CN115216861B - PUF device based on metal-dielectric-luminous coaxial multilayer composite nanofiber and method for generating secret key by using device - Google Patents
PUF device based on metal-dielectric-luminous coaxial multilayer composite nanofiber and method for generating secret key by using device Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06N—COMPUTING ARRANGEMENTS BASED ON SPECIFIC COMPUTATIONAL MODELS
- G06N20/00—Machine learning
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06T—IMAGE DATA PROCESSING OR GENERATION, IN GENERAL
- G06T7/00—Image analysis
- G06T7/10—Segmentation; Edge detection
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04L—TRANSMISSION OF DIGITAL INFORMATION, e.g. TELEGRAPHIC COMMUNICATION
- H04L9/00—Cryptographic mechanisms or cryptographic arrangements for secret or secure communications; Network security protocols
- H04L9/08—Key distribution or management, e.g. generation, sharing or updating, of cryptographic keys or passwords
- H04L9/0861—Generation of secret information including derivation or calculation of cryptographic keys or passwords
- H04L9/0877—Generation of secret information including derivation or calculation of cryptographic keys or passwords using additional device, e.g. trusted platform module [TPM], smartcard, USB or hardware security module [HSM]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02D—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN INFORMATION AND COMMUNICATION TECHNOLOGIES [ICT], I.E. INFORMATION AND COMMUNICATION TECHNOLOGIES AIMING AT THE REDUCTION OF THEIR OWN ENERGY USE
- Y02D30/00—Reducing energy consumption in communication networks
- Y02D30/70—Reducing energy consumption in communication networks in wireless communication networks
Abstract
The invention belongs to the technical field of PUF device preparation, and particularly relates to a PUF device based on metal-dielectric-luminous coaxial multilayer composite nanofiber and a method for generating a secret key by using the device. The PUF device is obtained by packaging coaxial three-layer nano fibers, wherein the coaxial three-layer nano fibers comprise a core layer, a middle layer and a shell layer which are sequentially arranged from inside to outside; the core layer is a plasmon metal layer, and the plasmon metal layer is prepared from plasmon metal nano particles, plasmon metal nano wires or plasmon metal nano fibers; the middle layer is a polymer dielectric layer; the shell layer is a light-emitting layer. The PUF device prepared by the invention can generate a key with higher randomness and uniqueness, the key entropy source is the space distribution uncertainty of the plasmon electromagnetic field under the nanoscale, the key with ultrahigh space storage capacity can be generated, and the space storage capacity of the key can exceed 4Tbit/mm 3 。
Description
Technical Field
The invention belongs to the technical field of PUF device preparation, and particularly relates to a PUF device based on metal-dielectric-luminous coaxial multilayer composite nanofiber and a method for generating a secret key by using the device.
Background
The generation and distribution of keys is a bottleneck problem in the information security infrastructure. The key is generated and distributed by adopting a cryptographic technology based on a physical entity so as to reduce the risk of key management and improve the security, and the key is one of the hot spot directions of the development of the information security technology in the world at present. Typical representatives of physical cryptographic techniques are quantum key distribution techniques and physical unclonable function (physical unclonable functions, PUF) techniques. The PUF can be used as a Hash function for product anti-counterfeiting and authentication, and also as a random number generator for key production. Since the PUF is random, it can be used to generate random numbers and then encapsulate various keys. Since each PUF device is unique and unclonable, it is functionally equivalent to a cryptographic algorithm with a "key" (black box). While neither the legitimate user nor the attacker can detect this "key", the party in possession of the device can use the black box functionality exclusively to enable key deployment.
In recent years, PUF devices can be classified into electrical SRAM-PUFs, which acquire a stable electrical noise sequence PUF, and optical PUFs, which calculate a key sequence, and which generate unique and random keys through optical responses or optical images. The unclonable pattern-based optical PUF keys are mainly optical speckle (Pappu, r., physical One-Way functions.science,2002.297 (5589): p.2026-2030.), fluorescent particles (Hu, y.w., et al, flexible and Biocompatible Physical Unclonable Function Anti-counterworking label.advanced Functional Materials,2021.31 (34): p.2102108), quantum dots (CN 110784312A), plasmonic nanoparticles (Smith, j.d., et al, plasmonic Anticounterfeit Tags with High Encoding Capacity Rapidly Authenticated with Deep Machine learning.acs Nano,2021.15 (2): p.2901-2910.), raman responses (Gu, y., et al, gap-enhanced Raman tags for physically unclonable anticounterfeiting laser Communications,2020.11 (1 p.516), etc. However, these optical specks or particles are generated based on brownian motion of the dispersion, which inevitably faces the problem of aggregation due to poor dispersion, resulting in unstable, non-robust key generation sequences.
