Process and device for surface-modification by physico-chemical reactions of gases or vapors on surfaces, using highly-charged ions

• US 5,645,897 A
• Filed: 01/18/1995
• Issued: 07/08/1997
• Est. Priority Date: 02/15/1992
• Status: Expired due to Fees

• Current Assignee: Jurgen Andra
• Original Assignee: Jurgen Andra
• Inventors: Andra, Jurgen
• Primary Examiner(s): PADGETT, MARIANNE L
• Application Number:
  US08/284,632
• Time in Patent Office: 902 Days
• Field of Search: 427/523, 427/524, 427/526, 427/561, 427/562, 427/566, 427/569, 427/571, 427/575, 427/596, 427/530, 216/65, 216/66, 216/68, 216/69, 216/70, 204/192.11, 204/192.13, 204/192.32
• US Class Current: 427/526
• CPC Class Codes: C23C 16/27 Diamond only
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/342 Boron nitride
• CPC Class Codes: C23C 16/402 Silicon dioxide
• CPC Class Codes: C23C 16/44 characterised by the method of coating C23C16/04 takes precedence
• CPC Class Codes: C23C 16/486 using ion beam radiation
• CPC Class Codes: C30B 33/00 After-treatment of single crystals or homogeneous polycrystalline material with defined structure C30B31/00 takes precedence
• CPC Class Codes: H01J 2237/006 Details of gas supplies, e.g. in an ion source, to a beam line, to a specimen or to a workpiece, H01J37/3244 takes precedence; environmental cells for electron microscopes H01J2237/2003; microscopes with environmental specimen chamber H01J2237/2608
• CPC Class Codes: H01J 2237/31732 Depositing thin layers on selected microareas ion plating H01J2237/3142
• CPC Class Codes: H01J 2237/31744 introducing gas in vicinity of workpiece
• CPC Class Codes: H01J 37/3056 for microworking, e.g. etching of gratings, trimming of electrical components trimming of resistors H01C17/22
• CPC Class Codes: H01J 37/317 for changing properties of the objects or for applying thin layers thereon, e.g. for ion implantation H01J37/36 takes precedence

Abstract

The invention concerns a process and a device for surface-modification by physico-chemical reactions with the following steps: a) contacting a solid surface having a crystalline or amorphous structure with a reactive, gaseous fluid (gas, gas mixture, vapour or vapour mixture) which is to interact with the surface; (b) supplying activating energy to the contact area between fluid and surface by means of ions or plasmas, in order to trigger reactions between said partners. In order to improve such a process and device, the activating energy is supplied as ions having at least a double charge and low kinetic energy or plasma streams with a sufficient proportion of ions having at least a double charge and low kinetic energy. The kinetic energy imparted to the ions is selected so that it allows the ions to closely approach the surface atoms but no to enter the surface.

Claims

1. In a process for surface modification by physico-chemical reactions, said process comprising the steps of:

(a) contacting a solid surface having a crystalline or amorphous structure with a reactive, gaseous fluid which is to interact with the surface; and

(b) supplying activating energy to both said fluid and said surface by means of ions or plasmas, in order to trigger reactions between said fluid and said surface,

the improvement comprising providing an activating energy in the form of an electronic potential energy of ions having a charge of q≧

2 with a low kinetic energy, or by streams of plasmas, which contain a high proportion of an arithmetically averaged charge state Σ

q·

ƒ

(g)=qm ≧

2, where ƒ

(g) is a fraction of particles in charge state q=0,1,2, . . . , with said low kinetic energy, wherein said low kinetic energy is below about 100·

q eV and determined to meet a condition that said ions are allowed to closely approach atoms of said surface, but not to penetrate said surface.

2. The process according to claim 1, wherein the surface modification comprises an etching process.

3. The process according to claim 1, wherein the surface modification comprises a coating process.

4. The process according to claim 1, wherein the surface modification comprises a deposition process.

5. The process according to claim 1, wherein said fluid is provided as spatially homogeneous atomic or molecular ion beams directed toward said surface at an arbitrarily selected angle in a vacuum between about 10^-2 and 10^-9 Pa such that said low kinetic energy, ions are injected from a region of said vacuum traverse a limited region of gas, and then impinge said surface.

6. The process according to claim 1, wherein the surface modification is conducted at a surface temperature below 600°

C.

7. The process according to claim 1, wherein one or several mono-layers of said fluid are adsorbed at said surface and are physicochemically activated by said low kinetic energy ions.

8. The process according to claim 1, wherein further comprising the step of adsorbing a portion of said fluid at said surface by either:

(i) providing said low kinetic energy ions as a continuous ion beam and supplying said fluid in the form of pulses of defined quantity corresponding to one to three mono-layers of said adsorbed fluid at said surface or

(ii) providing said low kinetic energy ions as intermittent pulses of ions and supplying fluid pulses of said fluid having defined quantity of said fluid corresponding to one to three mono-layers of adsorbed fluid, a quantity of an ion pulse being adapted to a necessary activating energy of said adsorbed mono-layers

a flux and an adsorption of said fluid at said surface being adapted to said continuous ion beam or said ion pulses such that said ions statistically interact with a fresh mono-layer of said adsorbed fluid.

9. The process according to claim 1, wherein said fluid is produced by sputtering a solid material with ions having a sufficient kinetic energy to cause said sputtering.

10. The process according to claim 9, wherein said solid material is boron.

11. The process according to claim 1, wherein said process of surface modification is started with a stream of highly charged ions, having a high kinetic energy sufficient to penetrate said surface, directed at said surface which is subsequently changed to a stream of said low kinetic energy ions whereby said high kinetic energy ions penetrate into said surface at the beginning of the etching process, or to improve adhesion at the beginning of a coating process by the linking to crystalline defects.

12. The process according to claim 1, wherein said activating energy is provided as a stream of said ions of an element which represents a significant constituent of said surface to be modified.

13. The process according to claim 1, wherein said highly charged ions are:

produced in an ion source;

extracted, and optionally separated with respect to a charge to mass ratio (q/m);

transported to a processing chamber; and

decelerated to said low kinetic energy per charge in front of said surface to be modified.

14. The process according to claim 1, wherein an angle of incidence, a position of impact, and a size of an impact spot of said ions on said surface to be modified are controlled.

15. The process according to claim 1, wherein said ions are produced in a region with magnetic plasma confinement by feeding energy via electron beams or via microwaves employing electron cyclotron resonance, and wherein the plasma with low kinetic energy ions is brought into direct contact with said surface to be modified.

16. The process according to claim 1, wherein one or more devices selected from the group consisting of an electron-cyclotron-resonance ion source with magnetic plasma confinement, an electron impact ion source, and an electron beam ion source is used to produce said ions.

17. The process according to claim 1, wherein said highly charged ions irradiates a perforated mask which is imaged onto said surface, such that an etched or coated image of said mask is produced on said surface.

19. The process according to claim 1, wherein the reactions take place at a surface temperature of below 0°

C.

20. The process according to claim 1, wherein said kinetic energy of said ions is between about 1·

q eV and 60·

q eV.

18. The process according to claim wherein said fluid homogeneously streams out of a matrix of nozzles on to said surface, and wherein said low kinetic energy ions are injected from a region of vacuum sufficient to impinge said surface and impinge said surface through holes in said matrix of nozzles.