Title of Invention

A METHOD OF MARK ON A SURFACE OF A DIAMOND OR GEMSTONE

Abstract A method of forming a mark on a surface of a diamond or gemstone A method of forming a mark on a surface of a diamond or gemstone which mark comprises one or more unitary indicia, the method comprising the step of forming a plurality of grooves on the surface of the diamond or gemstone, which grooves define the indicium or indicia, the mark being such that it cannot be distinguished by the naked eye, the grooves producing a visible diffraction effect under appropriate lighting and magnification conditions.
Full Text

The present invention relates to a method and apparatus for forming a mark on a surface of a diamond or gemstone, which mark comprises one or more unitary indicia. The mark may be any mark, but the invention is particularly but not exclusively directed to applying an information mark to the diamond and the indicia can be alphanumeric characters or the like. The diamond may be, for instance, an industrial diamond such as a wire-drawing die, though the invention is of particular interest in marking gemstone diamonds, and especially for applying a mark which is invisible to the naked eye or invisible to the eye using a x10 loupe (which is the loupe used by jewellers), when the mark can be applied to a polished facet of the gemstone without detracting from its clarity grade.
The marks can be used to uniquely identify the gemstone by a serial number or as a brand or quality mark, but it should not detract from the value or appearance of the stone, and should preferably not exhibit blackening.
There is a detailed description of the nature of the marks that can be applied in WO-97/03846, in which the marks are applied by irradiating a diamond gemstone with ultraviolet laser radiation using a projection mask.
It is generally desirable to produce marks of improved resolution and visibility when viewed using appropriate magnification and illumination conditions, the marks being such that they do not detract from the value and appearance of the diamond or other gemstone. It is an object of the invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to produce a useful alternative.

The Invention
In accordance with a first aspect of the present invention, there is provided a method of forming a mark on a surface of a diamond or gemstone, which mark comprises one or more unitary indicia, the method comprising the step of forming a plurality of grooves on said surface of the diamond or gemstone, which grooves define the indicium or indicia, the mark being such that it cannot be distinguished by the naked eye, the grooves producing a visible diffraction effect under certain lighting (or illumination) and magnification conditions.
Also in accordance with the first aspect of the present invention, there is provided an apparatus for performing the above-mentioned method. The present invention further extends to a diamond or gemstone which has been marked by the above-mentioned method.
In accordance with the second aspect of the present invention, there is provided a method of forming a mark on the surface of a diamond or gemstone, comprising the step of forming a plurality of grooves on the surface of the diamond or gemstone, said grooves producing a visible diffraction effect under certain lighting (or illumination) and magnification conditions, without detrimentally affecting the clarity grade of the diamond or gemstone.
Also in accordance with the second aspect of the present invention, there is provided an apparatus for performing the above-mentioned method. The present invention further extends to a diamond or gemstone which has been marked by the above-mentioned method.
The mark cannot be distinguished by the naked eye. However, the grooves provide a visible diffraction effect under certain lighting conditions. The greater the depth of the grooves, the more visible the mark will be when viewed. The grooves should be of a suitable depth so that the mark is highly visible under appropriate viewing conditions, but not so deep that the clarity grade of the diamond or other gemstone is detrimentally affected. In one preferred embodiment, each groove is

not less than about 10 nm deep and/or not more than about 50 nm deep with no evidence of blackening. A specific example would be around 30 nm.
The grooves may be in the form of parallel lines, or even a plurality of intersecting grooves forming cross-hatched pattern, depending on the effect desired.
Although the marking can be carried out using any suitable means, e.g. etching with an excimer laser or plasma etching, marking is preferably carried out using an ion beam, and most preferably by direct writing on the diamond surface with a focused ion beam. By limiting the dose, sputtering of carbon atoms can be avoided, sputtering causing direct material removal; this enables a mark to be applied with a controlled depth and good resolution. Typically Gallium ions are used, but a beam of other suitable ions may alternatively be used.
It is thought that each incident ion displaces a number of carbon atoms from their sites to create interstitials and vacancies in the diamond crystal. As the amount of damage (crystal lattice disorder) increases there is a tendency for the diamond sp3 bonds to be replaced by the graphite like sp bonds. These bonds can be attacked by a chemical etch to remove the disordered layer. By limiting the dose, and providing there is sufficient dose, the incident ions cause disordering that converts the diamond to a graphite-like or other non-diamond structure that can be cleaned using, for example, a powerful oxidizing agent, such as molten potassium nitrate, at a temperature of approximately 380-550 Centigrade for a period of between a few minutes and several hours.
The use of potassium nitrate has been found to be more effective in removing disordered diamond than other known processes, thus allowing a mark of a given depth to be produced with a relatively low dose of ions.
Other suitable oxidising agents may be molten compounds such as alkali metal salts; compounds in the form XnYm where the group X may be Li+, Na+, K+, Rb+, Cs+ or