Some random fibers have unique fiber distribution characteristics, such as fiber number, cross points, short fiber vertexes and the like, and have been gradually applied in the unclonable anti-counterfeiting field, such as an invention patent of a random fiber silk texture anti-counterfeiting mark identification method and system (CN 113128406A), a random texture anti-counterfeiting fiber and random texture anti-counterfeiting mark (CN 107798993A), a fragile anti-counterfeiting label of oriented random arranged fibers and a preparation method thereof (CN 109461366A), a random fiber code anti-counterfeiting database construction method (CN 104536999A) based on image processing, a random distribution fiber and substance anti-counterfeiting method (CN 101748659A), a random fiber distribution anti-counterfeiting sampling method (CN 1591520A) and a micro-nano optical unclonable anti-counterfeiting mark based on electrostatic spinning nano fiber cloth and a preparation method and application thereof (CN 113293448A). The random fibers are all characterized in that the images of the fibers are directly used as anti-counterfeiting marks or anti-counterfeiting codes, and the generation field of secret keys and random numbers is still blank at present. On the other hand, random fibers are used in the fields of anti-counterfeiting and encryption only based on reflection or fluorescence single optical response, and encryption level is low.
The invention patent application with the application publication number of CN110784312A discloses a preparation method of a PUF device and a key generation method thereof: the method comprises the steps of sulfur S and dichlorinationLead PbCl 2 The PbS quantum dots are synthesized by using the existing cheap basic chemical substances such as oleylamine OLA, methanol and toluene, a basic chemical experiment instrument is used in the process of synthesizing the PbS quantum dots, the distribution of the PbS quantum dots in a PUF device is derived from the Brownian motion of nanoparticles in a solution, the distribution of the PbS quantum dots has higher uniqueness and randomness, a graythresh function and an im2bw function in MATLAB software are utilized to convert a distribution diagram TEM of the PbS quantum dots in the PUF device into a black-white image, then the pixel dots are identified to obtain an initial key, and the initial key is subjected to Von Neuman processing and then grouped to obtain a final key; the method has the advantages that the PUF device is easy to obtain raw materials for preparing, and a key with high randomness and uniqueness can be generated.
Disclosure of Invention
The invention provides a PUF device based on metal-dielectric-luminous coaxial multilayer composite nanofiber and a method for generating a key by adopting the device.
The invention adopts the following technical scheme:
the PUF device based on the metal-dielectric-luminous coaxial multilayer composite nanofiber is obtained by packaging coaxial three-layer nanofiber, wherein the coaxial three-layer nanofiber comprises a core layer, an intermediate layer and a shell layer which are sequentially arranged from inside to outside;
the core layer is a plasmon metal layer and is specifically prepared from plasmon metal nano particles, plasmon metal nano wires or plasmon metal nano fibers;
the middle layer is a polymer dielectric layer;
the shell layer is a light-emitting layer.
In the PUF device, the metal is preferably gold or silver; the polymer of the polymer dielectric layer is preferably polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polymethyl methacrylate (PMMA), polystyrene (PS), polyethylene oxide (PEO) or Polyacrylonitrile (PAN) with good light transmittance; the luminous layer is prepared from fluorescent rare earth fluorescent particles, fluorescent dye, quantum dots, carbon dots or photoelectric polymers.
The preparation method of the PUF device comprises the following steps:
(1) Preparation of Metal-dielectric-luminescent coaxial three-layer nanofiber
And preparing a core layer, an intermediate layer and a shell layer through a triaxial electrostatic spinning process to obtain the metal-dielectric-luminous coaxial three-layer nanofiber.
