CN107595292B - Photothermal imaging fingerprint detection method - Google Patents

Photothermal imaging fingerprint detection method Download PDF

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CN107595292B
CN107595292B CN201710868126.4A CN201710868126A CN107595292B CN 107595292 B CN107595292 B CN 107595292B CN 201710868126 A CN201710868126 A CN 201710868126A CN 107595292 B CN107595292 B CN 107595292B
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fingerprint
detection method
material powder
black phosphorus
photo
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CN107595292A (en
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喻学锋
谢寒寒
童睿锋
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Shenzhen Institute of Advanced Technology of CAS
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Abstract

The invention provides a photothermal imaging fingerprint detection method, which comprises the following steps: (1) fumigating the fingerprint to be detected by adopting a fumigating agent; (2) covering photo-thermal material powder on the to-be-detected fingerprint subjected to fuming; (3) irradiating a fingerprint area to be detected by using an infrared excitation light source, and shooting a fingerprint image by using an infrared camera; the preparation method of the black phosphorus photo-thermal material powder used by the invention comprises the following steps: (1) weighing red phosphorus and putting into grinding balls, wherein the mass ratio of the grinding balls to the red phosphorus is 10-80: 1; (2) under the condition that the rotating speed is 1000-2000rpm/min, ball milling is carried out for 5-10h to obtain black phosphorus photo-thermal material powder with uniform particle size, and the black phosphorus photo-thermal material powder prepared by the method can obtain a latent fingerprint image with good imaging effect by combining the detection method provided by the invention.

Description

Photothermal imaging fingerprint detection method
Technical Field
The invention belongs to the technical field of fingerprint identification, and particularly relates to a photothermal imaging fingerprint detection method.
Background
The skin on the surface of the finger has secretion such as sweat, grease and the like, and when the finger touches an object, the secretion is correspondingly remained on the surface of the object to form a corresponding texture print. Some of these texture prints are directly visible, while more are fingerprints that are difficult to see directly with the naked eye and cannot be seen directly with the naked eye, which are called latent fingerprints.
Since fingerprints are unique marks for everyone, fingerprints are also recognized as the "first line of evidence" by the judicial community, and thus fingerprint detection plays a very important role in the criminal field. The most critical technology in fingerprint detection is the visualization of latent fingerprints, and various fingerprint visualization technologies are used in order to make the latent fingerprints visible. The method of latent fingerprint appearance can be divided into three methods according to the principle of appearance: optical visualization, physical adsorption, and chemical visualization. The optical display method mainly comprises a common optical inspection method, an ultraviolet light inspection method, an infrared light inspection method and the like, wherein the optical display method mainly utilizes light rays to act on fingerprints to generate photochemical effect to display the fingerprints, and can directly display the image characteristics of the marks through photographing on the basis of not touching the marks on the surfaces of objects, but the method has limited display enhancing capability and cannot independently solve all problems encountered in practice. The physical adsorption method mainly comprises a powder developing method, a metal deposition method and the like, and the method mainly enables the fingerprint to develop color by adsorbing substances on the surface of the fingerprint, is simple and quick to operate, but causes a plurality of defects of the developed fingerprint because the adsorption capacity between the material and the fingerprint is limited. The chemical visualization method mainly comprises a silver nitrate method, an indantrione method, a DFO method and the like, and the method mainly utilizes the reaction of chemical substances and amino acids in fingerprints to visualize the fingerprints, however, the method has strict requirements on the environment, the visualization effect is greatly influenced by an operation method, the sensitivity is weak, and the interference of background color and autofluorescence is caused, so that the better application of the method is limited.
The nano particles can effectively convert electromagnetic radiation into heat, and have relatively low toxicity and good biocompatibility, so that the nano particles are greatly developed in various fields such as photothermal therapy and the like. Nanoparticles are also currently gaining more attention in the field of photothermographic imaging, which is mainly due to local temperature changes, exhibits low background noise, is non-destructive, and is highly photosensitive. Chinese patent document (application No. CN201410680319.3, a two-step latent fingerprint developing method based on nanoparticles) discloses a two-step latent fingerprint developing method based on nanoparticles, which combines zinc oxide or aluminum oxide nanoparticles with trace substances on the surface of fingerprints, and then uses organic fluorescent dye coloring solvent to perform adsorption treatment on the developed fingerprints, and the method can realize high-contrast fluorescence characteristic development of fingerprints, however, the developing solution used in the method has complex preparation steps and takes a long time.
