阅读说明：本技术 一种用于宝石标记的透光标记 (Light-transmitting mark for marking precious stone ) 是由 安德烈·阿列克谢耶维奇·伊欧宁 谢尔盖·伊万诺维奇·库德里亚索夫 尼基塔·亚历山德罗维奇·斯米尔 于 2019-05-16 设计创作，主要内容包括：本发明涉及用于标记宝石的标记,包括钻石或闪光体,并携带各种目的的信息,例如,识别码,尤其涉及使用放大镜和各种类型的显微镜,通过肉眼无法的看到的标记,尤其涉及位于钻石或闪光体体积内部的标记而不会影响其特征,从而对钻石或闪光体的质量产生损害。所要求保护的解决方案的技术问题是扩大在具有不同含量的自然杂质(包括氮)的钻石上使用标记的范围,以实现一种技术结果,即解决上述问题,同时简化标记过程并减少在标记期间对钻石的品质的影响。所述技术结果是通过使用位于钻石或闪光体体积内的透光标记实现的,该标记包含预定义的编码信息,并由一组给定的微米或亚微米尺寸的透光元素组成,这些透光元素是钻石或闪光体晶格中原子缺陷的浓度增加的区域,其中钻石晶格中的原子缺陷是空位和间隙,并且其中信息被编码在所述原子缺陷的浓度增加的至少两个区域中。(The present invention relates to a mark for marking a gemstone, including a diamond or a glitter, and carrying information for various purposes, such as an identification code, and more particularly to a mark that is invisible to the naked eye using a magnifying glass and various types of microscopes, and more particularly to a mark that is located within the volume of the diamond or glitter without affecting its characteristics, thereby causing damage to the quality of the diamond or glitter. The technical problem of the claimed solution is to extend the range of using marking on diamonds with different contents of natural impurities, including nitrogen, to achieve a technical result, i.e. to solve the above mentioned problems, while simplifying the marking process and reducing the impact on the quality of the diamond during marking. The technical result is achieved by using a translucent mark located within the diamond or flash volume, the mark containing predefined encoded information and consisting of a set of light transmitting elements of a given micron or sub-micron size, which are regions of increased concentration of atomic defects in the diamond or flash crystal lattice, wherein the atomic defects in the diamond crystal lattice are vacancies and interstitials, and wherein the information is encoded in at least two regions of increased concentration of said atomic defects.)

1. A light transmissive marking located within the volume of a diamond or a flash body, said marking containing predefined coded information and consisting of a set of light transmissive elements of a given micron or sub-micron size, which are regions of increased concentration of atomic defects in the diamond or flash body lattice,

it is characterized in that

The atomic defects in the diamond or flash crystal lattice are vacancies and interstitials, and wherein

The information is encoded in at least two regions where the concentration of atomic defects increases.

2. A tag as claimed in claim 1, characterized in that said information is encoded in the mutual spatial arrangement of said regions.

3. The marking of claim 1, wherein the information is encoded in a variation of a concentration of the atomic defects in the region.

4. A tag as claimed in claim 1, characterized in that the information is encoded in a variation of the size of the area.

5. A tag as claimed in claim 1, characterized in that the information is encoded in a variation of the geometry of the region.

Technical Field

The present invention relates to a mark for marking a gemstone, including diamonds and glitters, and carrying information such as identification codes for various purposes known to only a small group of people, and more particularly to marks in cut faces (glitters) and uncut natural and synthetic diamonds (hereinafter simply referred to as diamonds) that cannot be seen by the naked eye using a magnifying glass and various types of microscopes without affecting their characteristics, thereby causing damage to the quality of the diamonds.

Background

The problem of generating images in the volume of a diamond crystal, for example to mark a diamond to identify and track the diamond, without compromising its quality and ultimately its cost, is well known, as some properties of the diamond make it very difficult to generate such a pattern.

