Methods for making deposited films with improved microstructures

• US 4,336,118 A
• Filed: 03/21/1980
• Issued: 06/22/1982
• Est. Priority Date: 03/21/1980
• Status: Expired due to Term

• Current Assignee: Battelle Memorial Institute
• Original Assignee: Battelle Memorial Institute
• Inventors: Patten, James W., Moss, Ronald W., McClanahan, Edwin D.
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US06/131,922
• Time in Patent Office: 823 Days
• Field of Search: 204/192 EC, 427/255.5, 427/255.7, 427/270, 427/271
• US Class Current: 204/192.12
• CPC Class Codes: C23C 14/00 Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
• CPC Class Codes: C23C 14/22 characterised by the process of coating
• CPC Class Codes: C23C 14/505 for rotation of the substrates
• CPC Class Codes: Y10S 428/938 Vapor deposition or gas diffusion
• CPC Class Codes: Y10T 428/12063 Nonparticulate metal component

Abstract

Methods for improving microstructures of line-of-sight deposited films are described. Columnar growth defects ordinarily produced by geometrical shadowing during deposition of such films are eliminated without resorting to post-deposition thermal or mechanical treatments. The native, as-deposited coating qualities, including homogeneity, fine grain size, and high coating-to-substrate adherence, can thus be retained. The preferred method includes the steps of emitting material from a source toward a substrate to deposit a coating non-uniformly on the substrate surface, removing a portion of the coating uniformly over the surface, again depositing material onto the surface, but from a different direction, and repeating the foregoing steps. The quality of line-of-sight deposited films such as those produced by sputtering, progressively deteriorates as the angle of incidence between the flux and the surface becomes increasingly acute. Depositing non-uniformly, so that the coating becomes progressively thinner as quality deteriorates, followed by uniformly removing some of the coating, such as by resputtering, eliminates the poor quality portions, leaving only high quality portions of the coating. Subsequently sputtering from a different direction applies a high quality coating to other regions of the surface. Such steps can be performed either simultaneously or sequentially to apply coatings of a uniformly high quality, closed microstructure to three-dimensional or larger planar surfaces.

Claims

1. A line of sight deposition method comprising:

emitting material from a source spaced apart from a substrate surface;

depositing a first amount of said material on a first region of said surface to form a first deposit having a first deposition characteristic;

simultaneously depositing a second amount of said material, less than said first amount, on a second region of said surface to form a second deposit having a second deposition characteristic including columnar growth defects due to geometric shadowing; and

removing an amount of said deposited material approximately uniformly from said substrate surface including said first and second regions;

the amount removed being less than said first amount, at least as great as said second amount, and sufficient to remove a portion of the deposited material having said second characteristic and to reduce said columnar growth defects.

2. A method according to claim 1 including:

simultaneously depositing a third amount of said material less than the first amount and greater than the second amount on a third region of said surface to form a third deposit having a third deposition characteristic which is a blend of said first and second deposition characteristics and includes columnar growth defects to a lesser extent than said second deposit; and

removing an amount of said deposited material from said surface, including said third region, which is not less than approximately the amount deposited on said second region.

3. A method according to claim 2 in which the amount of said material removed from said surface is not less than the amount deposited in said third region;

whereby substantially all of the deposited material containing said columnar growth defects is eliminated from both the second and third regions.

4. A method according to claim 2 in which the amount of material removed from said first region is less than the amount deposited in said third region;

whereby a specifiable portion of material having said third deposition characteristic remains.

5. A method according to claim 1 including emitting material from a source at a different position relative to the substrate so that material having said first deposition characteristic can be deposited on said second region.

6. A method according to claim 5 including

performing the steps of claim 1 sequentially;

changing the position of the substrate with respect to the source; and

repeating the steps of claim 1 sequentially.

7. A method according to claim 1 in which the removing of said deposited material is performed simultaneously with the depositing of said material, the first and second amounts of material being deposited at first and second rates of deposition, respectively, and the amount of material removed being removed at a rate of removal less than the first rate of deposition and sufficient to prevent accumulation of material in said second region but not in said first region.

8. A method according to claim 7 including simultaneously changing the position of the substrate with respect to the source.

9. A method according to claim 6 or 8 in which said regions partially overlap, including controlling the amount of material removed to remove substantially all of the material deposited with said second characteristic before it is overlain by material with said first characteristic so that only material having said first characteristic accumulates where said regions overlap.

10. A method according to claim 1 in which the emitting step includes emitting said material from a source comprising at least two different sources spaced apart along said substrate surface.

11. A method according to claim 10 in which said two sources emit material simultaneously.

12. A method according to claim 10 in which said two sources emit material alternately.

13. A line of sight deposition method comprising:

emitting material from a source to establish a flux of said material in the direction of a substrate surface;

depositing a portion of said material on regions of said surface which are exposed to at least a portion of said source along a line of sight, including;

depositing material on a first said region whose surface tangent forms a first angle with the direction of said flux;

depositing material on a second said region whose surface tangent forms a second angle with the direction of said flux less than said first angle;

the material deposited in the first region having a first deposition characteristic and the material deposited in the second region having a second deposition characteristic including defects due to geometric shadowing;

the amount of material deposited per unit area of said surface being greater in the first region than in the second region; and

removing deposited material approximately uniformly from said surfce so as to reduce the accumulation of deposited material having said second characteristic and to increase the relative proportion of deposited material having said first characteristic.