Chinese patent document (application No. CN201410059253.6, a method for smoking latent fingerprints with candle soot) discloses that a burning candle is used as the main display material, and the difference between the comprehensive abilities of candle ash and fingerprint valley and ridge areas is utilized to place a latent fingerprint sample in the flame of the burning candle to enrich soot for smoking, and then the sample is removed from the flame and applied with external force to make the valley area candle ash with relatively weak binding degree fall off, leaving the ridge area candle ash with higher binding degree, thereby displaying latent fingerprints. The method is simple and convenient to operate, materials are easy to obtain, however, the method is limited in applicable objects, latent fingerprints on inflammables such as paper sheets and plastic films cannot be displayed through the method, and meanwhile, the method has high requirements on skills and experience of operators.
In summary, the existing fingerprint visualization methods have many disadvantages, such as complicated reagent preparation, limited technical application range, defects in the visualized fingerprints, poor sensitivity, easy manipulation of visualization effect, interference of background color and environment, and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a fingerprint detection method with strong binding property, high contrast, background color resistance and autofluorescence interference resistance based on the photothermal imaging property of nano particles.
In order to achieve the purpose, the invention adopts the following technical scheme:
a photothermal imaging fingerprint detection method comprises the following steps:
(1) carrying out fuming treatment on the fingerprint to be detected by adopting a fuming agent;
(2) covering photo-thermal material powder on the to-be-detected fingerprint subjected to fuming;
(3) and irradiating the fingerprint area to be detected by using an infrared excitation light source, and shooting a fingerprint image by using an infrared camera.
Preferably, the fingerprint to be detected is located on a solid object.
Further preferably, the solid object comprises a plastic, glass, metal, wood or paper.
Preferably, the fumigant is prepared by mixing a compound at least containing or generating alpha-ethyl cyanoacrylate with an inorganic alkali solution.
Further preferably, the agent at least containing or generating alpha-ethyl cyanoacrylate compound is 502 glue; the concentration of the inorganic alkali solution is 10-50 mg/mL.
More preferably, the volume ratio of the reagent at least containing or generating the alpha-cyanoacrylate compound to the inorganic base solution is 1:1-1: 2.
Further preferably, the inorganic base solution comprises NaOH, KOH, Na2CO3And K2CO3At least one of the solutions.
Preferably, the fuming time in step (1) is 10-20min, preferably 10-15 min.
Preferably, the fuming treatment in the step (1) can be performed in a fuming box, specifically, 502 glue and inorganic alkali solution are mixed and then placed in one position in the fuming box, then the solid object to be detected with the fingerprint is placed in another position in the fuming box, and the fuming is performed for 10-20min or until white fuming fingerprint appears.
Preferably, the fuming treatment in the step (1) may be performed by mixing 502 glue with an inorganic alkali solution, dripping the mixture on the absorbent cotton, and inverting the surface of the solid object to be detected with the fingerprint above the absorbent cotton by 1cm for fuming for 10-20min or fuming until white fuming fingerprint appears.
Preferably, the range of the fuming in the step (1) is not less than the area where the fingerprint to be detected is located.
Preferably, the photothermal material powder includes at least one of black phosphorus, graphene, molybdenum disulfide, tungsten disulfide, and bismuth selenide.
Further preferably, the average particle diameter of the photo-thermal material powder is 0.1 to 2 μm.
More preferably, the photothermal material powder has an average particle diameter of 0.1 to 1 μm.
Further preferably, the photothermal material powder has an absorption wavelength of 200-2000 nm.
More preferably, the photo-thermal material powder has an absorption wavelength of 300-1100 nm.
Further preferably, the photo-thermal material powder is black phosphorus.