It is well known that diamond is transparent at wavelengths in the visible spectrum range 400-700nm, a very hard material that is easily broken under strong mechanical stress or excessive local heating, and therefore the marking images, preferably in the form of readable codes, samples, serial numbers and alphanumerics, must be very small and inaccessible to mechanical and chemical action to avoid unauthorized detection or removal without altering the appearance and commercial value of the diamond.

Various methods are known for applying images to the surface of faceted diamonds. However, the facets of a faceted diamond surface are oriented in different directions and are of small dimensions and may not be capable of being marked and detected if the stone is inserted into the frame. In addition, the surface markings can be destroyed by mechanical and chemical treatments, such as polishing, etching. Thus, especially for expensive diamonds, it is preferable to create the marking image under the surface layer of the diamond without altering the outer surface.

The generation of two-dimensional and three-dimensional images in a diamond volume is a promising technique, whether for the purpose of storing information or for use in optical techniques.

Labels that are opaque to optical radiation are known for several reasons, including: the development of a volume of disturbed diamond microstructure surrounding the natural impurity, or the incorporation of impurity ions (e.g. phosphorus) into the diamond structure, forms a detectable defect region.

It is known to obtain a marking by a method (RU 2357870C 1; WO 2006/092035; US 7284396B 1) and a system for laser marking of diamonds, wherein an authentication code in the form of a mark is engraved in a diamond volume, wherein an engraved authentication code in the form of a mark in a diamond volume is proposed, generated by exposure to a controlled series of laser pulses in the femtosecond range (from a few femtoseconds to 200 picoseconds), and the energy of each laser pulse is above a threshold for damaging the diamond crystals. In this case, the damage is caused by defects or impurities (nitrogen, hydrogen, sulfur, phosphorus, nickel, boron atoms, etc.) present in the material of which the recording laser beam reaches its minimum lateral dimension and maximum intensity. In this case, the radiation is concentrated in the diamond volume, resulting in a grown defect microstructure opaque to the light radiation at randomly distributed locations of the designated defects. These marks consist of carbon in non-diamond form and are formed by several microscopic spot marks of a size of a few micrometers (2-5 μm), the distance between adjacent spot marks being about 50 μm, wherein the area of the array of spot marks is 250 x 250 μm, which needs to be read using a special detection device. However, at the same time:

the point marks produced are larger than the natural defects in the diamond, thereby reducing the quality and commercial value of the diamond;

the mutual arrangement of the marked points can only determine certain geometrical combinations thereof, for example, the vertices of a virtual triangle based on three points, and not the image of the triangle itself;

-after the diamond has been faceted, when the position of the partial point marks relative to the facet and between them can be changed, it is not reliable to authenticate the stone based on the mutual spatial arrangement of the point marks generated in the rough diamond;

due to the random arrangement of natural defects in diamonds, it is not possible to generate miniature images with visual and semantic effects.

It is known that a marking is obtained by a method (SU 329899 a) in a transparent material in which a latent image is generated in a transparent diamond plate having a size of 50 x 50mm and a thickness of 300 μm. A metal mask with a thickness of 50 μm is applied to the surface of such a sample, wherein the desired image is etched in the mask using photolithography, and the sample is then bombarded with phosphorus ions. In this case, in addition to the appearance of a coloured surface image, an internal image is also present, and the plate is then subjected to a subsequent thermal annealing, followed by the disappearance of the coloured image. The resulting image is thermally stable up to 1200 c and is not destroyed by the action of light, electric fields and magnetic fields. However, since the lattice hardness is high, the penetration depth of phosphorus ions into diamond and the depth of internal image placement cannot be large, and therefore, a thin surface layer containing a mark can be removed by polishing or etching, and the content of phosphorus impurities in diamond increases and the presence of visually distinguishable images affects its commercial value.

