# Fileset

[ALD_Interlayers_for_robust_metal-polymer_interfaces_supporting-info.pdf](https://mdr.nims.go.jp/filesets/44597de4-c1d6-4a81-8e03-07df1b7204e2/download)

## Creator

[Johanna Byloff](https://orcid.org/0000-0001-6026-6845), [Claus Othmar Wolfgang Trost](https://orcid.org/0000-0002-7570-688X), Vivek Devulapalli, Shuhel Altaf Husain, [Damien Faurie](https://orcid.org/0000-0001-7259-3958), Pierre-Olivier Renault, [Thomas Edward James Edwards](https://orcid.org/0000-0002-3089-0062), [Megan J. Cordill](https://orcid.org/0000-0003-1142-8312), [Daniele Casari](https://orcid.org/0000-0003-2113-5070), Barbara Putz

## Rights

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials & Interfaces, copyright ©  2025 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsami.5c05156.[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)

## Other metadata

[Atomic Layer-Deposited Interlayers for Robust Metal–Polymer Interfaces](https://mdr.nims.go.jp/datasets/e18cc7e8-ca7e-4623-a0ac-85db960bddc0)

## Fulltext

Supporting InformationAtomic Layer Deposited Interlayers for RobustMetal–Polymer InterfacesJohanna Byloff,†,‡ Claus O. W. Trost,¶ Vivek Devulapalli,† Shuhel AltafHusain,§,∥ Damien Faurie,§ Pierre–Olivier Renault,∥ Thomas Edward JamesEdwards,†,⊥ Megan J. Cordill,¶ Daniele Casari,† and Barbara Putz∗,†,#†Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory forMechanics of Materials and Nanostructures, Feuerwerkerstrasse 39, Thun, 3603,Switzerland‡Laboratory for Nanometallurgy, ETH Zurich, Vladimir–Prelog–Weg 5, Zurich, 8093,Switzerland¶Erich Schmid Institute of Materials Science, Austrian Academy of Sciences, Jahnstraße12, Leoben, 8700, Austria§LSPM–CNRS, UPR3407, Université Sorbonne Paris Nord, 99 Avenue Jean–BaptisteClément 93430, Villetaneuse, France∥Institut Pprime, CNRS – Université de Poitiers, 86073 Poitiers Cedex, France⊥Research Center for Structural Materials, National Institute for Materials Science, 1-2-1Sengen, Tsukuba 305-0047, Japan#Department of Materials Science, Montanuniversität Leoben, Franz Josef Straße 18,Leoben, A–8700, AustriaE-mail: barbara.putz@empa.ch11 PVD ParametersPVD deposition parameters for the Al top layer are summarized in Table S1 below.Table S1: PVD parameters for deposition of the Al top layerInterface type native artificialTesting method uniaxial biaxial uniaxial biaxialCurrent [mA] 280 280 280 280Ar flow rate [sscm] 10 10 10 10Base pressure [mbar] 1.5× 10−7 1.9× 10−5 2.5× 10−6 8.7× 10−8Working pressure [mbar] 9.8× 10−3 9.2× 10−3 7× 10−3 7× 10−3Deposition rate [nm / s] 0.080 0.075 0.080 0.0812 Additional IPF mapsFigure S1 shows ACOM IPF y maps of the investigated microstructures to ascertain theabsence of thin film texture.Figure S1: ACOM IPF y (in-plane direction) maps of the investigated Al microstructures.A, B: Al films on polyimide (native interlayer system). C: Al film with am–AlOxHy artificialALD interlayer on polyimide. Grain boundaries are marked with black lines. Note that onlythe Al layer is shown.23 FWHM evolution at different chi anglesFor uniaxial XRD measurements, FWHM values at χ = 90° are shown in Figure S2 be-low. Regarding FWHM recovery during unloading, the data (parallel measurement, top andtransverse, bottom) show a similar trend for native (A) and artificial (B) interface systemsas biaxial FWHM measurements discussed in the main manuscript, however, as the signalintensity is lower for this experiment, the scatter is increased.Figure S2: FWHM evolution as a function of applied strain at χ = 90° recorded duringuniaxial measurements parallel (top) and transverse (bottom) to the tensile direction. A:native interlayer, B: artificial interlayer.For the discussion of deformation domains for biaxial measurements, FWHM at χ =90° (equivalent to ψ = 0°) is plotted in the manuscript (Figure 4) together with the Alfilm stress as a function of applied strain. Figure S3 shows all FWHM versus applied straincurves recorded at different χ angles