Visualization of Individual Images in Patterned OrganicâInorganic

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Visualization of individual images in patterned organic-inorganic multilayers using GISAXS-CT Hiroki Ogawa, Yukihiro Nishikawa, Mikihito Takenaka, Akihiko Fujiwara, Yohei Nakanishi, Yoshinobu Tsujii, Masaki Takata, and Toshiji Kanaya Langmuir, Just Accepted Manuscript • Publication Date (Web): 24 Apr 2017 Downloaded from http://pubs.acs.org on April 29, 2017

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Visualization of individual images in patterned organic-inorganic multilayers using GISAXS-CT Hiroki Ogawa1,2,4,7, Yukihiro Nishikawa3, Mikihito Takenaka1,7, Akihiko Fujiwara5, Yohei Nakanishi1, Yoshinobu Tsujii1, Masaki Takata6,7 and Toshiji Kanaya1, 8 1

Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan 2 3

JST, PRESTO, 4-1-8Honcho, Kawaguchi, Saitama, 332-001, Japan

Department of Macromolecular Science and Engineering, Kyoto Institute of Technology, Kyoto 606-8585, Japan

4

Japan Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Hyogo 679-5198, Japan 5

Department of Nanotechnology for Sustainable Energy, Kwansei Gakuin University, Hyogo 669-1337, Japan

6

Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan 7 8

Riken SPring-8 Center, Hyogo 679-5148, Japan

High Energy Accelerator Research Organization, Ibaraki 319-1195, Japan

Abstract Using grazing-incidence small-angle scattering (GISAXS) with computed tomography (CT), we have individually reconstructed the spatial distribution of a thin gold (Au) layer buried under a thin poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) layer. Owing to the difference between total reflection angles of Au and PS-b-P2VP, the scattering profiles for Au nanoparticles and self-assembled nanostructures of PS-b-P2VP could be independently obtained by changing the X-ray angle of incidence. Reconstruction of scattering profiles allows to separately characterize spatial distributions in Au and PS-b-P2VP nanostructures. 1.

Introduction

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Grazing-incidence small-angle X-ray scattering (GISAXS) have been used for nanometer level structural analysis of thin organic and in-organic films1-8. Two-dimensional (2D) patterns of GISAXS enable quantitative morphological analysis on the length scales ranging from 1 nm to 100 nm. Owing to the reflection geometry in the GISAXS measurements, it is possible to obtain structural information along the in-plane and out-of-plane directions. Information on the size, shape, and surface and interface roughness is contained in the scattering intensities of all q components9-12. In case of X-ray computed tomography (CT), cross-sectional images inside the bulk of organic and inorganic materials can be observed by measuring the attenuation coefficient 13-15. The images can be obtained applying the Radon transformation to the series of the transmission images of samples. In the case of GISAXS coupled with CT, owing to the reconstruction based on the scattering intensities, it is possible to obtain spatial distribution images of nanostructures in thin film samples on the substrate16,17. Using CT with scattering intensities, structural information can be visualized directly18-20. In our previous manuscript11, we demonstrated that individual CT images related to size and shape of nanoparticles could be reconstructed from the scattering intensities at q positions by using GISAXS-CT measurements. However, we had not shown the CT images coupled with the GISAXS measurements as a function of penetration depth. GISAXS have often been applied to obtain qualitative depth profiling measurement through variation of the incidence angle (αi) of X-rays 21,22. In Figure 1, we showed the penetration depth (Λ) for poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) as a function of αi, for the wavelength of 0.10 nm. The total reflection angle of PS-b-P2VP is αc,

PS-b-P2VP

≈ 0.11o. For incidence angles under 0.10o, the incident

X-rays penetrate only into the surface layer of the PS-b-P2VP thin film (Λ ≈ 10.0 nm).

On the other hand, for incidence angles above 0.10o, the incident X-rays penetrate deep

into the PS-b-P2VP layer (Λ > 1,000 nm). In the case of inorganic materials, the penetration depth Λ for gold (Au) is shown in Figure 1 as a function of αi.