It is known a mark obtained in the synthesis of diamond by chemical vapour deposition from the vapour phase by a method (RU 2382122C 1) in which a dopant of at least one chemical element, such as nitrogen, is incorporated into a layer of synthetic diamond material in the form of defect centres which, when excited, emit radiation having a characteristic wavelength. In this case, the dopant forms a production marking or identification marking in the form of a layer, in which fluorescence with a peak at 575nm and/or 637nm occurs under suitable light excitation, which practically disappears immediately when the excitation source is switched off. The identification (detection) of the manufacturing mark or the identification mark can be carried out, for example, visually or using special optical equipment. In general, it is preferred that the observer directly identifies the production marking or the identification marking with the naked eye, since this method allows spatial information, in particular binocular or depth information, to be obtained.

However, it is well known that the trapping of impurities depends on the growth region involved in the process, e.g., the growth region {111} typically traps a higher concentration of impurities than the growth region {100}, thereby distorting the resulting mark. In addition, in this method of marking synthetic diamond growth, additional impurities, defects are introduced into the diamond, which does not improve the quality of the diamond.

In addition, the marking cannot be used to mark natural or synthetic diamonds grown using other techniques.

Labels comprising diamond nanocrystals having active centers that fluoresce under the influence of external radiation are known for use in article protection methods: NV centres (RU2357866C1) or N-E8 centres (RU 2386542C 1) are obtained by exposing diamond crystals to an electron or ion beam, followed by annealing at high temperature, to form NV centres or N-E8 centres which are relatively uniformly located throughout the volume of the nanocrystal. Nanocrystals containing the designated optically active centers are then introduced into the article and the presence or absence of the label is judged by the presence of fluorescence upon excitation light irradiation and/or dual radio optical resonance.

It is known that the detection of such fluorescent radiation of NV centres (RU2357866C1) can be carried out in a device comprising an optical excitation source in the wavelength range 500-.

In this case, the conclusion that the article contains such a marking is drawn by: the spectral characteristics of the fluorescence are consistent with the known spectral characteristics of the fluorescence of the NV centres and the difference in the fluorescence signals when excited simultaneously with and without the resonant microwave field, indicating the presence of diamonds with NV centres in the article.

However, a tag consisting of diamond nanocrystals enriched in N-V or N-E8 centers can be effectively used on an object having a relatively porous surface, effectively retaining nanodiamonds in the pores of the object. Nanodiamonds on the smooth polished surface of the faceted diamond can be easily removed.

The closest analogue is a mark produced using a method (RU2465377) for producing a transmission image within a diamond, the method comprising producing an image within the diamond, the image consisting of a set of given micron or sub-micron sized transmission elements, which are NV centre clusters that fluoresce under excitation radiation, the NV centre clusters being formed by: treating the diamond with working optical radiation focused in a focal zone located in a region of the desired location of the NV centre cluster and providing working ultrashort radiation pulses to form vacancy clusters in the designated focal zone while providing fluence at the designated focal zone that is below a threshold fluence at which the diamond is converted locally to carbon in graphite or other non-diamond form; annealing at least designated regions of the expected locations of the clusters of NV centres, which can drift the vacancies formed in those regions, and form NV centres grouped in clusters in the same region as the cluster of vacancies; exciting at least these regions of the picture element by exciting light radiation providing excitation of NV centres, thereby controlling the generated picture element based on the fluorescence light distribution of the NV centres; a digital and/or three-dimensional model of the generated image is formed. Those images of the cluster of NV centres that are generated by the diamond crystals cannot be seen by the naked eye through a magnifying glass, and any type of optical or electron microscope.

However, it is not possible to generate marks in diamond without (or very small) natural nitrogen incorporation by this method, because it is not possible to ensure formation of NV centre clusters, whereas at high concentrations of impurities in the diamond, concentration quenching of so-called fluorescence is observed or no significant drift of vacancies is observed due to their being trapped by closely spaced defects.

Disclosure of Invention

The technical problem of the claimed solution is to extend the range of using marking on diamonds with different contents of natural impurities, including nitrogen, to achieve a technical result, i.e. to solve the above mentioned problems, while simplifying the marking process and reducing the impact on the properties of the diamond during marking.