during sin2ψ analysis for Al/PI and am-AlOxHy interfacesystems, respectively, showing the same trends as the curves discussed in the main text.3Figure S3: FWHM evolution as a function of applied strain recorded at different χ anglesduring sin2ψ analysis for biaxial tensile straining. A: native interlayer, B: artificial interlayer.Note the different FWHM scales in A and B.4 Post-mortem SEM imagesPost-mortem SEM images of biaxially tested samples with mud-crack crack patterns areshown in Figure S4 below. Cracks visible on the surface are indicated with white arrows,growth hillocks with white circles.Figure S4: Post-mortem SEM images of equi-biaxially tested samples. A: Native interlayersystem, B: artificial interlayer system. Hillocks grown during the deposition are indicatedwith white circles, while cracks are indicated with white arrows.45 Theoretical yield stress calculationsThe Hall–Petch (H-P) relation:1σyield,H−P = σ0 +K ∗ d−12 (S1)with σ0 = 11.3 MPa the bulk strength and K = 0.07 MPa m12 the Hall–Petch constant2 andthe Nix model combined with the H-P relation:3σyield,Nix+H−P = 3.464∗ b2π ∗ (1− ν) ∗ h∗[µf ∗ µsµf + µs∗ ln(βs ∗ hb) +µf ∗ µoµf + µo∗ ln(βo ∗ tb)]+σyield,H−P(S2)were used for yield stress calculations in the main manuscript, with b = 0.286 ∗ 10−9(Burgers vector), βo = 17.4, βs = 2.6 (constants), µf = 24.8 GPa, µo = 178.9 GPa,µs = 1 GPa (shear moduli of film, oxide, and substrate), ν = 0.31 (Poisson’s number), h(film thickness) and t (oxide thickness).6 Additional resistance curvesTo determine the adhesion energy and saturation crack and deformation spacings, as well asR/R0 at high strains, samples were uniaxially loaded to 40% strain, with in-situ resistancemeasurements, the representative results of which are shown in Figure S5. COS and EFSvalues as well as the maximum R/R0,max ratio follow the same trend as the measurementspresented in the manuscript, with an added artificial interlayer increasing both COS andEFS and decreasing R/R0,max.5Figure S5: In-situ resistance curves of native (A) and artificial (B) interlayer samples testedto 40% uniaxial strain. Note the different R/R0 scales.7 Adhesion energy calculationBuckle geometry measurements for both native and artificial interlayer systems (δ = heightand b = half width of the buckle) are reported in Figure S6.Figure S6: Adhesion analysis of native (A) and artificial (B) interlayer systems using theTID model. Upper and lower bounds for the fitted α value (green line) are marked with redand blue dashed lines, respectively. The data used for the R2 analysis of the fitting functionis marked with star symbols.Measured values can be fitted with the α value using the tensile induced delamination(TID) model,46√δh= (2α)14bh1 +√1 +34αbh4− 14(S3)where α is directly related to the adhesion energy Γ via:α =4ΓhE ′f(2π)4 (S4)with E ′f = Ef/(1− ν2f ) (E′f = 7.95× 1010) as the modified Young’s modulus to accountfor the Poisson effect. Average α values of 6.5×10−4 (native) and 9.0×10−4 (artificial) wereused in the analysis to provide a lower bound for the adhesion energy. Average α valueswere chosen to be within 10% deviation of the lowest data points. Upper and lower boundsfor this value are shown in Figure S4. An R2 fit analysis was applied to a subset of the data(red stars) to determine the fit correspondence.References(1) Hall, E. O. The Deformation and Ageing of Mild Steel: III Discussion of Results. Pro-ceedings of the Physical Society. Section B 1951, 64, 747.(2) Cordero, Z. C.; Knight, B. E.; Schuh, C. A. Six decades of the Hall–Petch effect – a surveyof grain-size strengthening studies on pure metals. International Materials Reviews 2016,61, 495 – 512.(3) Nix, W. D. Mechanical properties of thin films. Metallurgical Transactions A 1989, 20,2217–2245.(4) Cordill, M.; Fischer, F.; Rammerstorfer, F.; Dehm, G. Adhesion energies of Cr thin filmson polyimide determined from buckling: Experiment and model. Acta Materialia 2010,58, 5520–5531.7