A novel AFM Mode for Nondestructive Compositional

A novel AFM Mode for Nondestructive Compositional Electromechanical Study of Biopiezoelectrics A.S. Kalinin1,2, V.V. Polyakov1, V.A. Bykov1,2 1 NT-MDT 2

Spectrum Instruments, Zelenograd, Moscow, Russia Moscow Institute of Physics and Technology, Dolgoprudny, Moscow Region, Russia

Introduction. Jumping-like modes working principle

Patent US 5229606 “Jumping probe microscope” Applied in 1989 by Virgil B. Elings, John A. Gurley

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NT-MDT S.I. HybriD mode working principle1 Recording and processing 300÷3000 Force-Distance curves per second to get FB loop input signal and quantitative nanomechanical properties for each scanning point

Magonov, S. Belikov, J. D. Alexander, C. G. Wall, S. Leesment, and V. Bykov, “Scanning probe based apparatus and methods for low-force profiling of sample surfaces and detection and mapping of local mechanical and electromagnetic properties in non-resonant oscillatory mode,” US9110092B1, 2015.

Introduction. HybriD mode capabilities

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PS/HDPE Height

Elastic Modulus

Elastic Modulus

2 mm

2 mm

PS-b-PMMA

1 mm Images courtesy: Dr. Sergey Magonov, NT-MDT Development

400 nm

Introduction. HybriD mode capabilities Bismuth-Tin Alloy a) Topography b) Elastic modulus. Tip – 50 GPa, Bismuth – 32 GPa. (Si – 70 GPa) c) Surface Potential

Sn

Bi

CNT on Si a) Topography b) Current c) Elastic modulus

Images courtesy: Dr. Sergey Magonov, NT-MDT Development

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Scanning Thermal Microscopy combined with HybriD mode Scan size:18×30 µm Topography

Surface Potential

Sample courtesy: Dr. Sergey Magonov, NT-MDT Development

Topography

Surface Potential


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WS2 Monolayers Grown on Epitaxial Graphene Measured in vacuum. Scan size: 14×14 µm

Steam cell in liquid Scan size:18×30 µm

Topography

Image courtesy: Sergey Zayats, NT-MDT Spectrum Instruments

Surface Potential

HybriD mode

Tapping mode

Topography

Surface Potential

Sample courtesy: Dr. Stanislav Leesment, NT-MDT S.I. Sample courtesy: Dr. Cristina Giusca (NPL, UK), Prof. Mauricio Terrones (PSU, USA).

Compositional electromechanical studies E modulus: Force vs Distance Curves Dielectric permittivity: Electrostatic Force Microscopy (EFM) in 2nd pass

Electromechanical properties that currently can be studied by Jumpinglike modes

Surface potential: Kelvin Probe Microscopy (KPFM) in 2nd pass Conductivity: Spreading resistance (SRM)

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Compositional electromechanical studies E modulus: Force vs Distance Curves Dielectric permittivity: Electrostatic Force Microscopy (EFM) in 2nd pass

Electromechanical properties that currently can be studied by Jumpinglike modes

Surface potential: Kelvin Probe Microscopy (KPFM) in 2nd pass Conductivity: Spreading resistance (SRM) Piezoresponse: Piezoresponse Force Microscopy (PFM)

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HybriD PFM: Motivation for development (a)

(b)

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(d)

Molecular structure of diphenylalanine nanotubes2 (a) Hexagonal unit cell of the diphenylalanine-based molecular crystal, projected onto the xy plane. (b) Multiple equivalent unit cells, projected on the xy plane, resulting in the characteristic porous molecular crystal structure. The white frame denotes a single unit cell. (c) Schematic illustration of the peptide nanotube structure. (d) SEM image

(a) AFM topography and contact PFM (b) amplitude and (c) phase images of FF nanotubes3 2Azuri,

I., Adler-Abramovich, L., Gazit, E., Hod, O. & Kronik, L. Why are diphenylalanine-based peptide nanostructures so rigid? Insights from first principles calculations. J. Am. Chem. Soc. 136, 963–969 (2014). 3Ryan, K. et al. Nanoscale Piezoelectric Properties of Self-Assembled Fmoc-FF Peptide Fibrous Networks. ACS Appl. Mater. Interfaces 7, 12702–12707 (2015)

HybriD PFM: Principle of operation

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Voltage (up to 150 V amplitude) is applied exactly during the contact between sample and probe Amplitude and Phase of piezoresponse are measured exactly during the contact between sample and probe Simultaneous mapping of sample topography, E-modulus, work of adhesion along with piezoresponse and capacitance contrasts Minimization of lateral forces between probe and sample Compensation of DFL drift during scanning