For Au, the

total reflection angle is αc, Au ≈ 0.44o. For incidence angles below the total reflection angle of Au, the incident X-rays only penetrate into the outermost surface layer of the Au (Λ ≤ 1.50 nm). Above αi > αc, Au, the incident X-rays penetrate into the Au layer (10.0 nm < Λ < 40.0 nm). For incidence angles between 0.10o and 0.20o (αc, Au > αi > αc, PS-b-P2VP), the incident X-rays penetrate into the PS-b-P2VP layer, but only into the


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outermost surface layer of Au (Λ ≤ 1.50 nm). For incidence angles above 0.45o (αi > αc, Au),

it is possible to measure the scattering intensities associated with nanostructures in

Au layer (Λ ≥ 10.0 nm), as well as those associated with the PS-b-P2VP layer. T scattering intensities are dominated by nanostructures of Au because the atomic scattering power of Au is much stronger that these of PS-b-P2VP. Thus, when GISAXS measurements are performed for different incidence angles, it is possible to individually reconstruct images of nanostructures in the surface PS-b-P2VP layer, and nanostructures in the PS-b-P2VP and Au layers, respectively. In the present work, GISAXS-CT measurements are performed for reconstructing the images of spatial distributions of Au nanoparticles buried under self-assembled nanostructures of PS-b-P2VP. As an example, GISAXS measurements carried out at αi of 0.10o and 0.50o. By the CT images coupled with the GISAXS measurements at the different incident angle, we showed spatial distribution images of individual nanostructures, demonstrating that the present method can be used for characterizing these images on surfaces and at interfaces. This method also allows one to reconstruct individual spatial distribution images of nanostructures of multilayer organic-inorganic cells, and interface nanostructures having interlayer mixed layers for novel devices23-25.

2.

Experiment

2.1 Preparation of samples We prepared "F", "S", "B" and "L" shaped Au nanoparticle layers covered with circular PS-b-P2VP layers on a Si substrate, as shown in Figure 2. Au thin layers, shaped as “F”, “S”, “B”, and “L”, were deposited using the plasma sputter-coating method. The sputtering was accomplished using Ar ion beams for the Au targets (ESC-101, ELIONIX). To form the shaped layers, we made “F”, “S”, “B”, and “L” shaped through-holes on a 0.5-mm-thick aluminum mask by using a drilling device. The scale bar in Figure 2 is 0.1 mm. The samples were fabricated as follows. First, the masks were deposited on the Si substrate, and Au was sputtered on the substrate for 2,800 s. The resulting Au-patterned layers were ~100 nm thick each. Next, poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) was dissolved in a 4wt% toluene solvent and spin-coated at 2,000 rpm on the Au-patterned layer. For this study, PS-b-P2VP was purchased from Polymer Source, Inc. The average molecular weight, the polydispersity


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index and the volume fraction of PS were 4.05 × 104 g/mol, 1.07, and 0.50, respectively. The thickness of the resulting layers was ~200 nm. Finally, using a 3-mm-diameter circle patterned mask put on the “S” and “B” parts, the PS-b-P2VP thin layer was milled using a focused ion beam (IM4000, Hitachi High-Technologies). Thus, the covered polymer thin layers were left on the “S” and “B” parts. The beam’s energy was 1.5 keV and the ion milling was performed for 5.0 min. The angle of incidence onto the fabricated thin films was 20°. 2.2 FE-SEM and OM observations Surface morphology measurements for the fabricated thin Au layers were conducted using a field-emission scanning electron microscope (FE-SEM, JSM-6700F, JEOL Ltd.), with the acceleration voltage of 1.0 kV. The images of the fabricated Au-patterned thin layers on the substrate were acquired using a digital microscope (OM, VHX-5500, KEYENCE). 2.3 GISAXS measurements GISAXS measurements were performed at the first experimental hutch of the beamline BL03XU at SPring-8, Advanced Softmatter Beamline (FSBL), which is dedicated to GISAXS experiments, using an intense beam (1013 photons s-1) with very low divergence (12.3 µrad (horizontal) × 1.1 µrad (vertical))26. The X-ray wavelength λ and the sample-detector distance were 0.1 nm and 2275 mm, respectively. The full width at half maximum of the beam at the sample position was 120 µm (horizontal) × 100 µm (vertical), and the beam footprint (which could entirely cover the pattern configurations) was extended to 57.3 mm and 11.5 mm at the incidence angle of 0.10o and 0.50o. The scattering images were detected using an X-ray image intensifier with a cooled charge coupled device (CCD) consisting of 672 × 512 pixels, with each pixel

covering 126 µm2. We acquired 2D GISAXS images with the exposure time of 500 ms.

To reconstruct the images in the lateral directions using the CT method, for each sample we scanned a distance spanning 10 mm in steps of 100 µm, in the direction normal to that of the beam incidence (y - direction). The scanning steps were comparable to the incident beam’s width (the beam’s size in the horizontal direction). In the rotation scan θ, images were acquired in 3.0o steps for 0.0o ≤ θ < 180.0o. The

direction of the incident beam at θ = 0.0o is indicated by an arrow in Figure 2.