Still more preferably, the black phosphorus is obtained by the following steps: weighing 2-4 parts of red phosphorus, and putting into a stainless steel ball with the diameter of 8-12mm, wherein the mass ratio of the stainless steel ball to the red phosphorus is (10-80):1, preferably (20-70):1, and more preferably (30-50): 1; under the condition that the rotating speed is 1000-; wherein, the grinding balls are stainless steel balls, and the diameter of the grinding balls is 8-12mm, preferably 8-10 mm.
Further preferably, the average particle diameter of the black phosphorus powder is 0.1 to 2 μm.
More preferably, the black phosphorus powder has an average particle diameter of 0.1 to 1 μm.
Further preferably, the absorption wavelength of the black phosphorus powder is 300-1100 nm.
More preferably, the absorption wavelength of the black phosphorus powder is 760-1100 nm.
Preferably, the photo-thermal material powder is brushed or coated on the fingerprint to be detected by using a brush in the step (2), wherein the coating thickness of the photo-thermal material powder is 0.5-1mm, and the surplus photo-thermal material powder is removed.
Further preferably, the extent of the brush or paint is not less than the area in which the fingerprint is to be detected.
Preferably, the infrared excitation light source comprises an excitation light source with a wavelength range of 760-2000 nm.
Further preferably, the infrared excitation light source is a 808nm laser, a 980nm laser or a 1064nm laser.
Preferably, the irradiation time of the infrared excitation light source is 1-5 min.
The invention has the advantages of
The photothermal imaging fingerprint detection method provided by the invention is characterized in that a to-be-detected fingerprint is fumigated in advance by adopting a fumigant, then photo-thermal material powder is brushed on the to-be-detected fingerprint, then an infrared excitation light source is used for irradiating a fingerprint area, and finally a fingerprint image is shot by an infrared camera. The black phosphorus photo-thermal material is obtained by high-energy ball milling, so that the particle size is uniform. Meanwhile, by means of the fuming action of the fuming agent, the black phosphorus photo-thermal material can be tightly combined with the fuming fingerprint and uniformly dispersed; and the damage to the surface characteristics of the fingerprint caused by brushing or painting the phosphorescent thermal material in the follow-up process is reduced. In addition, the black phosphorus photo-thermal material powder obtained by high-energy ball milling has a good photo-thermal effect, can perform high-contrast photo-thermal imaging, and effectively reduces the interference of latent fingerprint appearing background color and autofluorescence. In addition, the black phosphorus photo-thermal material powder adopted by the invention has simple preparation method and low powder toxicity.
Drawings
Fig. 1 is a scanning electron micrograph of black phosphorus of the photothermal material prepared in example 1.
Fig. 2 is a graph showing an ultraviolet-visible-near infrared absorption spectrum of black phosphorus of the photothermal material prepared in example 1.
Fig. 3 is a graph showing a photo-thermal temperature rise of black phosphorus of the photo-thermal material prepared in example 1.
Fig. 4 is a schematic diagram of a fingerprint detection method in embodiment 4.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific examples. The present invention can be modified and implemented as appropriate within the scope of the main claim.
Example 1
The embodiment of the invention provides a preparation method of black phosphorus powder of a photo-thermal material, which comprises the following steps:
(1) weighing 4g of red phosphorus, putting into a stainless steel ball mill, wherein the diameter of a stainless steel ball is 10mm, and the mass ratio of the stainless steel ball to the red phosphorus is 40: 1;
(2) high-energy ball milling is carried out for 7h under the condition of the rotating speed of 1000rpm, and black phosphorus powder with uniform particle size is obtained.
The product obtained in example 1 was characterized and shown in fig. 1-3, wherein fig. 1 is a scanning electron microscope image of the black phosphorus powder, fig. 2 is an ultraviolet-visible-near infrared absorption spectrum of the black phosphorus powder dispersed in an aqueous solution, and fig. 3 is a temperature rise curve of the black phosphorus powder under irradiation of an infrared lamp. It can be seen from FIG. 1 that the average particle size of the black phosphorus powder is 200nm, and the particle size distribution is relatively uniform. It can be seen from fig. 2 that the black phosphorus exhibits significant absorption characteristics in the region of 250-900nm, and fig. 3 shows that the black phosphorus gradually increases in temperature with time under the irradiation of the infrared lamp, and has a good photo-thermal effect.