HybriD PFM: Implementation • • •

HybriD 2.0 controller

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Digital generator and high-speed lock-in amplifiers with 4 MHz bandwidth HV amplifier module: +/-150 V Signals windowing: real time application of ac/dc voltage and signals measurement exactly in or out of contact between probe and sample KFM, MFM, EFM measurements 2-pass modes Automated calibration of OBD sensitivity and cantilever force constant Real time calculation of Young modulus and work of adhesion PLL module for FM-AFM

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HybriD PFM: Implementation

Height

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HD VPFM Amplitude HD VPFM Phase -900 +900

HybriD PFM images of LiNbO3 test sample. VPFM Phase change of 180 degrees is demonstrated. Scan size 50x67 um

HybriD and contact PFM comparison. Scan size 10x10 um

HybriD PFM: Peptide nanotubes

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The matrix for the direct piezoelectric effect:

 0 0 0 d14 d15 0    d   0 0 0 d15  d14 0  d d d 0 0 0  13 31 33 

Height

In-plane PFM Phase

Work of Adhesion

EFM Phase, d2C/dz2

HybriD PFM images of FF peptide nanotubes. Diameter of the tubes is 250÷300 nm. Arrows demonstrate the direction of polarization. Scan size 8×8 um. Sample courtesy: Prof. V.Y. Shur, S.G. Vasiliev UCSU “Modern Nanotechnologies” UFU; A.L. Kholkin, University of Aveiro


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The matrix for the direct piezoelectric effect:

 0 0 0 d14 d15 0    d   0 0 0 d15  d14 0  d d d 0 0 0  13 31 33 

Height

In-plane PFM Phase

Work of Adhesion

EFM Phase, d2C/dz2

HD PFM images of FF peptide nanotubes. Diameter of the tubes is 250÷300 nm. Arrows demonstrate the direction of polarization. Scan size 8×8 um. Sample courtesy: Prof. V.Y. Shur, S.G. Vasiliev UCSU “Modern Nanotechnologies” UFU; A.L. Kholkin, University of Aveiro

HybriD PFM: mechanical properties

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FF peptide tubes E modulus

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4Zelenovskiy,

P., Kornev, I., Vasilev, S. & Kholkin, A. On the origin of the great rigidity of self-assembled diphenylalanine nanotubes. Phys. Chem. Chem. Phys. 18, 29681–29685 (2016).


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Tubes diameter: 30÷70 nm DMT E modulus: 10±3 GPa

HD PFM images of peptide nanotubes. Arrows demonstrate the direction of polarization. Scan size 7×7 um and 3×3 um (right) Sample courtesy: Prof. V.Y. Shur, S.G. Vasiliev UCSU “Modern Nanotechnologies” UFU; A.L. Kholkin, University of Aveiro


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HD PFM images of peptide nanotubes. Arrows demonstrate the direction of polarization. DMT E modulus is 10±3 GPa Scan size 8×8 Sample courtesy: Prof. V.Y. Shur, S.G. Vasiliev UCSU “Modern Nanotechnologies” UFU; A.L. Kholkin, University of Aveiro

HybriD PFM: Measurements of highly rough surfaces

Height

HD LPFM Phase

E-modulus

Adhesion

HD PFM images of matrix of retinal stroma collagen. Heigh contrast corresponds to 0-900 nm. Scan size 15×15 um.

Sample courtesy: M. Paukshto, Fibralign Corporation, USA

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HybriD PFM: Measurements at variable temperatures Heigh t

HD VPFM Amplitude

HD VPFM Phase

Cantilever deflection Т, оС 60 0nm 100nm 35

Curie temperature (T=49 оС)

HD PFM images of triglycine sulfate crystal. Temperature dependence of domain structure is shown. Scan size 8×15 um.

Sample courtesy: R. Gainutdinov, Institute of Crystallography RAS

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Conclusions

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The novel AFM approach for piezoresponse study was developed. It allows:  Nondestructive measurements of soft and loose samples  Continuous measurements under variable temperature  Simultaneous mapping of E modulus, adhesion and electrostatic properties It was demonstrated on:  Diphenylalanine peptide nanotubes  Collagen matrix  Temperature dependence of domain structure of triglycine sulfate

Acknowledgments: V. Atepalikhin, Dr. V. Polyakov, Prof. V. Bykov from NT-MDT Spectrum Instruments Dr. A. Kholkin, University of Aveiro, Portugal Dr. S. Vasilev, Ural Federal University, Russia

E-mail: [email protected]

Thank you!