CN116002689B - Silicon-based optical PUF, preparation method and application thereof - Google Patents

Silicon-based optical PUF, preparation method and application thereof Download PDF

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CN116002689B
CN116002689B CN202211619742.3A CN202211619742A CN116002689B CN 116002689 B CN116002689 B CN 116002689B CN 202211619742 A CN202211619742 A CN 202211619742A CN 116002689 B CN116002689 B CN 116002689B
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optical puf
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CN116002689A (en
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皮孝东
王坤
何强
杨德仁
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Zhejiang University ZJU
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Abstract

The invention discloses a silicon-based optical PUF, a preparation method and application thereof. The optical PUF of the present invention comprises a substrate 1 and a nanomaterial layer 2 attached to the substrate 1. The average value of the side length and the average value of the depth of the rugged structure of the substrate 1 are respectively smaller than the central luminous wavelength of the nano material layer 2, and the resistivity of the substrate 1 is less than or equal to 0.005 omega cm. The material of the nanomaterial layer 2 is erbium-doped silicon nanomaterial, 7 different optical response signals can be generated at any point on the nanomaterial layer 2, and the 7 different optical response signals are generated by the erbium-doped silicon nanomaterial. The erbium-doped silicon nanomaterial comprises silicon element and erbium element, wherein the silicon element exists in the form of nano silicon, and the erbium element completely exists in the form of Er 3+ Morphology exists within the crystal lattice of the silicon nanomaterial and is optically active. The invention realizes the coding capacity of 7 by doping one element without numerical processing of the optical signal 10000 Silicon-based optical PUFs of (a).

Description

Silicon-based optical PUF, preparation method and application thereof
Technical Field
The invention relates to the field of PUF anti-counterfeiting, in particular to a silicon-based optical PUF, a preparation method and application thereof.
Background
With the rapid development of emerging technologies such as artificial intelligence and the internet of things, the amount of chips used for information generation, transmission, reception and processing has been increasing explosively. From a security point of view, one must prevent these chips from being counterfeited, thus ensuring the authenticity of the information. In 2017, the total amount of the global counterfeit product reaches 1.2trillion dollars, and by 2020, 1.82trillion dollars (In 2017,the amount of total counterfeiting In global has reached 1.2Trillion U.S.dollars and is boundto 1.82trillion U.S.dollars by the year 2020.WangJ,Zhang Q,Chen R,et al.Triple-layer unclonable anti-counterfeiting enabled by huge-encoding capacity algorithm and artificial intelligence authentication [ J ]. Nano Today,2021, 41:101324.) are reached, which not only causes huge economic loss, but also brings false information to the counterfeit product, and disturbs the economic market. Therefore, from the standpoint of ensuring the security of information or reducing economic loss, there is an urgent need for a non-replicable security tag to provide safe and effective protection for chip products. The physical unclonable function (Physical Unclonable Function, PUF) has the advantages of cloning prevention, economy, high efficiency and resistance to various physical attacks (One alternative approach is to use Physical Unclonable Functions (PUFs), which are cloneproof, cost efficient andresistantto various physical attacks. Gao Y, al-Sarawi S F, abbott D.physical Unclonable Functions [ J ]. Nature Electronics,2020,3 (2): 81-91.), and is a very ideal anti-counterfeit label.
A Physical Unclonable Function (PUF) is a device that exploits inherent randomness introduced in the manufacturing process to give a unique "fingerprint" or trust anchor to a physical entity (Aphysical unclonable function (PUF) is a device that exploits inherent randomness introduced during manufacturing to give aphysical entity a unique 'finger print' or trust anchor. Gao Y, al-Sarawi S F, abbott d. Physical Unclonable Functions [ J ]. Nature Electronics,2020,3 (2): 81-91.). Upon identification verification of the protected object, the stimulus will cause the PUF to output a unique and uncloneable response, i.e. a unique stimulus-response pair (CRP) (For each PUF, an input query or 'challenge' receives an instance-specific output or 'response', a process known as a challenge-response pair (CRP). Gao Y, al-Sarawi S F, abbott D.physical Unclonable Functions [ J ]. Nature Electronics,2020,3 (2): 81-91.).