The preparation method of the core layer electrostatic spinning solution comprises the following steps:
gold nanoparticles, silver nanocubes or silver nanowires are dissolved in polyvinylpyrrolidone solution or polyvinyl alcohol solution, and then are vigorously stirred for 5 hours at 40 ℃ to obtain core layer electrostatic spinning solution.
In the polyvinylpyrrolidone solution or the polyvinyl alcohol solution, the concentration of the silver nano particles and the silver nano cubes is 2.5-10 mM, and the molar ratio of PVP/Ag or PVA/Ag is 530 (1-4); the concentration of the silver nanowire is 5-20 mg/mL; the concentration of the gold nanoparticles is 0.01-1 mM.
The side length of the silver nanocubes is 55nm; the diameter of the silver nano particles is 30nm; the diameter of the silver nanowire is 120nm, and the length-diameter ratio is 100-1000; the diameter of the gold nanoparticle was 50nm.
The concentration of the polyvinylpyrrolidone solution or the polyvinyl alcohol solution is 5-7wt%, the polyvinylpyrrolidone solution is an ethanol solution of polyvinylpyrrolidone or an aqueous solution of polyvinylpyrrolidone, and the polyvinyl alcohol solution is an ethanol solution of polyvinyl alcohol or an aqueous solution of polyvinyl alcohol.
The preparation method of the intermediate layer electrostatic spinning solution comprises the following steps:
and (3) dissolving polymer polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, polystyrene, polyethylene oxide and polyacrylonitrile in a solvent, and then vigorously stirring for 5 hours at 40 ℃ to obtain the intermediate layer electrostatic spinning solution. The final polymer concentration is between 0.1 and 3 wt%. The solvent is water, ethanol, toluene, water or DMSO.
The preparation method of the shell spinning solution comprises the following steps:
and (3) dissolving fluorescent substances in a polyvinyl alcohol solution, a polystyrene solution or a polyvinylpyrrolidone solution, and then vigorously stirring for 5 hours at 40 ℃ to obtain a shell spinning solution.
The fluorescent material is rhodamine B and rare earth CePO 4 :Tb 3+ Nanoparticles, quantum dots, carbon dots or optoelectronic polymers. The concentration of the fluorescent substance after dissolution is 0.01-1 mM or 1-100 mg/mL.
(2) Packaging
And packaging the metal-dielectric-luminous coaxial three-layer nanofiber with silicone adhesive to prepare the coaxial multi-layer composite nanofiber, namely the PUF device.
The method for generating the key by adopting the PUF device comprises the following steps:
(1) Coaxial three-layer composite nanofiber intrinsic entropy extraction
The fluorescence intensity image and the fluorescence lifetime image of the single composite nanofiber are obtained through a super-resolution fluorescence microscope and a fluorescence lifetime microscope, and pretreatment such as segmentation, standardization, enhancement and the like is carried out on the fluorescence intensity image or the fluorescence lifetime image of the single composite nanofiber. The fluorescence intensity image is a super-resolution fluorescence image, the fluorescence lifetime image is a super-resolution lifetime image, the fluorescence lifetime image and the super-resolution lifetime image are both super-resolution images, and the spatial resolution reaches the level of 10 nm.
The super-resolution fluorescent image and the super-resolution life image are not necessarily consistent, so that the same fiber corresponds to the two images, and two secret keys can be obtained. This is defined in terms of a physical unclonable function, which is a pair of two stimulus-response (response).
The plasmon metal is a source of a nanoscale electric field and can generate a fluorescence enhancement effect. The polymer dielectric layer is used for adjusting the distance between the metal core layer and the luminous body in the luminous layer, so that the adjustment of fluorescence enhancement is realized. The plasmonic metal and the polymer dielectric layer act together to form an extractable entropy at the nanoscale.
(2) Key generation
The key is generated by adopting perceptual hash, differential hash, mean hash, gabor transform, hough transform or machine learning.