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Theory of GISAXS-CT The reconstruction image was based on filtered-back projection (FBP), which formula is simply written as follows27: ∞ ∞ 1 π f x,y = dθ dRRei x cos θ+y sin θ R dr , ! e-irq π 0 -∞ -∞

where , ! is a sinogram of the scattered intensities at (qy, qz) position of 2D scattering patterns, and is a 2D image consists of a stack of one-dimensional projection ( ) of the object along the rotation of the object (!). The scattering intensities depend on the wave vector (q), therefore, the reconstructed images can change with (qy, qz) position of 2D scattering patterns. 3.

Results and discussion Figure 3(a) shows a 2D scattering pattern for the buried “F” and “S” parts, with a

circular pattern of the PS-b-P2VP layer, for the incidence angle of 0.10o. The scattering peaks were clearly observed at (qy, qz) = (±0.15 nm-1, 0.24 nm-1). Figure 3(b) shows the intensity profiles in the in-plane direction at qz = 0.24 nm-1, revealing the first scattering peak at qy = 0.15 nm-1.

This peak was attributed to the self-assembled nanostructures

of PS-b-P2VP. When an image was reconstructed from the intensities at this first scattering peak at qy = 0.15 nm-1 (at the α position in Figure 3(b)), the reconstructed image exhibited two circular patterns, one at x = -2.6–0.4 mm and y = -2.5–0.5 mm and another one at x = -0.2–2.8 mm and y = 0–3.0 mm, respectively, as shown in Figure 4(a). The reconstructed image was agreed with the OM image of the PS-b-P2VP thin film. In Figure 4(b), we also showed a cross-sectional profile of the reconstructed image at the y = -1.45 mm position, as a function of the image’s x position. The image intensities were nearly constant in the -2.2 < x < 0.6 range; hence, we concluded that PS-b-P2VP exist in that region. There is a height gap between coating and non-coating area at the boundary. The gap may influence the X-ray penetration depth. In this experiment, we used the large beam size that the horizontal size was 120 µm at the sample position. Hence, we considered that the influence from the boundary condition relatively lower. In Figure 4(a), we observed a defect around region A. The corresponding area in the OM image have a different color in region A, indicating that self-assembled nanostructures are not formed in the area containing the defect. The reconstructed image


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also suggests strong-intensity areas at parts B in Figure 4(a). These strong-intensity areas match with impurities at parts B in Figure 2. At the α position in Figure 3(b), the scattering profile was affected by the high-intensity scattering profiles originating from these impurities; hence, impurities were amplified in the reconstructed images. Figure 4(c) shows the image that was reconstructed using the scattering intensities for the typical lower qy position of qy = 0.12 nm-1 (at the β position in Figure 3(b)), and two circular patterns were observed. This result indicates that the scattering intensities at this q position can also be attributed to the self-assembled nanostructures in the PS-b-P2VP layer. Besides the two circular patterns, the defect and impurities were also detected in regions A, B in Figure 4(c). This result suggests that these scattering intensities contain the scattering intensities from the self-assembled nanostructures in the PS-b-P2VP and parasitic scattering intensities from impurities contributions. Figure 4(d) shows the image that was reconstructed using the scattering intensities at qy = 0.06 nm-1 (at the γ position in Figure 3(b)). Interestingly, some impurities were detected, while the previously detected pattern of two circles was not detected here (parts B in Figure 4(d)). In our previous work, we concluded that nano-cylindrical structures of the P2VP component were aligned normally to the film28, and the first peak at qy = 0.15 nm-1 corresponded to the correlation length of cylindrical microdomains. As mentioned above, the reconstruction result indicated that the scattering intensities at qy = 0.15 nm-1 were related to the patterned PS-b-P2VP layer (Figure 4(a)). On the other hand, Figure 4(d) shows only some impurities. We could identify the scattering intensities at qy = 0.06 nm-1 that contributes parasitic scattering intensities, and were attributed to impurities. Thus, impurities, but not two circular patterns, contributed to the results in Figure 4(d). In the case of the higher qy region of qy = 0.36 nm-1 (at the δ position in Figure 3(b)), impurities were only detected at B parts in Figure 4(e). This result also suggests that the scattering intensities of the higher qy regions were considerably affected by impurities-related parasitic scattering intensities. Owing to weaker signals associated with the patterned PS-b-P2VP layer for the higher qy region, two circular patterns were not detected in the reconstructed image. Next, we characterized image reconstruction for the incidence angle of 0.50o. The incidence angle was above the critical incidence angle for Au and PS-b-P2VP, and Λ of the Au layer was 16.2 nm for the incidence angle of 0.50o. We measured a 2D scattering