Over the years, various PUFs have been developed, including optical PUF (optical PUF), magnetic PUFs, electrical PUFs. Among them, optical PUFs are receiving attention because of their fast response speed and non-contact excitation-response modes (Optical PUFs, … …, due to the non-contactand fast Optical reading properties, hu Y W, zhang T P, wang C F, et al flexible and Biocompatible Physical Unclonable Function Anti-Counterfeiting Label [ J ]. AdvancedFunctional Materials,2021, 2108:1-9.). Furthermore, thanks to the complex stimulus-response pattern and the massive information content of optical PUFs, optical PUFs have proven to be one of the most powerful PUFs in the face of machine learning based modeling attacks (Optical PUFs were proved to be one of the most strong PUFs when facing machine learning based modeling attacks, which benefits from the unpredictability of extremely complex input-output andthe vast information content. Chen F, li Q, li M, et al, uncloable Fluorescence Behaviors of Perovskite Quantum Dots/Chaotic Metasurfaces Hybrid Nanostructures for Versatile Security Primitive [ J ]. Chemical Engineering Journal,2021, 411:128350.). Therefore, the application of the optical PUF to the anti-counterfeiting label of the chip is a safe and efficient anti-counterfeiting means. The optical PUF according to the present invention refers to a PUF that outputs a response (response) as an optical signal under a certain excitation condition, where the signal is an optical response signal, and the optical response signal includes, but is not limited to: fluorescence (fluorescence), phosphorescence (phosphorescence), laser (laser), raman scattering (Raman scattering), and the like.
One core indicator for evaluating the performance of an optical PUF is the coding capacity, which is the smaller the coding capacity, the more easily the anti-counterfeit system is broken (Encoding capacity, which is fundamental to the effectiveness of PUF systems-the lower the encoding capacity, the easier the system to be coded. Gu Y, he C, zhang Y, et al gap-enhanced Raman tags for physically unclonable anticounterfeiting labels [ J ]. Nature Communications,2020,11 (1): 1-13.), and therefore, we need to have the coding capacity as large as possible to ensure the security of the anti-counterfeit system. The coding capacity is the theoretical maximum number of optical PUFs and the calculation formula is as follows (see Figure 1d,Hu Y W,Zhang T P,Wang C F,et al.Flexible and Biocompatible Physical Unclonable Function Anti-Counterfeiting Label [ J ]. AdvancedFunctional Materials,2021, 2108:1-9.):
coding capacity=a B (1)
Wherein A is the number of responses per pixel in the PUF (the number of responses for eachpixel in PUF), and B is the total number of pixels in the PUF (the total number of pixels in PUF); in an actual optical PUF pattern, each pixel corresponds to any point on the optical PUF, i.e. a is the number of optical response signals generated by any point in the optical PUF and B is the total number of all points in the optical PUF. The number B of all points of the resulting optical PUF is different due to the different test conditions of the different optical PUFs. As can be seen from the above formula, increasing a or B can increase the coding capacity, however, increasing B only needs to increase the total amount of all points in the test, B can freely set larger or smaller values according to different experimental needs, and the improvement of B is not a technical problem, but as B increases, the test time is correspondingly prolonged, which is unfavorable for the rapid detection of the performance of the optical PUF, so for the detection convenience and scientifically comparing the coding capacity between different optical PUFs, the person skilled in the art generally fixes B unchanged, i.e. the total amount B of all points of the optical PUF is generally set to 100×100. Therefore, based on the above encoding capacity calculation formula, increasing a can essentially increase the encoding capacity of the optical PUF, where a is the number of optical response signals generated at any point of the optical PUF, and the larger a, the larger the encoding capacity of the optical PUF. The number of optical response signals refers to the number of optical response signals (response) that the optical PUF generates when receiving a stimulus (challenge).