other cation, and the group Y may be OH", NO3-. O22-, O2-, CO32 or other anion, the integers n and m being used to maintain charge balance. Mixtures of such compounds may be used. Air or other oxygen-containing gases may also be present.
As an alternative, the disordered layer of the diamond can be removed using an acid or potassium nitrate dissolved in acid. However, the use of, for example, molten potassium nitrate eliminates acid fumes. Furthermore, the need to dispose of spent acid is eliminated, thereby offering safety, environmental and economic benefits.
It is required to minimise the depth of disordering inflicted by the ion beam on the surface of the diamond. The depth of disordering is determined by the range of ions. For 50 keV Gallium, this range is about 30 nm. The minimum dose may be around 1013 / cm2 and is preferably about 1014/cm2 to 1015/cm2, but good marks can be applied
with a fairly modest dose, the preferred maximum dose being about 1016/cm2 or even
Up to about 1017 /cm . However, the dose depends upon the ions being used and their energy (as measured in keV). The ion beam dose is a total number of incident ions per unit area at the sample surface, during the marking. The beam current may be about 0.5 nA, and the beam energy not less than about 10 keV or about 30 keV and/or not greater than about 100 keV or about 50 keV.
It has been found that if depth of mark is plotted against ion beam dose for a series of different beam energies, there is an increase of depth of mark with increasing beam energy. Characteristics of the mark may be optimised by selecting from the dose/energy combinations which will result in the desired depth of mark.
The region to be marked and/or the surrounding area may be coated with an electrically conducting layer, for instance gold, prior to forming the mark, so that an electrical connection can be provided before marking with an ion beam, to prevent charging. The thickness of the gold, or other coating alters the variation of depth of the mark with beam energy and may thus be chosen to optimise the mark produced. However, it is preferred to irradiate the region to be marked with a low energy source of electrons

(e.g. around 1-100eV) from, for example, an electron flood gun, during the marking process to prevent charging.
If a focused ion beam is used to form the plurality of grooves, the accuracy of the method is such that no masking is required: the ion beam is applied directly to the surface of the diamond at the positions where the grooves are required to be formed. However, if others less accurate mediods of forming the grooves are to be used, then it may be necessary to mask the areas between the grooved areas to avoid marking them.
In accordance with the third aspect of the present invention, there is provided apparatus for viewing a mark on the surface of a diamond or gemstone, said mark comprising a pluralfty of grooves which produce a visible diffractive effect when lit and magnified, the apparatus comprising two illumination means for illuminating the mark with light rays each at an angle which corresponds to the diffraction angle of light of a predetermined wavelength or band of wavelengths, the illumination means being such that the light rays are at substantially the same angle to the normal to said surface, but, as seen looking normal to said surface, are in substantially opposite directions, and viewing and magnification means for viewing said mark and for magnifying the viewed image of said mark. The invention also extends to a method of viewing the mark corresponding to the apparatus defined above.
The mark is preferably viewed against a dark background, ie. it is preferred that the illuminating light is substantially prevented from reflecting through the stone and appearing directly behind or close to the mark. It will be apparent to a person skilled in the art that, in order to achieve this, the angle and direction from which the illuminating light is supplied (and hence the orientation and spacing of the lines) must be chosen so as to ensure that no light can follow the undesired path.
The typical range of magnification required to view the mark is x10 to x50.