Example 2
The embodiment of the invention provides a preparation method of black phosphorus powder of a photo-thermal material, which comprises the following steps:
(1) weighing 4g of red phosphorus, putting into a stainless steel ball, wherein the diameter of the stainless steel ball is 10mm, and the ball weight ratio is 20: 1;
(2) high-energy ball milling is carried out for 10 hours under the condition of the rotating speed of 2000rpm, and black phosphorus powder with uniform particle size is obtained.
The average particle size of the black phosphorus powder obtained in the example is 100nm, and the particle size distribution is relatively uniform; the absorption wavelength is 250-900 nm.
Example 3
The embodiment of the invention provides a preparation method of black phosphorus powder of a photo-thermal material, which comprises the following steps:
(1) weighing 4g of red phosphorus, putting into a stainless steel ball, wherein the diameter of the stainless steel ball is 10mm, and the ball weight ratio is 80: 1;
(2) high-energy ball milling is carried out for 5 hours under the condition of the rotating speed of 1500rpm, and black phosphorus powder with uniform particle size is obtained.
The average particle size of the black phosphorus powder obtained in the example is 150nm, and the particle size distribution is relatively uniform; the absorption wavelength is 250-900 nm.
Example 4
The embodiment of the invention provides a method for detecting a photothermal imaging fingerprint, which comprises the following steps:
(1) pressing an oil latent fingerprint on the glass plate;
(2) dropping a mixture of 502 glue and NaOH solution with a volume ratio of 1:1 on the absorbent cotton, and inversely buckling a glass plate with a fingerprint pressed on the absorbent cotton for fuming for 10 minutes; wherein the concentration of the NaOH solution is 25 mg/mL;
(3) dipping a proper amount of the black phosphorus powder prepared in the example 1 by using a brush, lightly brushing the black phosphorus powder on the smoked fingerprints, and brushing off the redundant powder on the surfaces of the smoked fingerprints;
(4) the fingerprint area was irradiated with 808nm laser for 5min, and then an infrared camera was used to take a fingerprint image, and fig. 4 is a schematic view of the fingerprint detection method of this example.
Example 5
The embodiment of the invention provides a method for detecting a photothermal imaging fingerprint, which comprises the following steps:
(1) pressing an oil latent fingerprint on the glass plate;
(2) dropping a mixture of 502 glue and NaOH solution with the volume of 1:1 on the absorbent cotton, and inversely buckling a glass plate with a fingerprint pressed on the absorbent cotton for fuming for 10 minutes; wherein the concentration of the NaOH solution is 50 mg/mL;
(3) dipping a proper amount of the black phosphorus powder prepared in the example 1 by using a brush, lightly brushing the black phosphorus powder on the smoked fingerprints, and brushing off the redundant powder on the surfaces of the smoked fingerprints;
(4) the fingerprint area was illuminated with a 980nm laser for 5min and then the fingerprint image was taken using an infrared camera.
Example 6
The embodiment of the invention provides a method for detecting a photothermal imaging fingerprint, which comprises the following steps:
(1) pressing an oil latent fingerprint on the glass plate;
(2) dropping a mixture of 502 glue and NaOH solution with a volume ratio of 1:1 on the absorbent cotton, and inversely buckling a glass plate with a fingerprint pressed on the absorbent cotton for fuming for 10 minutes; wherein the concentration of the NaOH solution is 10 mg/mL;
(3) dipping a proper amount of the black phosphorus powder prepared in the example 1 by using a brush, lightly brushing the black phosphorus powder on the smoked fingerprints, and brushing off the redundant powder on the surfaces of the smoked fingerprints after brushing;
(4) the fingerprint area was irradiated with a 1064nm laser for 5 minutes, and then an infrared camera was used to take a fingerprint image.