However, the prior art study of optical PUFs has mainly two problems:
first, existing optical PUFs have complex and costly methods of increasing the encoding capacity (encoding capacity).
In order to increase the encoding capacity of an optical PUF, researchers have found that numerical processing of the collected optical response signals can effectively increase the encoding capacity of an optical PUF. Gu et al propose that the number A of optical response signals generated at any point of the optical PUF can be increased from 2 to 4 by using a Global Search (GS) algorithm, so that when the total number B of all points of the optical PUF is 100×100, the code capacity of the optical PUF is 4 10000 (Gu Y,He C,Zhang Y,et al.Gap-enhanced Raman tags for physically unclonable anticounterfeiting labels[J]Nature Communications,2020,11 (1): 1-13.). Wu et al propose the use ofDividing the wavelength range of the reflectance spectrum increases the number a of optical response signals generated at any point of the optical PUF from 2 to 10, so that the encoding capacity of the optical PUF is 10 when the total number B of all points of the optical PUF is 100×100 10000 (WuJ,Liu X,Liu X,et al.AHigh-Security mutual authentication system based on structural color-based physical unclonable functions labels[J]Chemical Engineering Journal,2022,439 (February): 135601.). Although the coding capacity of the optical PUF can be improved by performing numerical processing on the collected optical response signals, the optical PUF must first undergo a complex numerical processing process when receiving the excitation, so that the time of the optical PUF in the verification stage is increased, that is, the time of outputting the response signals is prolonged when the optical PUF receives the excitation, the working efficiency of the optical PUF is affected, and in addition, the complex numerical processing process may also cause signal errors and crosstalk, so that the method is difficult to apply to the industrial large scale.
Researchers in the prior art have also increased the encoding capacity of optical PUFs by doping with a variety of elements. Researchers find that the number a of optical response signals generated at any point in the optical PUF in the coding capacity calculation formula is related to the characteristics of the material itself, and the larger a is doped with multiple elements, the larger the coding capacity of the optical PUF, so that the researchers use the material doped with multiple elements to prepare the optical PUF. Carro-Temboury et al utilizes the incorporation of 3 rare earth elements (Eu) into zeolite 3+ ,Tb 3+ And Dy 3+ ) The method of (2) increasing the encoding capacity of an optical PUF by increasing the number a of optical response signals generated at any point of the optical PUF from 4 to 7, the encoding capacity of the optical PUF being 7 when the total number B of all points of the optical PUF is 60 x 60 3600 As previously known, when the total amount B of all points of the optical PUF is 100×100, the encoding capacity of the optical PUF is 7 10000 ，(Figure 2,Carro-Temboury M R,Arppe R,Vosch T,et al.An optical authentication system based on imaging of excitation-selected lanthanide luminescence[J]Science Advances,2018,4 (1): 1-8.). Song et al use NaGdF 4 @NaYF 4 Is doped with rare earth in 4 in the core-shell structureElement (Ce) 3+ ，Yb 3+ ，Er 3+ And Eu 3+ ) The method can make the material emit light under 3 different excitation wavelengths, so that the number A of optical response signals generated by any point of the optical PUF is 3, and when the total point number B of the optical PUF is 100×100, the encoding capacity of the optical PUF is 3 10000 (SongY,Sun R,Sun G,et al.Upconversion/Downshifting Multimode Luminescence of Lanthanide-doped Nanocrystals for Multidimensional Information Encoding Security[J]Chemistry-An Asian Journal,2022,17 (17). Kumar et al use in Y 2 O 3 Is doped with 3 medium rare earth element (Eu) 3+ ，Tb 3+ ，Ce 3+ ) The method can make the material emit light under 3 different excitation wavelengths, so that the number A of optical response signals generated by any point of the optical PUF is 3, and when the total point number B of the optical PUF is 100×100, the encoding capacity of the optical PUF is 3 10000 (Sun T,Xu B,Chen B,et al.Anti-counterfeitingpatterns encryptedwith multi-mode luminescent nanotaggants[J].Nanoscale,Royal Society of Chemistry,2017,9(8):2701–2705.)。
From the above documents, it is known that the number a of optical response signals can be increased by doping elements without performing numerical processing on the optical response signals, so as to increase the coding capacity of the optical PUF, but the optical PUF can only be realized by doping multiple elements, but each element is different in the introduction process due to the characteristic difference, so that the more the types of the doping elements, the more complicated the preparation process, so that the process cost is greatly increased, and the large-scale application is difficult.