The beneficial effects of the invention are as follows:
the invention is characterized in thatThe key generation method has the advantages that the metal-dielectric-luminous coaxial multilayer composite nanofiber is prepared through an electrostatic spinning process, and the randomness characteristics of the space position and orientation between metal-luminous bodies in the composite fiber are utilized as a function of the fluorescence intensity and the service life of the single fiber; the intrinsic entropy of nanometer scale in single fiber is extracted by a super-resolution fluorescence microscope or a fluorescence lifetime microscope, and then an image feature extraction tool or machine learning is adopted to convert a fluorescence intensity image or a fluorescence lifetime image into a 256-bit and 1024-bit secret key, and then the secret key with high space storage capacity is assembled. The key entropy source is the uncertainty of the spatial distribution of the plasmon electromagnetic field under the nanoscale, and can generate the ultra-high spatial storage capacity>1Tbit/mm 3 ) Can exceed 4Tbit/mm 3 。
Unlike the previous feature extraction of random pattern of several fibers, the present invention extracts the random feature of metal-dielectric layer-luminophor single composite fiber, and the space size is over 3 orders of magnitude higher than that of the previous one, so that the generated secret key space memory capacity is greatly raised to less than 0.1Tbit/mm 3 (even less than 1 Mbit/mm) 3 ) To 4Tbit/mm 3 The above.
Drawings
FIG. 1 (a) is a schematic diagram of an apparatus for preparing composite nanofibers by triaxial spinning; FIG. 1 (b) is a transverse cross-sectional view of a composite nanofiber; FIG. 1 (c) is a longitudinal section view of a composite nanofiber;
FIG. 2 is a scanning electron microscope image of a composite nanofiber;
FIG. 3 is a normal dark field optical microscope image of a composite nanofiber;
FIG. 4 is a super-resolution fluorescence microscope image of a composite nanofiber;
FIG. 5 is a one-dimensional random key derived from a super-resolution fluorescence microscope image of a single composite nanofiber;
fig. 6 is an intra-chip and inter-chip hamming distance distribution of the 20 sets of one-dimensional random keys in 5a of example 5.
Fig. 7 is an intra-chip and inter-chip hamming distance distribution of 20 sets of one-dimensional random keys in 5b of embodiment 5.
Fig. 8 is an intra-chip and inter-chip hamming distance distribution of 20 sets of one-dimensional random keys in 5c of example 5.
Detailed Description
The following detailed description of the present invention is provided to facilitate understanding of the technical solution of the present invention, but is not intended to limit the scope of the present invention.
The silver nanocubes, silver nanoparticles, silver nanowires, gold nanoparticles used in the examples are all commercially available products.
As shown in fig. 1a, a method for preparing a PUF device based on metal-dielectric-luminescent coaxial multilayer composite nanofibers, comprising:
(1) Preparation of Metal-dielectric-luminescent coaxial three-layer nanofiber
And preparing a core layer, an intermediate layer and a shell layer through a triaxial electrostatic spinning process to obtain the metal-dielectric-luminous coaxial three-layer nanofiber.
(2) Packaging
And packaging the metal-dielectric-luminous coaxial three-layer nanofiber with silicone adhesive to prepare the coaxial multi-layer composite nanofiber.
Example 1 preparation of core layer Electrostatic spinning solution
The core layer electrostatic spinning solution is prepared by adopting the following 4 methods:
the method comprises the following steps:
silver nanocubes with a side length of 55nm were dissolved in an ethanol solution (5 wt%,5 mL) of polyvinylpyrrolidone (PVP) (K30, 1300 kDa) and then vigorously stirred at 40 ℃ for 5h to obtain a mixed solution of PVP and silver nanoparticles for electrospinning. The silver concentration in the PVP solution was 10mM and the PVP/Ag molar ratio was 530:4.
The second method is as follows:
silver nanoparticles having a diameter of 30nm were dissolved in an aqueous solution (7 wt%,5 mL) of an aqueous solution (1800 kDa) of polyvinyl alcohol (PVA), and then vigorously stirred at 40 ℃ for 5 hours to obtain a mixed solution of PVA and silver nanoparticles for electrospinning. The silver concentration in the PVA solution was 10mM and the PVA/Ag molar ratio was 530:4.
And a third method:
silver nanowires with a diameter of 120nm and an aspect ratio of 100-1000 are dissolved in an aqueous solution (7 wt%,5 mL) of an aqueous solution (1800 kDa) of polyvinylpyrrolidone (PVP) and then vigorously stirred at 40 ℃ for 5 hours to obtain a mixed solution of PVP and silver nanowires for electrostatic spinning. The concentration of silver nanowires in the PVP solution was 20mg/mL.