Example 7
The embodiment of the invention provides a method for detecting a photothermal imaging fingerprint, which comprises the following steps:
(1) pressing an oil latent fingerprint on the glass plate;
(2) mixing the components in a volume ratio of 1:1, dripping the mixture of 502 glue and NaOH solution on absorbent cotton, and inversely buckling a glass plate with a fingerprint on the absorbent cotton for fumigating for 10 minutes; wherein the concentration of the NaOH solution is 25 mg/mL;
(3) dipping a proper amount of the black phosphorus powder prepared in the example 3 by using a brush, lightly brushing the black phosphorus powder on the smoked fingerprints, and brushing off the redundant powder on the surfaces of the smoked fingerprints;
(4) the fingerprint area was illuminated with a 808nm laser for 5min and then the fingerprint image was taken using an infrared camera.
Example 9
The embodiment of the invention provides a method for detecting a photothermal imaging fingerprint, which comprises the following steps:
(1) pressing an oil latent fingerprint on the glass plate;
(2) mixing 502 glue and Na in a volume of 1:12CO3Dropping the mixture of the solution on absorbent cotton, and inversely buckling a glass plate with a fingerprint on the absorbent cotton for fumigating for 10 minutes; wherein, Na2CO3The concentration of the solution is 25 mg/mL;
(3) dipping a proper amount of the black phosphorus powder prepared in the example 1 by using a brush, lightly brushing the black phosphorus powder on the smoked fingerprints, and brushing off the redundant powder on the surfaces of the smoked fingerprints;
(4) the fingerprint area was illuminated with a 808nm laser for 5min and then the fingerprint image was taken using an infrared camera.
Example 10
The embodiment of the invention provides a method for detecting a photothermal imaging fingerprint, which comprises the following steps:
(1) pressing an oil latent fingerprint on the glass plate;
(2) dropping a mixture of 502 glue and KOH solution with the volume ratio of 1:1 on the absorbent cotton, and inversely buckling a glass plate with a fingerprint pressed on the absorbent cotton for fuming for 10 minutes; wherein, the concentration of the KOH solution is 25 mg/mL;
(3) dipping a proper amount of the black phosphorus powder prepared in the example 1 by using a brush, lightly brushing the black phosphorus powder on the smoked fingerprints, and brushing off the redundant powder on the surfaces of the smoked fingerprints;
(4) the fingerprint area was illuminated with a 808nm laser for 5min and then the fingerprint image was taken using an infrared camera.
Example 11
A method for detecting a photothermographic fingerprint, comprising the steps of: (1) pressing an oil latent fingerprint on the glass plate;
(2) dropping a mixture of 502 glue and NaOH solution with a volume ratio of 1:1 on the absorbent cotton, and inversely buckling a glass cup with a fingerprint pressed on the absorbent cotton for fuming for 10 minutes; wherein the concentration of the NaOH solution is 25 mg/mL;
(3) dipping a proper amount of graphene powder by using a brush, lightly brushing the graphene powder on the smoked fingerprints, and brushing off the redundant powder on the surfaces of the smoked fingerprints after brushing;
(4) the fingerprint area was irradiated with 808nm laser radiation for 5 minutes, and then the fingerprint image was taken using an infrared camera.
Example 12
A method for detecting a photothermographic fingerprint, comprising the steps of:
(1) pressing an oil latent fingerprint on the glass plate;
(2) dropping a mixture of 502 glue and NaOH solution with a volume ratio of 1:1 on the absorbent cotton, and inversely buckling a glass cup with a fingerprint pressed on the absorbent cotton for fuming for 10 minutes; wherein the concentration of the NaOH solution is 25 mg/mL;
(3) dipping a proper amount of molybdenum disulfide powder by using a brush, lightly brushing the molybdenum disulfide powder on the smoked fingerprints, and brushing off the redundant powder on the surfaces of the smoked fingerprints after brushing;
(4) the fingerprint area was irradiated with 808nm laser radiation for 5 minutes, and then the fingerprint image was taken using an infrared camera.
