Data from: 3D nanoscale design of oxide morphology, anisotropy and chemical heterogeneity by glancing angle physical vapor deposition
Data files
Abstract
Nanoelectronic thin films are increasingly used in functional, electrochemical and nanoelectronic applications. Glancing angle deposition (GLAD) enables 3D control over bottom-up synthesis of highly tunable films with well-ordered yet complex nanostructures, such as inclined nanocolumn arrays with intercolumn nanoporosity or zig-zig columnar grains. Here we demonstrate the synthesis of crystallographically textured yttria-stabilized zirconia (YSZ) zig-zag films with tunable morphology, porosity, chemistry, and elucidated the mechanisms governing nanostructure modulation during GLAD pulsed laser deposition (PLD). A low oxygen partial pressure (P O₂ ) YSZ buffer layer enables (100)-textured growth on Si(100) substrates with native oxide, and this texture is preserved across GLAD-induced film morphological variations. By tuning the adatomic incidence angle (α) and P O₂ , we control the balance between ballistic shadowing and adatom surface diffusion, thereby determining transitions between vertical and inclined columnar grain growth. Critical thresholds of α ≈ 60° and P O₂ ≈ 0.15 mtorr were identified, marking the boundaries between shadowing-dominated inclined growth and diffusion-dominated vertical growth. Beyond geometric control, interlayer insertion enables the fabrication of nanocomposite and compositionally graded zig-zag thin films, such as 5YSZ-Y 2 O 3 -5YSZ and 5YSZ-45YSZ-5YSZ. Moreover, amorphous interlayers deposited at reduced temperature undergo crystallization during subsequent high-temperature growth, where crystallization-induced volume shrinkage reshapes corner grain morphology, increases porosity, and modulate interfacial chemistry. Overall, this work demonstrates that tuning the balance between adatom flux shadowing and in-plane diffusion, while simultaneously incorporating interlayer deposition strategies can substantially expand the GLAD nanostructure design space.
Dataset DOI: 10.5061/dryad.0zpc867dj
Description of the data and file structure
Images, spectroscopy, and data quantification used for each figure in the main manuscript.
Fig.2.zip contains SEM images and XRD patterns shown in Fig. 2
Fig. 2. A low-oxygen-partial-pressure (low-PO₂) buffer layer effectively promotes out-of-plane (200) YSZ texture imparted by Si substrates. (a) YSZ thin films grown (red) without a buffer layer at PO₂ of 0.6 mtorr and (green) with a buffer layer deposited at PO₂ of 0.015 mtorr with normal material incidence (α = 0°). (b-c) SEM cross-section image of the film (b) without and (c) with a buffer layer. (d) XRD of the film without and with a buffer layer recorded in grazing-incidence (GIXRD) and θ-2θ geometries, and XRD θ-2θ pattern of the 5.3YSZ PLD target (bottom). (e) I (200)/I (111) of the film without and with a buffer layer extracted from XRD θ-2θ patterns in (d). The film with a buffer shows much stronger out-of-plane (200) preferred orientation.
Fig.3.zip contains SEM images, XRD patterns and (S)TEM images shown in Fig. 3
Fig. 3. Effect of GLAD tilt angle on inclined growth of textured YSZ columnar grains at 750 °C. (a) Single-layer GLAD PLD at α = 0°, 45°, and 70° substrate tilt angles yield vertical, vertical, and inclined growth modes, respectively. (b, f, j) 0° tilt angle film with vertical columnar grains viewed in cross-section by (b) low-mag BFTEM, (f) HRTEM, and (j) SEM SE images. (c, g, k) 45° tilt angle film with vertical columnar grains viewed in cross-section by (c) STEM BF, (g) atomic-resolution STEM HAADF, and (k) SEM SE images. (d, h, l) 70° tilt angle film with inclined columnar grains viewed in cross-section by (d) STEM BF, (h) atomic-resolution STEM HAADF, and (l) SEM SE images. (e) Top-view SEM SE image of the film deposited at 70° tilt angle showing rough surface. (i) XRD θ-2θ of the film deposited at 70° showing preferred (200) orientation independent of grain morphology.
