Methods for in situ monitoring and control of defect formation or healing

• US 10,203,295 B2
• Filed: 04/14/2016
• Issued: 02/12/2019
• Est. Priority Date: 04/14/2016
• Status: Expired due to Fees

• Current Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Original Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Inventors: Swett, Jacob L., Bedworth, Peter V.
• Primary Examiner(s): Hollington, Jermele M
• Assistant Examiner(s): Nasir, Taqi
• Application Number:
  US15/099,056
• Publication Number:
  US 20170299537A1
• Time in Patent Office: 1,034 Days
• Field of Search: 324324, 324333, 324338, 324346, 324351, 324355, 324368, 324372, 324221, 324303, 324366, 324386, 3247541, 32475411, 32475424
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: G01N 2223/603 superlattices
• CPC Class Codes: G01N 2223/6462 microdefects
• CPC Class Codes: G01N 23/225 using electron or ion
• CPC Class Codes: G01N 25/72 Investigating presence of flaws
• CPC Class Codes: G01N 27/041 of a solid body
• CPC Class Codes: G01N 27/20 Investigating the presence of flaws
• CPC Class Codes: G01N 33/00 Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
• CPC Class Codes: G01N 33/0095 Semiconductive materials

Abstract

Production of perforated two-dimensional materials with holes of a desired size range, a narrow size distribution, and a high and uniform density remains a challenge, at least partially, due to physical and chemical inconsistencies from sheet-to-sheet of the two-dimensional material and surface contamination. This disclosure describes methods for monitoring and adjusting perforation or healing conditions in real-time to address inter- and intra-sheet variability. In situ or substantially simultaneous feedback on defect production or healing may be provided either locally or globally on a graphene or other two-dimensional sheet. The feedback data can be used to adjust perforation or healing parameters, such as the total dose or efficacy of the perforating radiation, to achieve the desired defect state.

Claims

1. A method for monitoring defect formation or healing, comprising:

exposing a surface of a material to incident radiation, the material being a two-dimensional material including a graphene or graphene-based film;

detecting scattered, emitted and/or transmitted radiation from at least a portion of the material exposed to the incident radiation; and

generating data indicative of defect formation or healing, wherein the method is performed in situ where the defect formation or healing occurs and the data indicative of defect formation or healing provide a rate of defect formation or healing, a temporal change in the rate of defect formation or healing, a temporal change in the size of the defects, a spatial change in the rate of defect formation or healing, a spatial change in the size of the defects, or combinations thereof.

2. The method of claim 1, wherein the step of exposing the surface of the material to incident radiation produces a plurality of defects in the material.

3. The method of claim 1, wherein the step of detecting radiation or particles comprises:

(i) performing secondary ion mass spectroscopy;

(ii) performing Raman spectroscopy;

(iii) performing residual gas analysis on particles being removed from the material;

(iv) detecting back scattered radiation or particles;

(v) detecting Auger electrons;

(vi) performing scanning probe microscopy;

(vii) performing scanning tunneling microscopy;

(viii) performing atomic force microscopy;

(ix) performing X-ray photoelectron spectroscopy;

(x) performing transmission electron microscopy;

(xi) detecting nanoparticles on one or more microbalances or Faraday cups positioned behind the material;

(xii) performing small angle electron diffraction;

(xiii) detecting nanoparticles on a surface positioned behind the material using surface enhanced Raman scattering (SERS);

(xiv) detecting secondary electrons;

(xv) detecting transmitted electron or ions;

or

(xvi) performing a combination of two or more of (i)-(xv).

4. The method of claim 3, wherein the back scattered radiation are selected from the group consisting of electrons, protons, helium, gallium, neon, argon, xenon or ions.

5. The method of claim 1, wherein the step of generating data indicative of defect formation comprises determining secondary electron yield.

6. The method of claim 1, wherein the steps of exposing and detecting occur simultaneously.

7. The method of claim 1, wherein the incident radiation is perforating radiation, interrogating radiation or both.

8. The method of claim 1, wherein the incident radiation and the scattered, emitted and/or transmitted radiation are the same type of radiation or different types of radiation.

9. The method of claim 1, wherein the scattered, emitted or transmitted radiation results from the incident radiation or an additional source of interrogating radiation.

10. The method of claim 1, wherein the scattered, emitted and/or transmitted radiation from the material is collected from a bulk portion of the surface having an area between 1 μ

m² and 100 cm².

11. The method of claim 1, wherein the scattered, emitted and/or transmitted radiation from the material is collected from a local portion of the surface having an area between 100 nm² and 10 mm².