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pattern by irradiating X-rays on the “F” and “S” parts buried under the circular-patterned PS-b-P2VP layer, as shown in Figure 5(a). Compared with 2D profiles obtained for the incidence angle of 0.10o, different images were obtained in the 0.50° case. Shoulder peaks were observed at around (qy, qz) = (±0.15 nm-1, 0.87 nm-1). Figure 5(b) shows the intensity profile along the in-plane direction for qz = 0.87 nm-1. The positions for qy = ±0.15 nm-1 were the same as those obtained for the incidence angle of 0.50o. Figures 6(a), 6(b), and 6(d) show the reconstructed images using the intensities at the qy positions of 0.15, 0.47, and 0.05 nm-1, respectively. In this method, we could reconstruct the images from the scattered intensities at every qy position. For the typical explanation, we chose only these qy positions. For the 2D image that was reconstructed using the intensity of a shoulder position at qy = 0.15 nm-1 (at the α position in Figure 5(b)), all figure parts were successfully reconstructed, as shown in Figure 6(a). Although the image was reconstructed for the same qy position for the incidence angle of 0.10o, it was interesting that the two previously observed circular patterns were not observed for the incidence angle of 0.50o. After confirming the surface structures in “S” using FE-SEM, averaged inter-particle distance of ~30.0 nm and averaged inter-particle distance of ~60.0 nm was observed in Figure 5(c). It is noted that we observed the inner part of “S”, and light parts were nanoparticles. We estimated the mean interparticle distance from the mean distances of light parts. This result suggests that the shoulder peaks for qy = 0.15 nm-1 in Figure 5(b) correspond to the inter-particle distance. Hence, the reconstructed image in Figure 6(a) reveals the spatial distribution of Au nanoparticles with the inter-particle distance of 60.0 nm. When we reconstructed the image for the typical higher qy position of qy = 0.47 -1

nm (at the β position in Figure 5(b)), the “S” and “B” parts could be more clearly seen than the “F” and “L” parts in Figure 6(b). The cross-sectional intensity profile for y = -0.75 mm was plotted in Figure 6(c) as a function of x. The intensities for the configuration parts of the “S” and “B” parts were higher than those for the inner parts. From the in-plane profile measurements, the scattering profiles were described by a

power law '()* +~)*-. in the )* range. For the higher qy region of qy > 0.38 nm-1, the fitted exponent was = 3.4, suggesting that the Au nanoparticles in this region were

not smooth but rather rough, and could be characterized as surface fractals29-31. This

result indicates that the nanoparticles deposited in the configuration regions have rougher surface, which is different from the results for the inner part of the figure. In


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parts B in Figures 6(a) and 6(b), we detected defects in the “C” parts, for the images reconstructed from the intensities at qy positions. This suggests that no nanoparticles were deposited in this region. Figure 6(d) shows the 2D image that was reconstructed using the intensities at the lower qy position of qy = 0.05 nm-1 (at the γ position in Figure 5(b)), and the “F” and “L” parts were clearly visible. From the cross-sectional profile in Figure 6(e), the intensities were almost constant in the “F” part (y = 1.55 mm). These results indicate that the “F” and “L” parts are composed of agglomerated nanoparticles of Au. Figure 5(d) shows the FE-SEM image for the inner “F” part of the Au thin film. We confirmed that grains coarsely formed agglomerates in the inner “F” part, under the same sputtering conditions. The reconstructed image demonstrated that it was possible to visualize not only the spatial distribution of Au nanoparticles but also that of the aggregation of Au nanoparticles. Moreover, Au nanoparticles with different shapes were also located in the configuration parts and inside the figure parts, respectively. We posited that Au nanoparticles were non-homogeneously deposited on the substrate due owing to a small line width of the mask. The “F” and “L” parts mainly composed of line parts, and the “S” and “B” parts composed of curved line parts. Hence, Au nanoparticles may easy to aggregate at the “F” and “L” parts. Alternatively, Au nanoparticles in the surface layer were partially milled by the focused ion beam when we used for milling the PS-b-P2VP layer. Finally, we discuss the reason for not observing circular patterns of the PS-b-P2VP layer. The scattering intensities for the deposited Au nanoparticles were higher than those for the self-assembled nanostructures of PS-b-P2VP. The angle of incidence was 0.10o, above the critical angle for silicon (Si) wafers (αc, Si≈ 0.14o) and distinct from the total reflection angle of PS-b-P2VP, the scattering intensities from the reflected beam decreases by a factor of 234 /16274 in terms of the reflection coefficient, where αc

and α0 denote the material’s critical angle and the incidence angle, respectively32,33.