The method four:
gold nanoparticles having a diameter of 50nm were dissolved in an aqueous solution (7 wt%,5 mL) of an aqueous solution (1800 kDa) of polyvinyl alcohol (PVA), and then vigorously stirred at 40 ℃ for 5 hours to obtain a mixed solution of PVA and gold nanoparticles for electrospinning. The concentration of gold nanoparticles in the PVA solution was 1mM.
Example 2 preparation of an intermediate layer Electrostatic spinning solution
The intermediate layer electrostatic spinning solution is prepared by adopting the following method:
the method comprises the following steps: the polymer polyvinyl alcohol (PVA, 1800 kDa) was dissolved in water and then vigorously stirred at 40 ℃ for 5h to give the corresponding polymer solution for electrospinning. The final polymer concentration was 0.5wt%.
The second method is as follows: polyvinylpyrrolidone (PVP-K30, 1300 kDa) was dissolved in ethanol and then vigorously stirred at 40 ℃ for 5h to give the corresponding polymer solution for electrospinning. The final polymer concentration was 0.1wt%.
And a third method: polymethyl methacrylate (PMMA, 1000 kDa) was dissolved in toluene and then vigorously stirred at 40℃for 5h to give the corresponding polymer solutions for electrospinning. The final polymer concentration was 1wt%.
Example 3 preparation of Shell spinning solution
The method comprises the following steps:
rhodamine B was dissolved in a toluene solution (5 wt%,5 mL) of polymethyl methacrylate (PMMA, 1000 kDa), and then vigorously stirred at 40℃for 5 hours to obtain a mixed solution of PMMA and rhodamine B for electrospinning. Rhodamine B was 1mM in concentration in the PMMA solution.
The second method is as follows:
rare earth CePO 4 :Tb 3+ The nanoparticles were dissolved in an aqueous solution (5 wt%,5 mL) of polyvinyl alcohol (PVA) and then vigorously stirred at 40℃for 5 hours to give PVA and CePO for electrospinning 4 :Tb 3+ A mixed solution of nanoparticles. CePO in PVA solution 4 :Tb 3+ The concentration of the nanoparticles was between 1mM.
Rare earth CePO 4 :Tb 3+ The preparation method of the nano particles comprises the following steps: cePO (CePO) 4 :Tb 3+ Nanoparticle reference (Chen Gongqi research on new fluorescent energy transfer analysis methods based on rare earth luminescent nanoparticles [ D ]]University of Shanghai transportation 2012) is prepared by hydrothermal method. Into a 50mL beaker was added 0.45mmol CeCl 3 ·7H 2 O，0.05mmol Tb(NO 3 ) 3 ·6H 2 O,1mmol of TPP,15mL of high-purity water, then stirred, mixed well, transferred to a 30mL steel reaction vessel with Teflon lining, and heated at 90℃for 2.5h. Naturally cooling to room temperature, pouring out supernatant, centrifuging, and washing twice with anhydrous ethanol and high-purity water. And vacuum drying at 40 ℃.
And a third method:
core-shell quantum dots (ZnSe/ZnS QDs) were dissolved in toluene solution (5 wt%,5 mL) of Polystyrene (PS), and then vigorously stirred at 40℃for 5 hours, to obtain a mixed solution of PS and quantum dots for electrospinning. The concentration of quantum dots in the PVA solution is between 1mM.
The method four:
citric acid-urea based carbon dots (reference (Zhi, b., et al Multicolor polymeric carbon dots: synthenis, separation and polyamide-supported molecular fluorescence Science,2021.12 (7): p.2441-2455.) were synthesized, red, green and blue luminescence colors were adjusted) were dissolved in an aqueous solution (5 wt%,5 mL) of polyvinylpyrrolidone (PVP), and then vigorously stirred at 40 ℃ for 5 hours to obtain a mixed solution of PVP and carbon dots for electrospinning. The concentration of carbon dots in PVP solution was 10mg/mL.