Fig.4.zip contains SEM images, XRD patterns and (S)TEM images shown in Fig. 4
Fig. 4. Effect of GLAD tilt angle on YSZ zig-zag thin film growth at 750 °C. (a) Bilayer GLAD PLD at α = 0°, 60°, 70° substrate tilt angles yield vertical, mixed, and zig-zag growth modes, respectively. (b, h, l) 0° tilt angle film with vertical columnar grains viewed in cross-section by (b) BFTEM, (h) HRTEM, and (l) SEM SE images. (c, i, m) 60° tilt angle film with mixed vertical, inclined and zig-zag columnar grains viewed in cross-section by (c) BFTEM, (i) HRTEM, and (m) SEM SE images. (d, j, n) 70° tilt angle film with zig-zag columnar grains viewed in cross-section by (d) BFTEM, (j) atomic-resolution STEM HAADF, and (n) SEM SE images. (e-g) Top-view SEM SE images of films deposited at (e) 0°, (f) 60°, and (g) 70° tilt angles showing increasing surface roughness and intergranular pore size with increasing tilt angle. (k) XRD θ-2θ of the film deposited at 70° showing preferred (200) orientation independent of grain morphology.
Fig.5.zip contains SEM images, XRD patterns and (S)TEM images shown in Fig. 5
Fig. 5. Effect of PO₂ on inclined growth of textured YSZ columnar grains at 750 °C. (a) Single-layer GLAD PLD at PO₂ of 0.015 mtorr and 0.6 mtorr yield vertical, and inclined growth modes, respectively. Both films grow on Si (100) with a low-PO₂ YSZ buffer. (b, f, i) PO₂ = 0.015 mtorr film with vertical columnar grains viewed in cross-section by (b) STEM BF, (f) HRTEM, and (i) SEM SE images. (c, g, j) PO₂ = 0.6 mtorr film with inclined columnar grains viewed in cross-section by (c) STEM BF, (g) atomic-resolution STEM HAADF, and (j) SEM SE images. (d-e) Top-view SEM SE images of films deposited at PO₂ of (d) 0.015 mtorr and (e) 0.6 mtorr showing increasing surface roughness with increasing PO₂ by reducing adatom in-plane diffusion. (h) XRD θ-2θ of the films deposited at PO₂ of 0.015 mtorr and 0.6 mtorr showing preferred (200) out-of-plane orientation independent of PO₂.
Fig.6.zip contains SEM images, XRD patterns and (S)TEM images shown in Fig. 6
Fig. 6. Effect of PO₂ on YSZ zig-zag GLAD film growth at 750 °C. (a) Bilayer GLAD PLD at PO₂ of 0.15 mtorr and 0.6 mtorr yield mixed, and zig-zag growth modes, respectively. (b, f, i) PO₂ = 0.15 mtorr film with mixed vertical, inclined, and zig-zag columnar grains viewed in cross-section by (b) BFTEM, (f) HRTEM, and (i) SEM SE images. At PO₂ of 0.15 mtorr, only partial columnar grains exbibit zig-zag morphology at 70° tilt angle. (c, g, j) PO₂ = 0.6 mtorr film with zig-zag columnar grains viewed in cross-section by (c) STEM BF, (g) atomic resolution STEM HAADF, and (j) SEM SE images. (d-e) Top-view SEM SE images of films deposited at PO₂ of (d) 0.15 mtorr and (e) 0.6 mtorr, showing increasing surface roughness and intergranular porosity with increasing PO₂. (h) XRD θ-2θ of the film deposited at PO₂ of 0.15 mtorr and 0.6 mtorr showing preferred (200) orientation independent of columnar grain morphology.