14. A method according to claim 13 including subsequently emitting material from a different position of the source relative to the substrate to expose different regions of said surface to a portion of said source along a line of sight to deposit material thereon at said first angle, so that material having said first deposition characteristic is deposited on said second region.

15. A method according to claim 14 in which the position of the source relative to the substrate is progressively changed so as to progressively expose substantially all of said surface to said flux at said first angle

so that substantially all of said surface is progressively coated with material having said first characteristic.

16. A method according to claim 13 in which the emitting step includes emitting material from first and second portions of said source, said portions being laterally separated such that:

the first portion establishes a flux in the direction of said surface including a first fraction in the direction of said first region and a second fraction in the direction of said second region; and

the second portion establishes a flux in the direction of said surface including a third fraction in the direction of said first region and a fourth fraction in the direction of said second region;

the first and third fractions defining a first net flux incident to the surface tangent of the first region at an angle approximating said first angle;

the second and fourth fractions defining a second net flux incident to the surface tangent of the second region at an angle approximating said second angle;

the magnitude of the first net flux being greater than the magnitude of the second net flux.

17. A method according to claim 13 in which:

the substrate surface includes a surface asperity in each of said first and second regions;

the emitting step includes emitting material from first and second portions of said source, said portions being laterally separated such that;

the first portion establishes a flux in the direction of said surface including a first fraction in the direction of said first region and a second fraction in the direction of said second region; and

the second portion establishes a flux in the direction of said surface including a third fraction in the direction of said first region and a fourth fraction in the direction of said second region;

the first and third fractions each having a magnitude and an angle of incidence to the surface tangent of the first region such that any tendency of one of said fractions to form a geometric shadow on a leeward side of said asperity is canceled out by the other fraction, so that material is deposited in approximately equal amounts on both sides of the asperity;

the second and fourth fractions each having a magnitude and an angle of incidence to the surface tangent of the second region such that both fractions tend to form a geometric shadow on a leeward side of said asperity so that a void develops on the leeward side as material is deposited around the asperity.

18. A method according to claim 17 in which:

the surface includes multiple asperities which cause numerous voids to develop in conjunction with columnar growth structures in said second region but not in said first region as material accumulates on said surface to define an open, generally porous coating in the second region and a closed, generally non-porous coating in the first region; and

the removing step includes removing sufficient material to substantially eliminate the open, generally non-porous coating while retaining the closed, non-porous coating.

19. A method according to claim 18 in which the surface includes a third region whose surface tangent forms a third angle with the direction of said flux;

the third angle being less than the first angle and more than the second angle so that material deposited on the third region forms a coating thereon which is generally closed but which can include voids extending through a portion of the thickness of the coating;

the removal step including removing sufficient material to limit the extent of voids in the third region to a small fraction of the thickness of the coating in said first region.

20. A physical vapor deposition method comprising:

emitting a physical vapor from a source spaced apart from a substrate surface;

depositing a portion of said vapor non-uniformly onto said surface to form a solid coating thereon, the coating including a first portion on a first region of said surface having a first thickness and a second portion on a second region having a second thickness less than the first thickness; and

removing a thickness of the coating uniformly over said surface;

whereby the thickness of the second portion is reduced in proportion to the thickness of the first portion.

21. A method according to claim 20 in which the emitting of said physical vapor establishes an adatom flux from said source in the direction of said surface such that a first fraction of the flux is incident upon the first region at a first angle to the surface tangent of the first region and a second fraction of the flux is incident upon the second region at a second angle to the surface tangent of the second region, the first angle being more nearly a right angle than the second angle, so that the first coating portion is less influenced by geometrical shadowing than the second coating portion on the second region and is also thicker than said second portion;

whereby uniform removal of a thickness of the entire coating removes a larger proportion of the second portion than of the first portion.

22. A method according to claim 20 in which a sufficient thickness of coating is removed to prevent accumulation of coating having an open microstructure including voids due to geometrical shadowing.

23. A method according to claim 20 in which:

emitting a physical vapor includes sputtering material from said source; and

removing includes re-sputtering a portion of the deposited coating from said surface.

24. A method according to claim 23 including ion etching said surface prior to depositing material thereon.

25. A method according to claim 20 including changing the position of the substrate relative to said source.

26. A method according to claim 25 in which changing relative position includes rotating the substrate.

27. A method according to claim 25 in which:

the source includes two sources spaced apart to emit an adatom vapor flux toward the substrate surface from two different directions; and

changing relative position includes alternately emitting said flux from each source.

28. A method according to claim 25 in which the emitting, depositing, removing and position changing steps are performed sequentially.

29. A method according to claim 25 in which the emitting, depositing, removing and position changing steps are performed simultaneously.

30. A method according to claim 20 in which:

the removing step includes removing a thickness of coating at least as great as the thickness of any coating deposited on regions of said surface not facing the source so as to be coated by the physical vapor emitted therefrom along the line of sight; and

the depositing step includes depositing another portion of said vapor nonuniformly on said surface after the removal step to cover said second region with a third portion of coating having approximately said first thickness.