And a fifth method:
the red light conjugated polymer MEH-PPV (available from sienna baolaet phototechnology, inc., mw=1000 kDa) was dissolved in a toluene solution (5 wt%,5 mL) of Polystyrene (PS), and then vigorously stirred at 40 ℃ for 5 hours to obtain a mixed solution of PS and MEH-PPV for electrospinning. The concentration of MEH-PPV in PVP solution is between 0.01 and 1mM.
Example 4 preparation of coaxial three-layer nanofibers
(1) Respectively adding core layer, middle layer and shell layer electrostatic spinning solution into core layer, middle layer and shell layer injectors, adopting a triaxial spinning head to carry out electrostatic spinning, controlling the propelling speeds of three microinjection pumps of the core layer injectors, the middle layer injectors and the shell layer injectors to be 1.5mL/h, 0.5 mL/h and 1.5mL/h respectively, wherein the spinning voltage is 12kV, the diameter of a nozzle is 0.7mm, and the receiving distance is 15cm.
The specific implementation conditions are as follows:
4a. The core layer electrostatic spinning solution (5 mL) prepared in the method I of example 1 is added into a core layer injector (namely a plasmon metal layer solution injector), the middle layer electrostatic spinning solution (5 mL) prepared in the method I of example 2 is added into a middle layer injector (namely a polymer dielectric layer solution injector), the shell layer electrostatic spinning solution (5 mL) prepared in the method I of example 3 is added into a shell layer injector (namely a luminescent layer solution injector), three micro injection pumps are adopted for electrostatic spinning, the advancing speeds of the core layer injector, the middle layer injector and the shell layer injector are controlled to be 1.5, 0.5 and 1.5mL/h respectively, the spinning voltage is 12kV, the nozzle diameter is 0.7mm, and the receiving distance is 15cm. The schematic cross-sectional views of the obtained metal-dielectric-luminous coaxial multilayer composite nanofiber are shown in fig. 1b and 1c, a scanning electron microscope image is shown in fig. 2, and a common optical microscope image is shown in fig. 3.
And 4b, adding the core layer electrostatic spinning solution (5 mL) prepared by the method I in the example 1 into a core layer injector, adding the middle layer electrostatic spinning solution (5 mL) prepared by the method II in the example 2 into a middle layer injector, adding the shell layer electrostatic spinning solution (5 mL) prepared by the method I in the example 3 into a shell layer injector, and carrying out electrostatic spinning by adopting a triaxial spinning head, wherein the three microinjection pumps of the core layer injector, the middle layer injector and the shell layer injector are respectively controlled to have the propelling speeds of 1.5, 0.5 and 1.5mL/h, the spinning voltage is 12kV, the nozzle diameter is 0.7mm, and the receiving distance is 15cm.
And 4c, respectively adding the core layer electrostatic spinning solution (5 mL) prepared by the method I in the example 1 into a core layer injector, adding the middle layer electrostatic spinning solution (5 mL) prepared by the method II in the example 2 into a middle layer injector, adding the shell layer electrostatic spinning solution (5 mL) prepared by the method IV in the example 3 into a shell layer injector, and carrying out electrostatic spinning by adopting a triaxial spinning head, wherein the three microinjection pumps of the core layer injector, the middle layer injector and the shell layer injector are respectively controlled to have the propelling speeds of 1.5, 0.5 and 1.5mL/h, the spinning voltage is 12kV, the nozzle diameter is 0.7mm, and the receiving distance is 15cm.
And 4d, respectively adding the core layer electrostatic spinning solution (5 mL) prepared in the first method in the example 1 into a core layer injector, adding the middle layer electrostatic spinning solution (5 mL) prepared in the third method in the example 2 into a middle layer injector, adding the shell layer electrostatic spinning solution (5 mL) prepared in the fifth method in the example 3 into a shell layer injector, and carrying out electrostatic spinning by adopting a triaxial spinning head, wherein the three microinjection pumps of the core layer injector, the middle layer injector and the shell layer injector are respectively controlled to have the propelling speeds of 1.5, 0.5 and 1.5mL/h, the spinning voltage is 12kV, the nozzle diameter is 0.7mm, and the receiving distance is 15cm.
