CN106340239A - Optical anti-counterfeiting mark formed on titanium dioxide mono-crystal surface by silver nanoparticles and manufacturing method thereof - Google Patents
Optical anti-counterfeiting mark formed on titanium dioxide mono-crystal surface by silver nanoparticles and manufacturing method thereof Download PDFInfo
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- CN106340239A CN106340239A CN201610918898.XA CN201610918898A CN106340239A CN 106340239 A CN106340239 A CN 106340239A CN 201610918898 A CN201610918898 A CN 201610918898A CN 106340239 A CN106340239 A CN 106340239A
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- counterfeiting mark
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention belongs to the technical field of anti-counterfeiting and particularly relates to an optical anti-counterfeiting mark formed on a titanium dioxide mono-crystal surface by silver nanoparticles and a manufacturing method thereof. According to the optical anti-counterfeiting mark, a silver nitrate solution is dropped onto the surface of a titanium dioxide mono-crystal sheet at first; then the surface is irradiated by an ultraviolet lamp for a plurality of minutes and the silver nanoparticles grow on the surface of the titanium dioxide mono-crystal; then, a micron-grade photoetching plate sleeves the surface of a sample; meanwhile, the silver nanoparticles are irradiated by monochromatic light; thermal electrons are transferred to have a chemical reaction and a plasma resonance peak position of the silver nanoparticles on the surface of the sample is changed, so that a pattern with a wavelength selecting property is formed. The pattern can be used as a micro-nano-grade anti-counterfeiting mark. The method provided by the invention is simple and feasible and has a very short period; the obtained anti-counterfeiting mark has the wavelength selecting property and high resolution ratio, which are not included in a common paper anti-counterfeiting mark.
Description
Technical field
The invention belongs to field of anti-counterfeit technology is and in particular to a kind of anti-counterfeiting mark and preparation method thereof.
Technical background
Existing anti-counterfeiting technology in the world, is broadly divided into following several:
(1) paper false proof technique
In traditional bank note, there is the paper formula of this country in each state, participates in certain material or element, make in paper
It is difficult to the special paper of print paper money copied.As a rule, the important raw and processed materials of the special paper of currency be cotton fiber with high-quality
Wood pulp assimilation quotient, without any brightening agent, this is the important difference of bank-note paper and other plain papers.However, in banknote stream
During logical, if causing careless through the rinsing of the solution containing brightening agent, in fact it could happen that fluorescent reflection under ultraviolet light；Meanwhile, paper money
Paper hits acid-base material, also can deliquescing, thinning.
In the manufacturing process of special bank-note paper, following false proof handicraft: 1, watermark can also be adopted；2nd, safe line, that is, exist
During papermaking, two compete in strength thin metal wire or plastic cords are embedded in paper using handicraft out of the ordinary；3rd, colored fiber and nothing
Color fluorescent fiber by the fibers of white, blue or other gorgeous colors, or is equably added in paper in paper-making process in proportion
In slurry, or it is added in paper portions.
The shortcoming of paper false proof technology is exactly the limitation of application, and the field in addition to paper can not be applied.
(2) ink false proof process
Ink false proof process is broadly divided into following several: 1, colored fluorescent ink, and it is popular that this kind of ink is seen under popular light
Ink color, but shine in ultraviolet light and lower can send different fluorescence；2nd, colorless fluorescent ink, the printed patterns of this kind of ink exist
It is invisible under natural light, and just can be seen that under ultraviolet light and send light and spacious fluorescence；3rd, magnetic ink, will more than ancient times banknote
Magnetic ink for machine-readable, also increase and fabricates difficulty as a detection by quantitative index；4th, photochromatic printing ink, photochromatic printing ink adopts
A kind of optical variable device out of the ordinary, after being printed as pattern, the color with the difference pattern inspecting angle can flash transformation.This kind of
Ink is cheap to be difficult to purchase, exist must anti-fabricate effect；5th, anti-copy ink, replicates banknote with color copy machine
When, the pattern of this kind of ink printing can produce color conversion, leads to the tone duplicating out complete with source tone at par
Difference；6th, infrared ink, infrared printing ink printed patterns under popular light, colored repercussion, but when being inspected with infrared light instrument
Then achromatization；7th, pearl ink, ink printed patterns with the difference metallic luster end that can flash light and spacious inspecting angle or
Rainbow end.
The false proof shortcoming of ink is that it cannot make the anti-counterfeiting mark of micron, simultaneously by fluorescence Lai false proof, is easier
It is replicated, thus losing antiforge function.