The distance between the plurality of grooves and the angle of the directional light determines the colour which the mark will appear when viewed. In general, for a diffraction grating:

d.sinθ = ±n.λ
where d is the distance between each groove, θ is the angle of the incident light, λ is the wavelength of the diffracted light and n is an integer. Preferably n=l.
Thus, when a mark has been formed on a diamond, d and n are fixed, and the wavelength of diffracted light, i.e. the colour which the mark will appear when viewed, can be varied by varying the angle of incident light. Thus, if it is desired that the mark appears blue when viewed, then the angle of the incident light, i.e. G, is set so that X is around 450nm, using the above equation. Similarly, if the mark is to appear red, then 0 is set so that X is around 620nm.
In one embodiment of the apparatus according to the third aspect of the present invention, the illuminating means may comprise a light source and an opaque screen located in the incident light path, the screen having two apertures formed therein, the apertures being formed on either side of a generally central position such that two angular directional light sources are produced. The distance between the apertures determines the angle of the incident light sources. However, it is envisaged that the directional light source(s) may be provided by any convenient means, e.g. two separate light sources. A conventional microscope may include illumination means comprising a circular ring-shaped source comprising optical fibres illuminated by a remote tungsten light bulb. The illumination means of the present invention can be obtained by masking off all but two diametrically opposite sections of the illuminator.
Preferred Embodiment
Embodiments of the present invention will now be described by way of examples only and with reference to the accompanying drawings, in which:

Figure 1 is a magnified schematic diagram of the type of mark which is formed using the method and apparatus of the first and second aspects of the present invention;
Figure 2 is a further magnified cross-sectional view along line A - A of Figure 1; and
Figure 3 is a schematic view of an embodiment of apparatus according to the third aspect of the present invention.
Referring to Figure 1 of the drawings, a mark in the form of an alphanumeric character may be formed by means of a plurality of equally spaced, parallel elongate grooves 10 each separated by a distance d. Each groove 10 may have a generally square or rectangular cross-section, as shown in Figure 2. Alternatively, a sinusoidal profile may be preferred to reduce unwanted higher order diffraction.
Example
A specific method of forming each groove will now be described.
A diamond gemstone is mounted in a suitable holder and placed in a vacuum chamber equipped with a focused ion beam source such as supplied by FEI or Micrion. During exposure, the region to be marked may be irradiated using an electron fiood gun supplied by Micrion, providing a low energy, e.g. 1-100 eV, source of electrons, to prevent the diamond from becoming charged.
Using a focused ion beam with a raster scan or similar to scan the beam with, for instance, electrostatic deflection (as an alternative, the diamond may be moved but this is less practical), and optionally any suitable software for controlling the ion beam, a series of closely spaced parallel lines are ' written' on the diamond facet.
The sample is removed from the vacuum chamber, placed in a stainless steel crucible, and covered with a powerful oxidising agent, such as molten potassium nitrate, for a

period of around one to two hours. The sample is subsequently cooled and removed from the potassium nitrate before being cleaned using water and ethanol, thereby removing the portions of the diamond surface which have been disordered by the ion beam, and leaving a series of closely spaced grooves each around 30 - 35 nm deep, with no evidence of blackening.
Upon examination before cleaning, the exposed region is identifiable by its graphitelike appearance when examined, for example, in a reflected light microscope. Such a mark would not be acceptable to a diamond grader, in that it would substantially reduce the'clarity grade of the diamond. However, after cleaning using the powerful oxidising agent, the mark is not easily visible in a microscope, with no contrast between the mark and surrounding areas. The mark only becomes visible when illuminated by preferably two directional light sources at an angle which corresponds to the angle of diffracted light of a particular wavelength, for example blue light, at which time the mark appears blue. Such a mark is acceptable to a diamond grader in that it does not detrimentally affect the clarity grade of the diamond.
The closely spaced grooves are preferably formed within an 'invisible outline' of an alphanumeric character or the like, as shown in Figure 1 of the drawings.
Referring now to Figure 3 of the drawings, a method and apparatus for viewing the mark produced by the process described above will now be described by way of example only.
The marked diamond 104 is placed on the viewing surface 100 of a conventional microscope 102. The diamond 104 is illuminated by two directional light sources 106 having an angle 6 relative to the vertical axis Y. As described above, 6 is chosen so that the mark appears to be, for example, blue or red, as desired. Thus, if the mark is to appear blue, and d is approximately 1200nm, then 6 is chosen to satisfy:
d.sinθ = (approximately) 450nm

where n=l and 450mn is the approximate wavelength of blue light, which is the wavelength of the diffracted light at X in Figure 3. In this case, θ = 22o.
The directional light sources may be provided by a generally ring-shaped illuminator, all but two diametrically opposite portions thereof being masked off. However, any suitable light source may be used to produce the same effect
Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive as opposed to an exclusive or exhaustive sense, that is to say, in the sense of "including, but not limited to".
The present invention has been described above purely by way of example, and modifications can be made within the spirit of the invention, which extends to the equivalents of the features described.