And 4e, respectively adding the core layer electrostatic spinning solution (5 mL) prepared in the method four in the example 1 into a core layer injector, adding the middle layer electrostatic spinning solution (5 mL) prepared in the method two in the example 2 into a middle layer injector, adding the shell layer electrostatic spinning solution (5 mL) prepared in the method four in the example 3 into a shell layer injector, and carrying out electrostatic spinning by adopting a triaxial spinning head, wherein the three microinjection pumps of the core layer injector, the middle layer injector and the shell layer injector are respectively controlled to have the propelling speeds of 1.5, 0.5 and 1.5mL/h, the spinning voltage is 12kV, the nozzle diameter is 0.7mm, and the receiving distance is 15cm.
(2) And (3) packaging: and packaging the coaxial three-layer nanofiber by using silicone adhesive to obtain the weather-proof and wear-resistant PUF device.
Example 5
The method for generating a key using the PUF device of example 4 (the electrostatic spinning part of which uses 4 a) is specifically implemented as follows: :
5a, reading a single fiber PUF device by adopting a fluorescence microscope, and acquiring a fluorescence intensity image (namely a super-resolution fluorescence image) of the fiber by utilizing a structured light illumination fluorescence microscopy (SIM), wherein imaging parameters are as follows: the laser source is 405nm continuous laser (power 50m W), and the objective lens is 60 times; the resolution of the image is 512 multiplied by 512, the frame frequency of the camera is 220Hz, and the super-resolution image is reconstructed through a digital pixel repositioning technology. The result of super-resolution fluorescence imaging is shown in fig. 4. The 128-bit key is then generated by a mean hash method, as shown in fig. 5. When the image is hashed, the fluorescence intensity image is segmented, normalized and enhanced. The fluorescence intensity image generates fingerprint through mean hash, and the specific process is as follows: converting the fluorescence intensity image into a data matrix containing 1024 rows by 1024 columns of data by utilizing a graythresh function and an im2bw function in MATLAB software, wherein the binary data is initial key data; and carrying out von Neumann processing on the initial key data to delete redundant data, and finally obtaining 128-bit binary data. The robustness and uniqueness of the generated key is measured using a hamming distance distribution. From the hamming distance distribution of fig. 6, it can be seen that: the intra-chip hamming distance is about 0.19 and the inter-chip hamming distance is about 0.50.
And 5b, acquiring super-resolution fluorescence images of the single fiber PUF devices by using a random optical reconstruction technique (STORM). The imaging parameters are: the laser source is 405nm continuous laser (power 50m W), the resolution of the EMCCD camera is 512 multiplied by 100, the pixel point size is 130nm, 5000 images are collected, and the exposure time of each frame is 25ms. A 128 bit key is then generated by means of a mean hash method. When the image is hashed, the fluorescence intensity image is segmented, normalized and enhanced. The fluorescence intensity image generates fingerprint through mean hash, and the specific process is as follows: converting the fluorescence intensity image into a data matrix containing 1024 rows by 1024 columns of data by utilizing a graythresh function and an im2bw function in MATLAB software, wherein the binary data is initial key data; and carrying out von Neumann processing on the initial key data to delete redundant data, and finally obtaining 128-bit binary data. The robustness and uniqueness of the generated key is measured using a hamming distance distribution. From the hamming distance distribution of fig. 7, it can be seen that: the intra-chip hamming distance is about 0.09 and the inter-chip hamming distance is about 0.49.
And 5c, acquiring a fluorescence lifetime image of the single fiber PUF device by utilizing a structured light illumination fluorescence microscopy (SIM) and a time-dependent single photon Technique (TCSPC). Life imaging parameters were: the laser source is 405nm pulse laser, the pulse width is 30ps, the repetition frequency is 10MHz, the power is 100nW, the objective lens is 60×, and the single photon detector is connected with TCSPC. A 128 bit key is then generated by means of a mean hash method. When the image is hashed, the fluorescence lifetime image is segmented, normalized and enhanced. The fluorescence lifetime image generates fingerprint through mean hash, and the specific process is as follows: converting the fluorescence lifetime image into a data matrix containing 1024 rows by 1024 columns of data by utilizing a graythresh function and an im2bw function in MATLAB software, wherein the binary data is initial key data; and carrying out von Neumann processing on the initial key data to delete redundant data, and finally obtaining 128-bit binary data. The robustness and uniqueness of the generated key is measured using a hamming distance distribution. From the hamming distance distribution of fig. 8, it can be seen that: the intra-chip hamming distance is about 0.14 and the inter-chip hamming distance is about 0.50.