Second, the current process for preparing optical PUFs is not compatible with chip preparation processes.
PUF structures are diverse, where optical PUFs are typical representatives of non-silicon based PUFs (Hu Yanwei. Preparation and application research of diamond-based flexible physical unclonable function tags [ D)]Henan, university of Zhengzhou, 2021.). Because silicon materials themselves have low luminous efficiency and cannot detect optical response signals, silicon materials are difficult to be used for preparing optical PUFs, and silicon-based PUFs in the prior art are all electrical PUFs (GaoY, al-Sarawi) S F,AbbottD.Physical Unclonable Functions[J]Nature Electronics,2020,3 (2): 81-91.). The silicon-based optical PUF refers to an optical PUF of a silicon-containing material of a luminous functional layer capable of generating an optical response signal. The compatibility of the invention means that the process for preparing the optical PUF can adopt one or more of the mainstream processes for preparing the existing chip, and no additional process is required to be introduced, so that the production cost is not greatly increased. The dominant process for chip fabrication is Complementary Metal Oxide Semiconductor (CMOS) process (Zhou Minxin. Research on capacitive pressure sensor with multilayer film structure and CMOS compatible process [ D ]]University of eastern, 2006, p 39), CMOS processes mainly include processes such as oxidation, spin coating, wet/dry etching, ion implantation, chemical vapor deposition, thermal annealing, etc. (semiconductor manufacturing technology/(meik, m.); han Zhengsheng, beijing: electronics industry publishers, 2004.1, P187). Whereas existing optical PUFs utilize radio frequency sputtering (Im H, yoon J, choi J, et al Chaotic Organic Crystal Phosphorescent Patterns for Physical Unclonable Functions [ J)]Advanced Materials,2021, 2102542:1-9.), electron beam evaporation (Chen F, li Q, li M, et al Unclonale Fluorescence Behaviors of Perovskite Quantum Dots/Chaotic Metasurfaces Hybrid Nanostructures for Versatile Security Primitive [ J ] ]Chemical Engineering Journal,2021, 411:128350.), physical stripping and stacking (Kim J H, jeon S, in J H, et al nanoscales Physical Unclonable Function Labels Based on Block Co-Polymer Self-Assembly [ J ]]Nature Electronics,2022,5 (7): 433-442.) and the like. The existing optical PUF preparation processes such as radio frequency sputtering, electron beam evaporation, physical stripping and stacking do not belong to the main process CMOS for chip preparation, and introducing additional processes into the CMOS process greatly increases the production cost, which results in serious impediments to the practical application of the existing optical PUF in chip anti-counterfeiting (Itspracticality is hindered by its inconvenient compatibility with current complementary metal-oxide-semiconductor (CMOS) manufacturing process. Gao, y., al-Sarawi, S.F).&Abbott, d.nat.electron.3,81-91 (2020). In addition, the method for improving the coding capacity of the optical PUF by doping multiple elementsThe doping object is zeolite, naGdF 4 @NaYF 4 、Y 2 O 3 Such materials, none of which is a silicon material, are incompatible with existing silicon material based CMOS processes and therefore greatly increase production costs. Although Silicon-based PUFs compatible with CMOS processes have been reported to date, they are all electrical PUFs, with the risk of being attacked by modeling (Silicon PUFs, and especially variants of APUFs, are potentially affected by powerful modelling attacks. Gao Y, al-Sarawi S F, abbott D.physical unclonable functions [ J) ]Nature Electronics Springer US 2020,3 (2): 81-91.). Thus, if the process of preparing the optical PUF is not compatible with the CMOS process, the optical PUF is difficult to apply on a large scale because the overall process is complex and not easy to control and the process cost is too high.