12. The method of claim 1, wherein the scattered, emitted and/or transmitted radiation is continuously collected.

13. The method of claim 1, wherein the incident radiation is pulsed, perforating radiation and the scattered, emitted and/or transmitted radiation is collected only when the incident radiation is off.

14. The method of claim 1, wherein the emitted radiation is secondary electrons.

22. The method of claim 1, wherein the incident radiation is a particle beam.

23. The method of claim 22, wherein the particle beam produces a spot on the surface of the material, the spot having an area between 1 μ

m² and 100 cm².

24. The method of claim 22, wherein the particle beam produces a spot on the surface of the material, the spot having an area between 1 nm² and 10 mm².

25. The method of claim 22, wherein the particle beam is an ion beam.

26. The method of claim 25, wherein the ion beam has an ion energy of at least 20 eV.

27. The method of claim 25, wherein the ion beam has a flux selected from the range of 10 pA/mm² to 1 μ

A/mm².

28. The method of claim 22, wherein the particle beam is an electron beam.

29. The method of claim 28, wherein the electron beam has an energy of at least 10 eV.

30. The method of claim 22, wherein the particle beam is a nanoparticle beam.

31. The method of claim 30, wherein the nanoparticle beam has an energy of at least 1 keV per nanoparticle.

32. The method of claim 30, wherein the nanoparticle beam has a flux selected from the range of 1.6×

10⁵ nanoparticles/s·

cm² to 1×

10¹⁵ nanoparticles/s·

cm².

33. The method of claim 1, wherein the two-dimensional material is a single atomic layer thick.

34. The method of claim 1, wherein the material comprises a stack of two or more sheets of two-dimensional material, wherein each sheet is a single atomic layer thick.

35. The method of claim 2, wherein the defects are pores having an average characteristic dimension less than or equal to 1 nm.

36. The method of claim 2, wherein the defects are pores having an average characteristic dimension ranging from 0.3 nm to 100 nm.

37. The method of claim 1, further comprising:

comparing the data indicative of defect formation or healing to a threshold range for the data; and

adjusting an energy or amount of the incident radiation if the data is outside of the threshold range.

38. The method of claim 1, further comprising translating the material at a rate dependent upon a rate of defect formation or healing.

15. A method for monitoring defect formation or healing, comprising:

exposing a surface of a material to incident radiation, the material being a two-dimensional material including a graphene or graphene-based film;

detecting movement of an analyte through defects in the material; and

generating data indicative of defect formation or healing, wherein the method is performed in situ where the defect formation or healing occurs and the data indicative of defect formation or healing provide a rate of defect formation or healing, a temporal change in the rate of defect formation or healing, a temporal change in the size of the defects, a spatial change in the rate of defect formation or healing, a spatial change in the size of the defects, a maximum size of the defects, or combinations thereof.

16. The method of claim 15, wherein the step of detecting movement of the analyte through the defects in the material comprises one or more of:

(i) determining the presence or absence of the analyte at a detector;

(ii) quantifying the analyte;

(iii) identifying a composition, mass, average radius, charge or size of the analyte;

(iv) determining a rate of movement of the analyte through the defects in the material;

or

(v) a combination of two or more of (i)-(iv).

17. The method of claim 15, wherein the analyte is a gas selected from the group consisting of hydrogen, helium, oxygen, nitrogen, xenon, neon, argon, SF₆, H₂O, C_xH_2x where x is 1 to 4, and combinations thereof.

18. The method of claim 15, wherein the analyte is a plasma.

19. The method of claim 15, wherein the incident radiation is a plasma and the analyte is one or more species of the plasma.

20. A method for monitoring defect formation or healing, comprising:

exposing a surface of a material to incident radiation;

applying an electrical bias to the material, the material being a two-dimensional material including a graphene or graphene-based film;

measuring electrical conductivity through a conductive probe in electrical contact with the material; and

generating data indicative of defect formation or healing, wherein the method is performed in situ where the defect formation or healing occurs and the data indicative of defect formation or healing provide a rate of defect formation or healing, a temporal change in the rate of defect formation or healing, a temporal change in the size of the defects, a spatial change in the rate of defect formation or healing, a spatial change in the size of the defects, or combinations thereof.

21. A method for monitoring defect formation or healing, comprising:

exposing a surface of a material to incident radiation, the material being a two-dimensional material including a graphene or graphene-based film;

heating the material;

subsequently measuring temperature of the surface of the material; and

generating data indicative of defect formation or healing, wherein the method is performed in situ where the defect formation or healing occurs and the data indicative of defect formation or healing provide a rate of defect formation or healing, a temporal change in the rate of defect formation or healing, a temporal change in the size of the defects, a spatial change in the rate of defect formation or healing, a spatial change in the size of the defects, or combinations thereof.