The above-described embodiments are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention, so that all equivalent changes or modifications of the structure, characteristics and principles described in the claims should be included in the scope of the present invention.
Claims (7)
1. The PUF device based on the metal-dielectric-luminous coaxial multilayer composite nanofiber is characterized in that the PUF device is obtained by packaging coaxial three-layer nanofibers, and the coaxial three-layer nanofibers comprise a core layer, an intermediate layer and a shell layer which are sequentially arranged from inside to outside;
the core layer is a plasmon metal layer, and the plasmon metal layer is prepared from plasmon metal nano particles, plasmon metal nano wires or plasmon metal nano fibers; the metal is gold or silver;
the middle layer is a polymer dielectric layer; the polymer of the polymer dielectric layer is polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, polystyrene, polyethylene oxide or polyacrylonitrile;
the shell layer is a luminous layer; the luminescent layer is prepared from fluorescent substances, wherein the fluorescent substances are rare earth fluorescent particles, fluorescent dyes, quantum dots, carbon dots or photoelectric polymers.
2. The PUF device of claim 1, wherein the PUF device is obtained by encapsulating a coaxial three-layer nanofiber with a silicone gel.
3. A method of manufacturing a PUF device according to claim 1 or 2, comprising the steps of:
(1) Preparing metal-dielectric-luminous coaxial three-layer nano fiber: preparing a core layer, an intermediate layer and a shell layer through a triaxial electrostatic spinning process to obtain metal-dielectric-luminous coaxial three-layer nano fibers;
(2) And (3) packaging: and packaging the metal-dielectric-luminous coaxial three-layer nanofiber with silicone adhesive to prepare the PUF device.
4. A process according to claim 3, wherein,
the preparation method of the core layer electrostatic spinning solution comprises the following steps:
gold nano particles, silver nano particles or silver nano wires are dissolved in a polyvinylpyrrolidone solution or a polyvinyl alcohol solution, and then are vigorously stirred at 40 ℃ for 5h, so that a core layer electrostatic spinning solution is obtained;
in the polyvinylpyrrolidone solution or the polyvinyl alcohol solution, the concentration of the silver nano particles is 2.5-10 mM, and the molar ratio of PVP/Ag or PVA/Ag is 530 (1-4); the concentration of the silver nanowires is 5-20 mg/mL; the concentration of the gold nano-particles is 0.01-1 mM.
5. A process according to claim 3, wherein,
the preparation method of the intermediate layer electrostatic spinning solution comprises the following steps:
the polymer polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, polystyrene, polyethylene oxide or polyacrylonitrile are dissolved in a solvent, and then are vigorously stirred for 5h at 40 ℃ to obtain an intermediate layer electrostatic spinning solution, wherein the final polymer concentration is 0.1-3 wt%, and the solvent is water, ethanol, toluene or DMSO.
6. A process according to claim 3, wherein,
the preparation method of the shell spinning solution comprises the following steps:
dissolving fluorescent substances in a polyvinyl alcohol solution, a polystyrene solution or a polyvinylpyrrolidone solution, and then vigorously stirring at 40 ℃ for 5h to obtain a shell spinning solution;
the concentration of the fluorescent substance is 0.01-1 mM or 1-100 mg/mL.
7. A method of generating a key using a PUF device according to claim 1 or 2, comprising the steps of:
(1) Extracting intrinsic entropy of coaxial three-layer composite nanofiber: obtaining the fluorescence intensity and fluorescence lifetime images of the single composite nanofiber through a super-resolution fluorescence microscope and a fluorescence lifetime microscope, and carrying out segmentation, standardization and enhancement pretreatment on the super-resolution fluorescence images or fluorescence lifetime images of the single composite nanofiber;
(2) And (3) key generation: the key is generated by adopting perceptual hash, differential hash, mean hash, gabor transform, hough transform or machine learning.
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