In summary, the existing optical PUF improves the encoding capacity mainly by performing complex numerical processing and/or doping of multiple elements on the optical response signal, and still has the problems of complex processing, complex preparation process and high cost of the optical response signal, which is difficult to apply on a large scale; in addition, for the existing optical PUF, the light-emitting functional layer capable of generating the optical response signal does not contain silicon materials, and the preparation process of the light-emitting functional layer is incompatible with the existing CMOS process based on the silicon materials, so that the production cost can be greatly increased, and the practical application of the existing optical PUF on chip anti-counterfeiting is seriously hindered. Therefore, the research on the optical PUF with high coding capacity, which is compatible with the existing CMOS technology based on the silicon material, simple in preparation method and low in cost, has great value by only doping one element without complex numerical processing on an optical response signal.
Disclosure of Invention
In order to overcome the defects of the prior art, the inventor provides a silicon-based optical PUF, and unexpectedly realizes that the quantity A of optical response signals generated by any point of the silicon-based optical PUF is 7 only through doping of one rare earth element and no complex numerical processing is required to be carried out on the optical response signals after long-time effort exploration, and the quantity A of the optical response signals generated by any point of the silicon-based optical PUF is 7 only through doping of one element at present 10000 Silicon-based optical PUF of (C) and overcomeThe technical prejudice that silicon materials cannot be applied to optical PUFs because they do not emit light. The silicon-based optical PUF preparation process is compatible with the existing CMOS process based on silicon materials, has low cost, is suitable for large-scale production, and has great application prospect.
The invention adopts the following technical scheme:
the present invention provides a silicon-based optical PUF comprising a substrate 1 and a nanomaterial layer 2 on the substrate 1, wherein:
the substrate 1 is used for providing an uneven structure, and the average value of the side length and the average value of the depth of the uneven structure are respectively smaller than the central light-emitting wavelength of the nano material layer 2; the resistivity of the substrate (1) is less than or equal to 0.005 omega cm;
the material of the nanomaterial layer 2 is erbium-doped silicon nanomaterial, and 7 different optical response signals can be generated at any point on the nanomaterial layer 2, which are respectively: blank back, surface morphology, luminous intensity of the silicon nanomaterial, luminous intensity of erbium ions, central luminous wavelength of the silicon nanomaterial, luminous life of the silicon nanomaterial, and luminous intensity ratio of the silicon nanomaterial to the erbium ions;
the 7 different optical response signals are generated from the erbium-doped silicon nanomaterial;
The erbium-doped silicon nanomaterial comprises silicon element and erbium element, wherein the silicon element exists in the form of nano silicon, and the erbium element completely exists in the form of Er 3+ Morphology exists within the crystal lattice of the silicon nanomaterial and is optically active; preferably, the average grain diameter of the erbium-doped silicon nano material is 3-5 nm;
the 7 different optical response signals, except for the blank back, and the rest 6 optical response signals are changed along with the change of the position of any point on the substrate;
the calculation formula of the coding capacity is as follows:
coding capacity=a B (1)
Wherein A is the number of responses per pixel in the PUF (the number of responses for each pixel in PUF), and B is the total number of pixels in the PUF (the total number of pixels in PUF); in a practical optical PUF pattern, each pixel may be described as any point on the optical PUF. In the present invention, a is the number of optical response signals generated at any point on the nanomaterial layer 2 in the silicon-based optical PUF, a=7, and b is the total amount of all points in the silicon-based optical PUF.