(3) antiforge technique
Antiforge technique is broadly divided into following several:
1st, manual chase intaglio plate, chase intaglio plate by hand with its complex process, pattern uniqueness, with extremely strong can not simulation and
Anti-counterfeiting performance, is that the general currency of countries of the world prints handicraft and currency security handicraft；2nd, intaglio printing, gravure through chasing and
Become, its pattern line is in groove type, the space of a whole page less than forme, and after dope inks out pattern, ink is attached on paper money paper, protrudes
In paper overview.Have that third dimension is strong, logical feature, being touched with handss has concave-convex sense；3rd, rainbow printing, the mass-tone of pattern
Adjust or setting is made up of the color of difference, but the difference color on lines or image is in continuity slowly transition, is very nature；4、
To print, printed using positive back simultaneously, meet x ray fluoroscopy x banknote, the pattern that can be appreciated that the same position of positive back is through tandem docking, group
Become a complete pattern, to by dislocation-free, no stacking phenomenon；5th, wiring printing, same two lines of nominal value decorative pattern are by two kinds
Above color composition, but between color and color, transition is thoughtfully natural, no leak white and overlapping phenomenon；6th, microfilm of characters printing, adopts
Mask-making technology out of the ordinary, word is narrowed down to the degree that naked eyes almost be can't see, prints on banknote, can need to regard by magnifier
Observe.
Antiforge manufacturing technology is easily replicated, thus easily losing antiforge function, is difficult the article of printing at some simultaneously
On be difficult to make anti-counterfeiting mark.
Content of the invention
It is an object of the invention to provide a kind of antifalse effect is good, preparation speed is fast, it is micro- on non-paper article to can be used for
Meter level other optical anti-counterfeiting mark and preparation method thereof.
The optical anti-counterfeiting mark that the present invention provides, is specifically made up of titanium dioxide single crystalline piece and silver nano-grain, wherein silver
The size of nano-particle is between 30 nanometers to 150 nanometers.Referring to Fig. 1, shown in 2,3.
The principle of the invention: various sizes of nano-particle can resonate the light of different wave length, when a branch of monochromatic light exposure
Understand the electronics to surface energy transmission with the granule (as in figure green particles) of this monochromatic photoresonance, surface electronic obtains energy
After overcoming the Schottky barrier of metal semiconductor detection, go in the conduction band of quasiconductor, thus silver atoms reform into silver simultaneously
Ion dissociates and opens, and now the size of Argent grain will change, and the wavelength of its resonance will change.
The manufacture method of the optical anti-counterfeiting mark of the micron level that the present invention provides, specifically comprises the following steps that
(1) first, by ethanol and silver nitrate solution (1 mol/l) according to 1:0.8-1.2 volume ratio (preferred volume ratio is 1:
1) mix homogeneously；Draw 15-30 ul(preferably 20 ul with liquid-transfering gun) mixed solution drops in clearly clean titanium dioxide single crystalline
Piece (crystal orientation: on 110)；Then the monochromatic light exposure sample being 365 nanometers with the uviol lamp of hand-held with wavelength, about 3-5 minute
Afterwards, form silver nano-grain in titanium dioxide single crystalline piece superficial growth, as shown in Figure 1；Use sem observation sample
Violet region, as shown in Figure 2.Can see from above-mentioned sample pictures, a lot of silver of titanium dioxide single crystalline piece superficial growth are received
Rice grain, due to the local surface plasma concussion of these silver nano-grains, so color can be produced；
(2) secondly, sample is placed in water and the solution of ethanol mixing, covers an optics mask, this light in sample surfaces
Learn and the anti-counterfeiting mark pattern (including word, figure etc., such as shown in Fig. 4 (a)) prepared as desired is had on mask, then
With monochromatic light exposure, monochromatic light light intensity is generally 10-18 milliwatt/every square centimeter, irradiation 4-8 minute, due to thermoelectron transfer
There is chemical reaction, so that the plasma resonance peak position of the silver nano-grain of sample surfaces is changed, thus form one having
The pattern of wavelength selectivity, this pattern can be used as anti-counterfeiting mark, referring to Fig. 4 (b) Suo Shi.
The gray-scale maps of anti-counterfeiting mark pattern same position are extracted it can be seen that the pattern worked it out is with respect to light
There is certain broadening for mechanical pattern, but its resolution also can reach 1.24 microns, this result illustrates that this kind of method is worked it out
Pattern can reach micron-sized resolution.See shown in Fig. 4 (c).
In the present invention, optics mask typically uses the preparation of ultraviolet photolithographic method it is also possible to directly buy.Such as the present invention is implemented
The preparation monogram of " fdu " and the pictorial pattern of Fudan University's school badge in example.
