 1 6 ) ). Particles were immobilized by fast-freezing in liquid N2 at 1 96 C. Sample is fractured (-1 96 C) to ex pose cross section. 3 nm sputter coated with platinum. Shapes of the nanoparticles after fracture were ev aluated as a function of crosslink density .

Fi gu r e 10: Cr y o-SEM im a g es of pla st ica lly dr a w n poly st y r en e a n d la t ex pa r t icles. A da pt ed fr om H. Ge, C. L. Zh a o, S. Por zio, L. Zh u o, H. T . Da v is, a n d L. E. Scr iv en , Macrom olecules , 2 0 0 6 , 39, 5 5 3 1 . Copy r ig h t : A m er ica n Ch em ica l Societ y (2 0 0 6 ).

Bibliography
H. Ge, C. L. Zhao, S. Porzio, L. Zhuo, H. T. Dav is, and L. E. Scriv en, Macromolecules , 2006, 39 , 5531 . J. Rzay ev , Macromolecules , 2009, 42 , 21 35. J. W. Andreasen, M. Jorgensen, and F. C. Krebs, Macromolecules , 2007 , 40 , 7 7 58. M. B. Runge and N. B. Bowden, J. Am. Chem. Soc. , 2007 , 129 , 1 0551 . P. J. Goodhew, J. Humphrey s, and R. Beanland, Electron Microscopy and Analysis , Tay lor & Francis Inc., New Y ork (2001 ).

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Q. Zhang, D. R. Lippits, and S. Rastogi, Macromolecules , 2006, 39 , 658.

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