Frequency-based detection of chemical expansion dynamics in thin films

Patent metadata

Field	Value
Publication number	US-10429175-B2
Application number	US-201715829022-A
Country	US
Kind code	B2
Filing date	Dec 1, 2017
Priority date	Dec 2, 2016
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

Current techniques for measuring chemical expansion in thin film structures are too slow, too imprecise, or require synchrotrons. In contrast, nanoscale electrochemomechanical spectroscopy (NECS) can be used to make nanoscale measurements at time scales of seconds with simple contact or non-contact sensors. In a NECS measurement, a sample, such as thin-film oxide structure, is subjected to a temporally modulated stimulus, such as a sinusoidally alternating voltage. The stimulus causes the sample to expand, contract, deflect, or otherwise deform. A sensor, such as a contact probe or optical sensor, produces an electrical signal in response to this deformation that is correlated with the temporal modulation of the stimulus. Because the stimulus and deformation are correlated, the temporal modulation of the stimulus can be used to filter the deformation signal produced by the sensor, producing a precise, sensitive measurement of the deformation.

First claim

The invention claimed is:

1. A method of characterizing a device, the method comprising:
applying a time-varying stimulus to the device, the time-varying stimulus causing a time-varying change in gas content of the device, the time-varying stimulus including an alternating bias voltage; and
measuring, with a probe in contact with a surface of the device, a time-varying deformation of the device caused by the time-varying change in gas content of the device, the time-varying deformation based on chemical expansion or a deflection of the surface of the device induced by the time-varying change in gas content of the device, the measuring including sensing displacement of the probe in response to the time-varying deformation.

2. The method of claim 1 , further comprising:
varying the alternating bias voltage at a rate of about 0.01 Hz to about 1 Hz.

3. The method of claim 1 , wherein the device comprises an oxide film and wherein the time-varying change in gas content of the device is a time-varying change in oxygen content of the oxide film.

4. The method of claim 1 , wherein the time-varying deformation is caused by chemical expansion.

5. The method of claim 1 , wherein the time-varying deformation is caused by deflection.

6. The method of claim 1 , further comprising:
constraining the device while applying the time-varying stimulus.

7. The method of claim 1 , further comprising:
keeping the device at a temperature of at least about 450 degrees Celsius while applying the time-varying stimulus.

8. The method of claim 1 , further comprising:
filtering a signal representing the time-varying deformation based on a spectral component of the time-varying stimulus to enhance the spectral component of the time-varying deformation.

9. The method of claim 1 , further comprising:
determining an amplitude of the time-varying deformation as a measure of the amount of chemical expansion or the deflection of the surface of the device.

10. The method of claim 1 , further comprising:
determining a phase difference between the time-varying deformation and the time-varying stimulus as an indicator of kinetically limiting processes associated with device.

11. A system for characterizing a device, the system comprising:
a stimulus source configured to apply a time-varying stimulus to the device, the time-varying stimulus causing a time-varying change in gas content of the device, the stimulus source including a voltage source and the time-varying stimulus including an alternating bias voltage; and
a sensor including a probe in contact with a surface of the device, configured to measure a time-varying deformation of the device caused by the time-varying change in gas content of the device, the time-varying deformation based on chemical expansion or a deflection of the surface of the device induced by the time-varying change in gas content of the device, wherein the probe measures the time-varying deformation by sensing displacement of the probe in response to the time-varying deformation.

12. The system of claim 11 , wherein the surface of the device comprises an oxide film and the time-varying change in gas content of the device comprises a change in oxygen content of the oxide film.

13. The system of claim 11 , wherein the voltage source is configured to vary the alternating bias voltage at a rate of about 0.01 Hz to about 1 Hz.

14. The system of claim 11 , wherein the sensor is configured to measure the time varying deformation based on chemical expansion.

15. The system of claim 11 , wherein the sensor is configured to measure the time varying deformation based on deflection.

16. The system of claim 11 , further comprising:
a heater configured to keep the device at a temperature of at least about 450 degrees Celsius during application of the time-varying stimulus.

17. The system of claim 11 , further comprising:
circuitry, in electrical communication with the sensor, to filter a signal representing the time-varying deformation based on a spectral component of the time-varying stimulus.

18. A method of characterizing deformation of a device comprising an oxide film, the method comprising:
heating the device to a temperature of at least 450 degrees Celsius;
applying a time-varying voltage to the device, the time-varying voltage causing a time-varying change in oxygen content of the oxide film;
measuring, with a probe in contact with a surface of the device, a time-varying deformation of the device caused by the time-varying change in oxygen content of the oxide film, the time-varying deformation based on chemical expansion or a deflection of the surface of the device induced by the time-varying change in oxygen content of the device, the measuring including sensing displacement of the probe in response to the time-varying deformation; and
determining an amplitude of the time-varying deformation as a measure of the amount of chemical expansion or deflection; and
determining a phase difference between the time-varying deformation and the time-varying stimulus as an indicator of kinetically limiting processes associated with device.

19. A method of characterizing a device, the method comprising:
applying a time-varying stimulus to the device, the time-varying stimulus causing a time-varying change in gas content of the device, the time-varying stimulus including an alternating bias voltage;
illuminating a surface of the device; and
measuring, with a detector configured to detect light reflected off the surface of the device in response to said illuminating, a time-varying deformation of the device caused by the time-varying change in gas content of the device, the time-varying deformation based on chemical expansion or a deflection of the surface of the device induced by the time-varying change in gas content of the device, the measuring including detecting a change in the reflected light in response to the time-varying deformation.

Assignees

• Swallow Jessica G
• Van Vliet Krystyn J
• Tuller Harry L
• Bishop Sean R
• Kim Jae Jin
• Smith James F
• Massachusetts Inst Technology

Inventors

• Swallow Jessica G
• Van Vliet Krystyn J
• Tuller Harry L
• Bishop Sean R
• Kim Jae Jin
• Smith James F

Classifications

• H01M10/42

  Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells (H01M10/60 takes precedence) · CPC title

• H01M8/00

  Fuel cells; Manufacture thereof · CPC title

• G01B11/16 Primary

  for measuring the deformation in a solid, e.g. optical strain gauge · CPC title

• G01N27/021

  before and after chemical transformation of the material · CPC title

• G01B3/002

  Details · CPC title