We Claim:
1. A method of forming a mark on a surface of a diamond or gemstone, which mark comprises one or more unitary indicia, the method comprising the step of forming a plurality of grooves on the surface of the diamond or gemstone, which grooves define the indicium or indicia, the mark being such that it cannot be distinguished by the naked eye, the grooves producing a visible diffraction effect under appropriate lighting and magnification conditions.
2. A method according to claim 1, wherein said mark does not detrimentally affect the clarity grade of the diamond.
3. A method of forming a mark on a surface of a diamond or gemstone, which mark comprises one or more unitary indicia, the method comprising the step of forming a plurality of grooves on the surface of the diamond or gemstone, which grooves define the indicium or indicia and produce a visible diffraction effect under appropriate lighting and magnification conditions, without detrimentally affecting the clarity grade of the diamond or gemstone.
4. A method according to any one of the preceding claims, wherein said mark is in the form of one or more alphanumeric characters or the like which cannot be read by the naked eye.
5. A method according to any one of the preceding claims, wherein the mark is a brand or quality mark.
6. A method according to any one of the preceding claims, wherein, in order to form said grooves, respective portions of the surface of the diamond or gemstone are irradiated so as to cause the crystal lattice to become disordered, and the disordered crystal lattice is removed.

7. A method according to claim 6, wherein the disordered crystal lattice is removed by means of a highly oxidising agent.
8. A method according to claim 7 wherein said highly oxidising agent is molten potassium nitrate.
9. A method according to claim 7, wherein said highly oxidising agent is a compound in the form XnYm, where the group X is Li+, Na+, K+, Rb+, Cs+ or other
cation, or mixtures thereof, and the group Y is OH', NO3-, O22-, O2- ', CO32- or other anion, or mixtures thereof, the integers n and m being used to maintain charge balance.
10. A method according to any one of the preceding claims, wherein said grooves are formed by means of a focused ion beam.
11. A method according to claim 10, wherein said focused ion beam has a beam energy of 50 keV or less.
12. A method according to claim 10 or 11, wherein said focused ion beam has a beam current of about 0.5 nA.
13. A method according to any one of claims 10 to 12, wherein the dosage of ions provided by said focused ion beam is approximately 10 16 /cm to 10 16 /cm .
14. A method according to claim 13, wherein said dosage is approximately 10 /cm to 1016/cml
15. A method according to any one of claims 10 to 14, wherein the region of said surface of a diamond or gemstone to be marked is irradiated with a low energy source of electrons, in order to eliminate charging.
16. A method according to claim 15, wherein the low energy source of electrons is an electric flood gun.

17. A method according to anyone of the preceding claims, wherein at least some of said grooves are parallel, elongate and substantially equally spaced apart.
18. A method according to claim 17, wherein a plurality of intersecting sets of grooves are formed so as to produce a cross-hatched effect.
19. A method according to anyone of the preceding claims, wherein said diamond is a gemstone diamond.
20. Apparatus for forming a mark on a surface of a diamond or gemstone, which mark comprises one or more unitary indicia, comprising means for forming a mark on the surface for guiding the forming means relative to the surface so that there is formed a plurality of grooves on said surface of the diamond or gemstone, the mark being such that it cannot be distinguished by the naked eye, the grooves defining the indicium or indicia and producing a visible diffraction effect under appropriate lighting and magnification conditions.
21. Apparatus for forming a mark on the surface of a diamond or gemstone which mark comprises one or more unitary indicia, comprising means including software for forming a plurality of grooves on the surface of the diamond, the grooves defining the indicium or indicia and producing a visible diffraction effect under appropriate lighting and magnification conditions, without detrimentally affecting the clarity grade of the diamond or gemstone.
22. Apparatus according to claim 20 or 21, wherein said means for forming said plurality of grooves comprises means for irradiating portions of said diamond or gemstone so as to cause the crystal lattice thereof to become disordered and produce a disordered layer, and means for removing said disordered layer.
23. Apparatus according to anyone of claims 20 to 22, wherein said means for irradiating portions of said diamond comprises a focused ion beam.