The technical result is achieved by using a translucent mark located within the diamond or flash body volume, the mark containing predefined encoded information and consisting of a set of given micron or sub-micron sized translucent elements which are regions of increased concentration of atomic defects in the diamond or flash body crystal lattice, wherein the atomic defects in the diamond or flash body crystal lattice are vacancies and interstitials, and wherein specified information is encoded in at least two regions of increased concentration of said atomic defects.

Another feature is that the information is encoded in a mutual spatial arrangement of the regions.

Another feature is that the information is encoded in a variation of a concentration of said atomic defects in said region.

Another feature is that the information is encoded in variations of the size of the region.

Another feature is that the information is encoded as a change in geometry of the region.

After the formation of relatively intense lasers in the picosecond and subpicosecond range, the physical effects associated with the accumulation of atomic defects in transparent crystals under the influence of laser pulses with high peak power were reported as early as the 80 s of the 20 th century. With repeated exposure to laser pulses, an increase in the absorption of the crystal and a gradual decrease in the radiation intensity are observed. In this case, the change occurring in the crystal cannot be visually observed until its optical breakdown.

Later, the accumulation of laser-induced defects in crystals was investigated from the perspective of laser processing of materials. The "cumulative" effect, which represents optical damage to a diamond after exposure to many laser pulses, is indicated in [ Konenko et al, Microprocessing of the diamond by induced ferromagnetic glasses pulses// Applied physics A.2008.Vol.90.P.645 ]. The authors attribute this effect to the "appearance and accumulation of stable nanoscale defects".

In the modern scientific literature, these effects are related to the accumulation of atomic defects, i.e. vacancies and interstitials, in the crystal lattice of diamond crystals.

To form a light transmissive mark in a diamond volume according to the invention, laser pulses in the visible or near infrared range of femtosecond or picosecond duration are focused at a predetermined depth within the volume. In the focal region where the highest intensity is reached, electrons are stripped from the atomic electron shells and form an electron-hole plasma. If the laser pulse energy is not large, the density and temperature of such a plasma is not sufficient to cause irreversible macroscopic damage to the crystals forming non-diamond forms of carbon (graphite, amorphous carbon), cracks, etc. In this case, there was no visible damage to the crystal; however, during the interaction of the plasma with the atoms of the crystal lattice, there is the possibility of individual atoms transitioning from the nodes of the crystal lattice to the interstitial spaces, i.e. forming pairs of atomic defect vacancies-interstitial spaces.

The probability of forming vacancy-interstitial pairs is small due to the high binding energy of the atoms in the crystal lattice. Thus, to produce its reliably detectable concentration, a number of series of ultrashort pulses are sent to the same focal region, resulting in a gradual accumulation of vacancies and gaps. In practice, it is sufficient that the concentration of vacancies and interstitials in the focal region only slightly exceeds the natural (background) values in the crystal. When the vacancy drifts, it may partially recombine with the interstitials, especially as the temperature increases. However, it is known from practice that complete recombination does not occur within a reasonable time and that the concentration of vacancies and interstitials remains elevated.

In this case, the energy of the laser pulses and their total number are chosen in such a way that there is no macroscopic damage visible to the crystal formation in the focal area due to local transformation to carbon in a non-diamond form.

Since the absorption of light by the vacancies and interstitials is minimal, and their concentration increase in the focal region is relatively small, this region appears to be absolutely transparent and indistinguishable from the rest of the crystal even under a powerful microscope.

After forming a region of increased vacancy and interstitial concentration, the focal region is moved within the crystal to a new predetermined position (or the crystal itself is moved accordingly) and a new such region is formed.

Due to the sequence of such operations, the transparent mark is formed inside the diamond volume and consists of a given set of transparent (invisible under normal conditions) elements of micron or submicron size, wherein said elements represent regions of increased concentration of atomic defects, i.e. vacancies and interstitials, in the crystal lattice.