Owing to this effect, the scattering intensities for the patterned PS-b-P2VP layer were weaker than the electric noise of the CCD detector. Hence, only the figure parts were reconstructed from the intensities at the incidence angle of 0.50o. 4.

Conclusion Grazing-incidence small-angle X-ray scattering coupled with CT measurements


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was employed for characterizing Au and PS-b-P2VP multilayers. Using this application, spatially distributed images of Au and PS-b-P2VP nanostructures in patterned thin films were individually reconstructed, allowing to reconstruct 2D images of individual Au and PS-b-P2VP structures given the scattering intensities at different angles of X-ray incidence onto the sample. As an imaging technique, GISAXS-CT is a powerful method for characterizing organic-inorganic nanostructures in thin films. This technique can be extended for 3D visualization of thin films.

Acknowledgements This work was supported by a Grant-in-aid from the Ministry of Education, Science, Sports, and Culture of Japan (No. 15K17489), and Japan Science and Technology Agency, PRESTO. SR GISAXS measurements were performed at the first hutch of the Consortium of Advanced Softmaterial Beamline (FSBL) with the proposal No. 2016A1828 and 2016B1934.

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17. Ogawa, H.; Nishikawa, Y.; Fujiwara, A.; Takenaka, M.; Wang, Y-C.; Kanaya, T.; Takata, M. Visualizing patterned thin films by grazing-incidence small-angle X-ray scattering coupled with computed tomography. J. Appl. Cryst. 2016, 48, 1645-1650. 18. Schroer, C. G.; Kuhlmann, M.; Roth, S. V.; Gehrke, R.; Stribeck, N. Mapping the local nanostructure inside a specimen by tomographic small-angle x-ray scattering. Appl. Phys. Lett. 2006, 88, 164102-1-164102-3. 19. Schaff, F.; Bech, M.; Zaslansky, P.; Jud, C.; Liebel, M.; Guizar-Sicairos, M.; Pfeiffer, F. Six-dimensional real and reciprocal space small-angle X-ray scattering tomography. Nature 2015, 527, 353-356. 20. Skjønsfjell, E. T.; Kringeland, T.; Granlund H.; Høydalsvik, K.; Diaz, A.; Breiby, D. W. Retrieving the spatially resolved preferred orientation of embedded anisotropic particles by small-angle X-ray scattering tomography. J. Appl. Cryst. 2016, 49, 902-908. 21. Wang, J.; Bedzyk, M. J.; Caffrey, M. Resonance-Enhanced X-rays in Thin Films: A Structure Probe for Membranes and Surface Layers. Science 1992, 258, 775-778. 22. Singh, M. A.; Groves, M. N. Depth profiling of polymer films with grazing-incidence small-angle X-ray scattering. Acta Cryst. 2009, A65, 190-201. 23. Maneeratana, V.; Bass, J. D.; Azaïs, T.; Patissier, A.; Vallé, K.; Maréchal. M.; Gebel, G.; Laberty-Robert, C.; Sanchez, C. Fractal Inorganic-Organic Interfaces in Hybrid Membranes for Efficient Proton Transport. Adv. Funct. Mater. 2013, 23, 2872-2880. 24. Bansal, N.; Reynolds, L. X.; Maclachlan, A.; Lutz, T.; Asharaf, R. S.; Zhang, W.; Nielsen C. B.; MCulloch, L.; Reibois, D. G.; Kirchartz, T.; Hill, M. S.; Molloy, K. C.; Nelson, J.; Haque, S. A. Influence of crystallinity and energetics on charge separation in polymer-inorganic nanocomposite films for solar cells. Sci. Rep. 2013, 3, 1531-1-1531-8. 25. Amgar, D.; Aharon, S.; Etgar, L. Inorganic and hybrid organic-metal perovskite nanostructures: synthesis, properties, and applications. Adv. Funct. Mater. 2016, 26, 8576-8593. 26. Ogawa. H et al. Experimental station for multiscale surface structural analyses of soft-material films at SPring-8 via a GISWAXS/GIXD/XR-integrated system. Polym. J. 2013, 45, 109-116. 27. G. T. Herman, Academic Press: New York, 1980, 1–39, 277–296.