In embodiments of the invention, monochromatic light uses 500 nanometers of halfwidths often to put down for 15 milliwatts for 30 nanometers of light intensity
Square centimetre of monochromatic light.
The pattern made by the inventive method is selective for monochromatic light, so, can be Information hiding in optical wavelength
In, thus obtaining the optical anti-counterfeiting mark of micron level.It is made that Fudan University's school badge of a micro-meter scale in the embodiment of the present invention
Pattern is (with 500 nanometers of monochromatic light, 14 mw/cm2, 5 minutes irradiating samples), result shows, ineffective monochromatic light, black and white or coloured silk
Form and aspect machine, or project observation or reflective observing with microscope, all just can only can see the thin of pattern under suitable wavelength clearly
Section.
Advantages of the present invention is as follows
First, raw materials simply easily obtain: 1, titanium dioxide single crystalline piece (110 crystal orientation)；2nd, silver nitrate solution；3rd, optical surface
Tool (can directly be bought, and can reuse, producing for large area needs to change large area mask)；4th, monochromatic
Light source；
Secondly, this manufacture method is simple and the cycle is very short it is only necessary to strictly according to manufacture method operation, a few minutes just can make
Out；
Again, the high resolution of this anti-counterfeiting mark, minimum resolution can reach 1.24 microns, disclosure satisfy that the anti-of the overwhelming majority
Pseudo- needs.This anti-counterfeiting mark has the characteristic of optical wavelength selection, and this is the feature not available for general papery anti-counterfeiting mark.
In sum, the invention provides one kind is quickly easily prepared, had wavelength selectivity and high-resolution anti-counterfeiting label
Know.
Brief description
Fig. 1 is using UV light-induced, in the sample of titanium dioxide single crystalline piece (crystal orientation 110) epontic silver nano-grain
Product photo.
Fig. 2 is sample in cross section schematic diagram.After irradiating monochromatic light, the size of some silver nano-grains there occurs change.
Fig. 3 is the electron scanning micrograph of silver nano-grain.
Fig. 4 is for micro-nano-scale anti-counterfeiting mark pattern optics mask (i.e. mask plate) of the present invention with through monochromatic light exposure
Optical design afterwards and the resolution diagram of pattern.Wherein, a represents the optics of the mask plate of the micro-nano-scale of a hollow out
Photo；B represents and blocks before sample using its mask plate, after being then passed through monochromatic light exposure, the Yin Na that stays on sample
The optical design of rice grain composition；C is that the gray value of black dotted lines (figure c orbicular spot line) in a figure a takes out, same in figure b
(black dotted line schemes c intermediate cam point line) gray value of one position takes out and is compared, and the resolution of the pattern made reaches
1.24 micron.
Fig. 5 utilizes the mask plate of the micro-meter scale of Fudan University's school badge of photoetching technique making, is enclosed within sample surfaces, irradiates
500 nanometers of monochromatic light, obtain the pattern of Fudan University's school badge, and this pattern is observed under the monochromatic light of different wave length simultaneously, obtains
The definition arriving is different.The reflection photo of the image that in Fig. 5, first row shoots for black and white camera, second row is clapped for black and white camera
The transmission photo of the image taken the photograph.
Specific embodiment
Further describe the present invention below by specific embodiment (Fudan University's school badge pattern).
1st, designed and produced the photolithography plate of different size of Fudan University school badge pattern first, this can be by related business
Company customizes.
2nd, first, by ethanol and silver nitrate solution (1 mol/l) according to 1:0.8-1.2 volume ratio (preferred volume ratio
For 1:1) mix homogeneously；Draw 15-30 ul(preferably 20 ul with liquid-transfering gun) mixed solution drops in clearly clean titanium dioxide
Single-chip (crystal orientation: on 110)；Then the monochromatic light exposure sample being 365 nanometers with the uviol lamp of hand-held with wavelength, about 3-5
After minute, form silver nano-grain in titanium dioxide single crystalline piece superficial growth.
3 and then the titanium dioxide single crystalline piece of long good silver nano-grain is put in surface plate, the inside imports ethanol and water
Mixed solution (volume ratio 1:2), covers on the surface of titanium dioxide single crystalline piece with figuratum photolithography plate making.
4th, the monochromatic light exposure after the narrow band pass filter of bromine tungsten filament lamp plus 500 nanometers being filtered on surface plate, now light intensity
The every one-storey house centimetre of about 14 milliwatts, waits about 5 minutes.