Example 13
A method for detecting a photothermographic fingerprint, comprising the steps of:
(1) pressing an oil latent fingerprint on the glass plate;
(2) dropping a mixture of 502 glue and NaOH solution with a volume ratio of 1:1 on the absorbent cotton, and inversely buckling a glass cup with a fingerprint pressed on the absorbent cotton for fuming for 10 minutes; wherein the concentration of the NaOH solution is 25 mg/mL;
(3) dipping a proper amount of tungsten disulfide powder by using a brush, lightly brushing the tungsten disulfide powder on the smoked fingerprints, and brushing off the redundant powder on the surfaces of the smoked fingerprints after brushing;
(4) the fingerprint area was irradiated with 808nm laser radiation for 5 minutes, and then the fingerprint image was taken using an infrared camera.
Example 14
(1) Pressing an oil latent fingerprint on the glass plate;
(2) dropping a mixture of 502 glue and NaOH solution with a volume ratio of 1:1 on the absorbent cotton, and inversely buckling a glass cup with a fingerprint pressed on the absorbent cotton for fuming for 10 minutes; wherein the concentration of the NaOH solution is 25 mg/mL;
(3) dipping a proper amount of bismuth selenide powder by a brush, lightly brushing the bismuth selenide powder on the smoked fingerprints, and brushing off the redundant powder on the surfaces of the smoked fingerprints after brushing;
(4) the fingerprint area was irradiated with 808nm laser radiation for 5 minutes, and then the fingerprint image was taken using an infrared camera.
Experiments show that the photo-thermal imaging effect of the photo-thermal material adopting black phosphorus is obviously superior to that of other photo-thermal materials under the same conditions. In addition, the black phosphorus is non-toxic and safe, and cannot cause harm to operators. In conclusion, black phosphorus is a more preferable photothermal material in the photothermographic fingerprint detection method of the present invention.
The above examples are provided for clarity of illustration only and are not intended to limit the invention to the particular embodiments described. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any obvious variations or modifications which come within the spirit and scope of the invention are desired to be protected by the following claims.

Claims (9)

1. The photothermal imaging fingerprint detection method is characterized by comprising the following steps of:
(1) carrying out fuming treatment on the fingerprint to be detected by adopting a fuming agent;
(2) covering photo-thermal material powder on the to-be-detected fingerprint subjected to fuming;
(3) irradiating a fingerprint area to be detected by using an infrared excitation light source, and shooting a fingerprint image;
the photo-thermal material powder is selected from black phosphorus.
2. The photothermographic fingerprint detection method according to claim 1, wherein said fumigant is formed by mixing a reagent containing or producing at least an α -cyanoacrylate compound with an inorganic base solution in a volume ratio of 1:1 to 1: 2.
3. The photothermographic detection method according to claim 2, wherein said reagent containing or generating at least an alpha-cyanoacrylate compound is 502 glue.
4. The photothermographic detection method according to claim 2, wherein said inorganic alkaline solution is selected from the group consisting of NaOH, KOH, Na2CO3And K2CO3At least one of the solutions.
5. The photothermographic detection method according to any one of claims 1-4, wherein the fuming time in step (1) is 10-20 min.
6. The photothermal imaging fingerprint detection method according to claim 1, wherein said black phosphorus is prepared by the following method: grinding red phosphorus by a ball mill to obtain black phosphorus powder with uniform particle size: wherein the mass ratio of the grinding balls to the red phosphorus in the ball mill is (10-80) to 1; the ball milling speed is 1000 plus 2000rpm, and the ball milling time is 5-10 h.
7. The photothermographic detection method according to claim 1 or 6, wherein the photothermal material powder has an average particle size of 0.1-2 μm and an absorption wavelength of 200-2000 nm.
8. The photothermographic fingerprint detection method according to claim 1, wherein said photothermal material powder is brushed or coated onto the fingerprint to be detected, wherein the coating thickness of said photothermal material powder is 0.5-1mm, and excess photothermal material powder is removed.
9. The method as claimed in claim 1, wherein the wavelength range of the infrared excitation light source is 760-2000 nm; the irradiation time is 1-5 min.
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