Fig.7.zip contains (S)TEM images and EDS maps shown in Fig. 7
Fig. 7. Chemistry of YSZ zig-zag thin films can be modulated by introducing an interlayer. (a) Schematic of introducing Y2O3 interlayer into corner of the YSZ zig-zag thin film deposited at substrate tilt angle of 70°. The Y2O3 interlayer was also deposited at high temperature. (b) STEM HAADF images of the columnar grains. The contrast change at the zig-zag corner arises from atomic number Z contrast between 5.3 YSZ and Y2O3. (c) Atomic-resolution STEM HAADF images of the corner of the zig-zag grains. The inset shows the FFT of (c). Although 5.3 YSZ and Y2O3 have different crystal structures, they generally maintain textured growth on the top of each other in each columnar grain. (d-i) STEM HAADF survey image of the thin film (d) and corresponding STEM EDS mapping of Zr-K (e), Y-K (f), O-K (g), Si-K (h), and composite of Zr and Y (i). Y shows concentrated EDS signals at the zig-zag corner, corresponding to the introduced Y2O3 interlayer.
Fig.8.zip contains (S)TEM images and EDS maps shown in Fig. 8
Fig. 8. Pore size between YSZ zig-zag columnar grains can be modulated by deposition temperature of interlayer. (a) Schematic of introducing a thin 45YSZ interlayer to the YSZ zig-zag thin film. The interlayer was deposited at 60 °C. The 45 YSZ interlayer crystallizes and shrinks during the second main layer deposition at 750 °C, creating large pores between columnar grains. (b) STEM BF image of the zig-zag columnar grains. Pores between columnar grains are considerably larger in the second layer compared to the first layer. (c-g) STEM HAADF survey image of the thin film cross-section (c) and corresponding STEM EDS mapping of Zr-K (d), Y-K (e), O-K (f) and composite of Zr and Y (g). (h, i) Atomic-resolution STEM HAADF images of the corner of the zig-zag thin film. Inset shows the FFT of (i). The 45YSZ interlayer is fully crystallized and shows textured growth with 5.3 YSZ main layers.
Fig.9.zip contains (S)TEM images and EDS and EELS maps shown in Fig. 9
Fig. 9. Effect of thick amorphous interlayer on zig-zag morphology, composition and defect chemistry. (a) STEM HAADF survey image and (b-f) corresponding STEM EDS maps of Zr-K, Y-K, O-K, Ir-L and a composite of Zr and Y. A thick Y-rich interlayer was observed at the corner of the zig-zag thin films, which increases pore size and modulates zig-zag morphology. (g) Elemental and point defect concentration profiles of cations, anions and oxygen vacancies across the interlayer in (f). (h) Depositing a thick 45YSZ interlayer into YSZ zig-zag thin films at 70° substrate tilt angle. The thick interlayer was deposited at 60 °C for 3,000 pulses between each main layer. The interlayer crystallizes and shrinks during the top layer deposition. (i,j) STEM HAADF survey image of the corner of the zig-zag thin film. (i-n) Atomic-resolution STEM EELS maps of Zr-L, Y-L, O-K, and the composite of Zr-L and Y-L. (o-r) STEM EDS maps of Zr-K, Y-K, O-K, and the composite of Zr-K and Y-K. Although the increased pore size and interlayer thickness disrupt the corner morphology of the zig-zag thin film, most columnar grains retain textured growth. (s) Elemental and point defect concentration profiles across the Y-rich interface in (r), showing the oxygen vacancy concentration increases with Y concentration.
Fig.10.zip contains (S)TEM images, EELS maps and EELS fine structures shown in Fig. 10
Fig. 10. Energy-loss near-edge fine structure (ELNES) analysis at the interfaces and within the interlayer. (a) Y concentration profile across the 45YSZ interlayer in the zig-zag thin film (shown in Fig. 9) obtained from STEM-EDS quantification. (b) The corresponding STEM-EELS Y L-edge map. (c) The corresponding STEM-HAADF survey image. (d) O K-edge ELNES spectra extracted from the 5YSZ layer 1, the Y-rich interface 1, the 45YSZ interlayer, and interface 2. The regions of interest over which the spectra were summed and analyzed in depth are indicated in (c).