5th, examine under a microscope sample pattern, just can obtain carrying the anti-of Fudan University's school badge pattern as show in Figure 5
Pseudo- mark.
Claims (3)
1. the manufacture method of the optical anti-counterfeiting mark that a kind of silver nano-grain is formed on titanium dioxide single crystalline surface, its feature exists
In concretely comprising the following steps:
(1) first, by ethanol and silver nitrate solution according to 1:0.8-1.2 volume ratio mix homogeneously；Draw 15-30 with liquid-transfering gun
Ul mixed solution drops on clearly clean titanium dioxide single crystalline piece, chip crystal orientation: 110；Then use hand-held uviol lamp with
Wavelength is 365 nanometers of monochromatic light exposure sample 3-5 minute, forms silver nano-grain in titanium dioxide single crystalline piece superficial growth；
(2) and then, by sample be placed on water and ethanol mixing solution in, sample surfaces cover an optics mask, this light
Learn, on mask, there is the anti-counterfeiting mark pattern prepared as desired, with monochromatic light exposure, monochromatic light light intensity be 10-18 milliwatt/
Every square centimeter, irradiate 4-8 minute, form an anti-counterfeiting mark pattern having wavelength selectivity.
2. according to claim 1 manufacture method it is characterised in that the size of described silver nano-grain is at 30 nanometers to 150
Between nanometer.
3. a kind of manufacture method described in claim 1 or 2 makes the silver nano-grain obtaining in titanium dioxide single crystalline surface shape
The optical anti-counterfeiting mark becoming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610918898.XA CN106340239B (en) | 2016-10-21 | 2016-10-21 | The optical anti-counterfeiting mark and preparation method thereof that silver nano-grain is formed on titanium dioxide single crystalline surface |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610918898.XA CN106340239B (en) | 2016-10-21 | 2016-10-21 | The optical anti-counterfeiting mark and preparation method thereof that silver nano-grain is formed on titanium dioxide single crystalline surface |
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| Publication Number | Publication Date |
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| CN106340239A true CN106340239A (en) | 2017-01-18 |
| CN106340239B CN106340239B (en) | 2019-04-05 |
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| CN201610918898.XA Expired - Fee Related CN106340239B (en) | 2016-10-21 | 2016-10-21 | The optical anti-counterfeiting mark and preparation method thereof that silver nano-grain is formed on titanium dioxide single crystalline surface |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114648494A (en) * | 2022-02-28 | 2022-06-21 | 扬州市苏灵农药化工有限公司 | Pesticide suspending agent production control system based on factory digitization |
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| CN101219377A (en) * | 2008-01-11 | 2008-07-16 | 山东大学 | Precious metal/one-dimensional titanium dioxide nanostructure composite material and method for producing the same |
| CN101592854A (en) * | 2008-05-26 | 2009-12-02 | 罗挺 | Multichannel laser antifalsification technology of nanometer material |
| CN102696062A (en) * | 2010-05-18 | 2012-09-26 | 韩国科学技术院 | Method for producing an anti-forgery label using a randomly distributed pattern of fine particles formed on a variety of substrates, and method for determining the authenticity of the label |
| CN103257379A (en) * | 2007-11-27 | 2013-08-21 | 3M创新有限公司 | Methods for forming sheeting with a composite image that floats |
| WO2016103132A1 (en) * | 2014-12-22 | 2016-06-30 | Eulitha A.G. | Method for printing colour images |
-
2016
- 2016-10-21 CN CN201610918898.XA patent/CN106340239B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103257379A (en) * | 2007-11-27 | 2013-08-21 | 3M创新有限公司 | Methods for forming sheeting with a composite image that floats |
| CN101219377A (en) * | 2008-01-11 | 2008-07-16 | 山东大学 | Precious metal/one-dimensional titanium dioxide nanostructure composite material and method for producing the same |
| CN101592854A (en) * | 2008-05-26 | 2009-12-02 | 罗挺 | Multichannel laser antifalsification technology of nanometer material |
| CN102696062A (en) * | 2010-05-18 | 2012-09-26 | 韩国科学技术院 | Method for producing an anti-forgery label using a randomly distributed pattern of fine particles formed on a variety of substrates, and method for determining the authenticity of the label |
| WO2016103132A1 (en) * | 2014-12-22 | 2016-06-30 | Eulitha A.G. | Method for printing colour images |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114648494A (en) * | 2022-02-28 | 2022-06-21 | 扬州市苏灵农药化工有限公司 | Pesticide suspending agent production control system based on factory digitization |
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| CN106340239B (en) | 2019-04-05 |
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Granted publication date: 20190405 Termination date: 20211021 |