The label can be read (detected) by its fluorescence under the influence of the excitation light radiation. For this purpose, a constant laser radiation in the blue or green range of the spectrum which is most effective for exciting vacancies is transmitted to the region which marks the intended position. Under the influence of said radiation, the marking elements start to fluoresce in the red and near infrared range of the spectrum. For observing their fluorescence, microscopes equipped with filters are used which can block the excited laser radiation and transmit the fluorescence radiation of the marking.

The information in the tag may be encoded in the mutual spatial arrangement of the tag elements, the combination of which may form a planar or three-dimensional image, a barcode, a QR code, a bit sequence, etc.

Information may also be encoded as a change in the concentration of atomic defects in the element, as a change in the size or geometry of the element. In this case, in order to control the concentration of atomic defects, the energy and/or the total number of laser pulses affecting a given area will be changed, and the size and geometry of the elements, e.g. the focusing conditions, will be controlled, the focal length of the focusing elements will be changed, or the focusing area will be slightly shifted, during the action of a series of laser pulses.

The main difference with the closest analogue, i.e. the mark created using the method of creating a transmission image inside a diamond (RU2465377), is that the elements of the mark consist of new physical objects, i.e. vacancies and interstitials, rather than Nitrogen Vacancy (NV) centers. This allows the use of new marks on crystals with any nitrogen impurity content, and furthermore the mark creation process means no annealing (as opposed to Nitrogen Vacancy (NV) centres), which has a positive effect on simplifying the marking process and significantly reduces the likelihood that diamond properties may be affected during the marking process.

Drawings

The invention is illustrated by the accompanying drawings:

FIG. 1 is a marking system for forming a light transmissive mark within a diamond or a flash;

FIG. 2 is a single marking element, which is a region of increased concentration of atomic defects (i.e., vacancies and interstitials);

fig. 3 is a system for detecting light-transmissive indicia.

Detailed Description

The laser 1 (fig. 1) of the marking system generates working radiation 2 in the form of a series of pulses, the parameters of which are set such that diamond is not converted into another non-diamond form of graphite or carbon. The radiation is focused by a focusing subsystem 3 (lens, objective lens) and forms the waist of a beam 4 in a focusing region inside the volume of a diamond 5 on the surface of which a polished optically transparent pavilion is prefabricated. The diamond 5 is mounted on a subsystem 6 for movement, which is configured to move along three spatial coordinates and two further angular coordinates. The laser radiation 2 (fig. 2) results in the formation of atomic defects in the region of micron or submicron size 7. The area 7 is a single element of the mark. After the marking elements have been formed in a given area inside the diamond, the subsystem for moving the diamond moves the diamond in space according to the digital model of the image to be recorded in the crystal volume input by the user, and then repeats the above operations.

The previously generated mark was detected by detecting the fluorescence of atomic defects, i.e. vacancies and interstitials, in the diamond lattice according to the protocol shown (fig. 3).

The system for detecting a transparent mark (fig. 3) comprises a laser 8, which laser 8 generates excitation light radiation 9, which is reflected by a semi-transparent mirror 10 and focused by a focusing subsystem 11 within a diamond 12, which focusing subsystem 11 is mounted on a subsystem 13 for movement, which subsystem 13 for movement moves it in space along three spatial coordinates and two further angular coordinates into the area of the desired position of the mark 14. Further, the lateral dimension of the waist is greater than or equal to the lateral dimension of the mark.

Due to the optical excitation, the marking elements emit fluorescent radiation 15, a portion of the fluorescent radiation 15 being collimated by the focusing subsystem 11, passing through the semi-transparent mirror 10 and then through a filter 16, which filter 16 passes the fluorescent radiation and blocks the scattered laser radiation. The radiation is then registered by a registration subsystem 17, e.g. a camera with a CCD matrix. The signal from the registration subsystem 17 containing the image of the fluorescent marker 18 is fed to the subsystem for registration and decoding of the signal 19, which displays the information encoded in the marker.