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28. Ogawa, H.; Takenaka, M.; Miyazaki, T. Fujiwara, A. Lee. B.; Shimokita, K.; Nishibori E.; Takata, M. Direct Observation on Spin-Coating Process of PS-b-P2VP Thin Films. Macromolecules 2016, 49, 3471-3477. 29. Schmidt, P. W. Small-Angle Scattering Studies of Disordered, Porous and Fractal Systems. J. Appl. Cryst. 1991, 24, 414-435. 30. Schmidt, P. W.; Bale, H. D. Small-angle X-ray scattering investigation of submicroscopic porosity with fractal properties. Phys. Rev. Lett. 1984, 53, 596-599. 31. Amamoto, Y.; Otsuka, H.; Takahara, A.; Matyjaszewski, K. Changes in Network Structure of Chemical Gels Controlled by Solvent Quality through Photoinduced Radical Reshuffling Reactions of Trithiocarbonate Units. ACS. Macro Lett. 2012, 1, 478-481. 32. Sinha, S. K.; Sirota, E. B.; Garoff, S.; Stanley, H. B. X-ray and neutron scattering from rough surface. Phys. Rev. B. 1998 38, 2297-2311. 33. Gibaud, A.; Hazra, S. X-ray reflectivity and diffuse scattering. CURRENT SCIENCE 2000, 78, 1467-1477.

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Individual reconstruction images of nanostructures of gold (Au) layers buried under thin poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) layers using by GISAXS-CT


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Figure 1. Penetration depths of Au and PS-b-P2VP thin films, as a function of the angle of incidence, at the wavelength of 0.10 nm. The arrows correspond to the incidence angles of 0.10 o and 0.50 o, respectively. 64x58mm (300 x 300 DPI)


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Figure 2. Schematic diagram and optical microscope image of the measured sample. Four characters were deposited by Au sputtering, and two circles of PS-b-P2VP thin films were made using the spin-coating method. The horizontal arrow indicates the X-ray incidence direction at θ = 0.0o. A region is a defect region. B parts are impurities. The scale bar in the OM image is 100 µm. 352x190mm (72 x 72 DPI)


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Figure 3. (a) 2D GISAXS pattern and (b) in-plane profile qz = 0.24 nm-1 of “F” and “S” parts made by depositing Au nanoparticles, covered with circular PS-b-P2VP layers on a Si substrate at the incidence angle of 0.10o. The scattering peaks are marked by down-pointing arrows, while horizontal arrows indicate the Yoneda line of PS-b-P2VP and the silicon wafer. Down-pointing arrows with full lines indicate the positions at which the images were reconstructed from the intensities. 212x103mm (288 x 288 DPI)


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Figure 4. (a),(c)-(e) Reconstructed images obtained from projections at the qy positions of 0.15, 0.12, 0.06, and 0.36 nm-1 in the in-plane profiles at qz = 0.24 nm-1 and (b) the cross-sections intensity profile at the y = -1.45 mm position in (a), as a function of x. A region corresponds to a defect region. B parts correspond to impurities. 89x94mm (288 x 288 DPI)


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Figure 5. (a) 2D GISAXS pattern and (b) in-plane profile qz = 0.87 nm-1 obtained from “F” and “S” parts of the Au nanoparticle layers covered with circular PS-b-P2VP layers on a Si substrate at the incidence angle of 0.50o. Horizontal arrows indicate the Yoneda line of Au and the silicon wafer. The line fit is the best fit. Down-pointing arrows with full lines indicate the positions at which the images were reconstructed from the intensities. (c), (d) FE-SEM images of the “S” and “F” parts. The scale bar in the FE-SEM images is 100 nm. 113x99mm (288 x 288 DPI)


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Figure 6. (a), (b) and (d) Reconstructed images obtained from projections at the qy positions of 015, 0.47, and 0.05 nm-1 in the in-plane profiles at qz = 0.87 nm-1. (c) Cross-sectional intensity profile at the y = -0.75 mm position in (b), and (e) that at the y = 1.55 mm position in (d), as a function of x. C parts correspond to impurities. 188x190mm (300 x 300 DPI)


Visualization of Individual Images in Patterned OrganicâInorganic

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