Apparatus according to claim 23, wherein said focused ion beam has a beam energy of 50 keV or less.
25. Apparatus according to claim 23 or 24, wherein said focused ion beam has a beam current of about 0.5 nA.
26. Apparatus according to any one of claims 23 to 25, wherein the dosage of ions provided by said focused ion beam is approximately 10 /cm to 10 /cm .
27. Apparatus according to claim 26, wherein said dosage is approximately 1016/cm2 to 1016/cml
28. Apparatus according to any one of claims 20 to 26, further comprising means for irradiating the region of said surface of a diamond to be marked with a low energy source of electrons, in order to eliminate charging.
29. A diamond or gemstone having a mark formed thereon by means of the method according to any of claims 1 to 19.
30. A method of viewing the mark on the surface of a diamond or gemstone of claim 29, in which an apparatus is used which comprises means for illuminating the mark with light rays each at an angle which corresponds to the diffraction angle of light of a predetermined wavelength or band of wavelengths, the illumination means being such that the light rays are at substantially the same angle to the normal to said surface, but, as seen looking normal to said surface, are in substantially opposite directions, and viewing and magnification means for viewing said mark and for magnifying the viewed image of said mark, and viewing the mark using the viewing and magnification means.
31. A method of viewing the mark on the surface of the diamond or gemstone of claim 29, comprising the steps of illuminating the mark with light rays each at an angle which corresponds to the diffraction angle of light of a predetermined wavelength or band of wavelengths, the light rays being at substantially the same angle to the normal to

said surface, but, as seen looking normal to said surface, being in substantially opposite directions, and viewing said mark and magnifying the viewed image of said mark.
32. A method according to claim 30 or 31, comprising the step of choosing the angle
and direction from which the illuminating light is supplied so as to view the mark
against a relatively dark background.
33. A method of forming a mark on a surface of a diamond or gemstone,
substantially as herein described with reference to the accompanying drawings.
34. Apparatus for forming a mark on a surface of a diamond or gemstone,
substantially as herein described with reference to the accompanying drawings.
35. The method of claim 30 or 31, wherein the apparatus is substantially as herein
described with reference to Figure 3 of the accompanying drawings.
36. A method of viewing a mark formed on the surface of a diamond or gemstone,
substantially as herein described with reference to Figure 3 of the accompanying
drawings.
37, A diamond or gemstone having a mark formed thereon by the method according to claim 33.


Documents:

in-pct-2000-0153-che abstract granted.pdf

in-pct-2000-0153-che claims duplicate.pdf

in-pct-2000-0153-che claims granted.pdf

in-pct-2000-0153-che description (complete) duplicate.pdf

in-pct-2000-0153-che description (complete) granted.pdf

in-pct-2000-0153-che drawings duplicate.pdf

in-pct-2000-0153-che drawings granted.pdf

in-pct-2000-153-che-abstract.pdf

in-pct-2000-153-che-claims.pdf

in-pct-2000-153-che-correspondence others.pdf

in-pct-2000-153-che-correspondence po.pdf

in-pct-2000-153-che-description complete.pdf

in-pct-2000-153-che-drawings.pdf

in-pct-2000-153-che-form 1.pdf

in-pct-2000-153-che-form 3.pdf

in-pct-2000-153-che-form 5.pdf

in-pct-2000-153-che-other documents.pdf

in-pct-2000-153-che-pct.pdf


Patent Number 201608
Indian Patent Application Number IN/PCT/2000/153/CHE
PG Journal Number 05/2007
Publication Date 02-Feb-2007
Grant Date 10-Aug-2006
Date of Filing 28-Jun-2000
Name of Patentee GERSAN ESTABLISHMENT
Applicant Address AEULESTRASSE 5, 9490 VADUZ, LIECHTENSTEIN, A COMPANY UNDER THE LAWS OF LIECHTENSTEIN.
Inventors:
# Inventor's Name Inventor's Address
1 SMITH, JAMES GORDEN CHARTERS 5 GLYNSWOOD HIGH WYCOMBE, BUCHINGHAMSHIRE HP 13, 5 QL, UK.
PCT International Classification Number B44B7/00
PCT International Application Number PCT/GB98/03889
PCT International Filing date 1998-12-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 9727364.3 1997-12-24 U.K.