Electrochemical force microscopy

Patent metadata

Field	Value
Publication number	US-9541576-B2
Application number	US-201514810605-A
Country	US
Kind code	B2
Filing date	Jul 28, 2015
Priority date	Jul 28, 2014
Publication date	Jan 10, 2017
Grant date	Jan 10, 2017

Abstract

A system and method for electrochemical force microscopy are provided. The system and method are based on a multidimensional detection scheme that is sensitive to forces experienced by a biased electrode in a solution. The multidimensional approach allows separation of fast processes, such as double layer charging, and charge relaxation, and slow processes, such as diffusion and faradaic reactions, as well as capturing the bias dependence of the response. The time-resolved and bias measurements can also allow probing both linear (small bias range) and non-linear (large bias range) electrochemical regimes and potentially the de-convolution of charge dynamics and diffusion processes from steric effects and electrochemical reactivity.

First claim

The invention claimed is:

1. A method of mapping dynamic charge screening, ionic diffusion, or electrochemical reactivity comprising:
providing an electrode separated by a distance from a sample material and in electrical communication with the sample material through an electrolyte solution;
applying an excitation voltage to the electrode to establish an electrical potential between the electrode and the sample material, the excitation voltage including a probing waveform component and an excitation waveform component superimposed thereon, wherein the probing waveform component includes a carrier waveform having a bias-on state and a bias-off state to elicit diffusion or faradaic reactions at the sample material, and wherein the excitation waveform component includes a frequency greater than a frequency of the probing waveform component to elicit double layer charging or charge relaxation at the sample material, the frequency of the excitation waveform component being between 5 kHz to 50 kHz inclusive, and the frequency of the probing waveform component being between 1 Hz to 10 Hz inclusive; and
measuring a force response induced on the electrode by the electrical potential, the force response including the bias and time dependent local response of the sample material.

2. The method according to claim 1 further including generating a two-dimensional spectra including the bias and time dependent local response of the sample material.

3. The method according to claim 1 wherein the electrode includes a cantilever having a current conductive tip.

4. The method according to claim 3 wherein measuring a force response includes detecting the deflection of the cantilever.

5. The method according to claim 1 wherein the probing waveform component includes a unipolar first order reversal curve or a bipolar first order reversal curve.

6. The method according to claim 1 wherein the excitation waveform component includes a periodic waveform having a fixed frequency operating at resonance.

7. The method according to claim 1 wherein the probing waveform component includes a bias that varies over time.

8. The method according to claim 6 wherein measuring the force response includes measuring the force response as a function of the bias of the probing waveform component.

9. A system for mapping dynamic charge screening, ionic diffusion, or electrochemical reactivity comprising:
a current conductive cantilever, the cantilever being separated by a sample material through an electrolyte solution;
a signal generator operable to provide an excitation signal to the cantilever, the excitation signal including a probing waveform component and an excitation waveform component, wherein the probing waveform component includes a carrier waveform having a bias-on state and a bias-off state to elicit diffusion or faradaic reactions at the sample material, and wherein the excitation waveform component includes a frequency greater than a frequency of the probing waveform component to elicit double layer charging or charge relaxation at the sample material, the frequency of the excitation waveform component being between 5 kHz to 50 kHz inclusive, and the frequency of the probing waveform component being between 1 Hz to 10 Hz inclusive, the excitation signal inducing an electrical potential between the electrode and the sample material;
a force detection sensor operable to measure the deflection of the cantilever over time; and
a signal analysis module operable to determine, based on the output of the force detection sensor, a response of the cantilever as a function of a magnitude of the probing waveform and as a function of time.

10. The system of claim 9 wherein the force detection sensor includes a laser and an optical detector to detect laser light reflected from the current conductive cantilever.

11. The system of claim 9 wherein the probing waveform component includes a time-varying magnitude.

12. The system of claim 11 wherein the probing waveform component includes a unipolar first order reversal curve or a bipolar first order reversal curve.

13. The system of claim 9 wherein the excitation waveform component includes a periodic waveform having a fixed frequency operating at resonance.

14. A method of mapping dynamic charge screening, ionic diffusion, or electrochemical reactivity comprising:
providing an electrode separated by a distance from a sample material and in electrical communication with the sample material through an electrolyte solution;
establishing an electrical potential between the electrode and the sample material, the electrical potential being induced by an excitation voltage applied to the electrode or to the sample material, the excitation signal including a probing waveform component and an excitation waveform component, wherein the probing waveform component includes a carrier waveform having a bias-on state and a bias-off state to elicit diffusion or faradaic reactions at the sample material, and wherein the excitation waveform component includes a frequency greater than a frequency of the probing waveform component to elicit double layer charging or charge relaxation at the sample material, the frequency of the excitation waveform component being between 5 kHz to 50 kHz inclusive, and the frequency of the probing waveform component being between 1 Hz to 10 Hz inclusive; and
measuring a force response induced on the electrode by the electrical potential, the force response including the bias and time dependent local response of the sample material.

15. The method according to claim 14 wherein the electrode includes a probe having a cantilever and a current conductive tip.

16. The method according to claim 15 wherein measuring a force response includes detecting the deflection of the cantilever.

17. The method according to claim 14 wherein the probing waveform component includes a bias that varies over time.

18. The method according to claim 17 wherein measuring the bias response includes measuring the force response as a function of the bias of the probing waveform component.

19. The method according to claim 14 wherein the probing waveform component includes a unipolar first order reversal curve or a bipolar first order reversal curve.

20. The method according to claim 14 further including generating a two-dimensional spectra including the bias and time dependent local response of the sample material.

Assignees

• Ut Battelle Llc

Inventors

• Kalinin Sergei V
• Jesse Stephen
• Collins Liam F
• Rodriguez Brian J

Classifications

• G01Q60/60 Primary

  SECM [Scanning Electro-Chemical Microscopy] or apparatus therefor, e.g. SECM probes · CPC title