It should be emphasized that the dimensions of the substrate 1 are in the order of centimeters (cm), while the preparation of special rugged structures on the surface of the substrate 1 are in the order of nanometers (nm), and the regulation of the nanoscale dimensions on the order of centimeters is very demanding and not easy to implement. The centimeter (cm) level refers to that the minimum size of an object is more than or equal to 1.5cm; the nanometer (nm) level refers to the maximum dimension of an object being less than or equal to 800nm. The invention skillfully realizes the cooperative coupling of the nano material layer (2) and the substrate (1) by controlling the cooperative effects of various parameters such as etching components, etching component proportion, adding volume, etching time, temperature, cleaning and the like, realizes that the quantity A of optical response signals generated by any point of the silicon-based optical PUF is 7 only through doping one rare earth element without complex numerical processing on the optical response signals, and realizes that the coding capacity is 7 only through the material doped by one element at present 10000 And overcomes the technical prejudice that silicon materials cannot be applied to optical PUFs because they do not emit light.
The blank back refers to an optical response signal under the condition of no excitation (excitation) among the 7 different optical response signals; the luminous intensity is a numerical value obtained by carrying out one-time integration on a luminous spectrum; the central luminous wavelength is the wavelength value corresponding to the highest point of the luminous spectrum curve; the luminescence lifetime is a value obtained by fitting a luminescence decay curve and calculating the luminescence decay curve.
The excitation condition of the surface topography is a white light source;
the excitation condition of the luminous intensity of the silicon nano material, the luminous intensity of erbium ions, the central luminous wavelength of the silicon nano material, the luminous service life of the silicon nano material and the luminous intensity ratio of the silicon nano material to the erbium ions is laser with the central luminous wavelength of 300-600 nm; preferably, the excitation condition is a laser with a central emission wavelength of 405 nm;
because the nanomaterial layer 2 can generate coupling effects such as reflection, refraction, scattering, absorption, localization and the like with the substrate 1, the quantity A of optical response signals generated at any point on the nanomaterial layer 2 is determined by the nanomaterial layer 2 and the coupling effect between the specific substrate 1 and the nanomaterial layer 2. When the nanomaterial layer 2 is attached to other common substrates (such as quartz plates and silicon wafers which are not etched specifically in the invention), the nanomaterial layer 2 and the substrates cannot be coupled, so that the number A of optical response signals generated at any point on the nanomaterial layer 2 is only determined by the nanomaterial layer 2, and at the moment, A=5; however, when the nanomaterial layer 2 is attached to the substrate 1 of the present invention, since the nanomaterial layer 2 and the substrate 1 will have a coupling effect, two optical response signals, that is, a central light-emitting wavelength of the silicon nanomaterial and a light-emitting lifetime of the silicon nanomaterial, are unexpectedly generated more, so that the number a of the optical response signals generated at any point on the nanomaterial layer 2 is increased, where a=7; thus greatly improving the coding capacity of 7 of the optical PUF 10000 。
The coupling action of the nanomaterial layer 2 with the substrate 1 is represented by the fact that the central emission wavelength of the silicon nanomaterial and the emission lifetime of the silicon nanomaterial change with the change of the position of the substrate 1 (fig. 18, fig. 21), while the uncoupling action is represented by the fact that the central emission wavelength of the silicon nanomaterial and the emission lifetime of the silicon nanomaterial do not change with the change of the position of the substrate (fig. 22, fig. 23); the "position" in the present invention refers to any point of the silicon-based optical PUF, and the "point" and "position" in the present invention have the same meaning, i.e. the "point 1" and "position 1" are equivalent, corresponding to the point 1-point n in fig. 5.
Further, the side length average value calculation formula is as follows:
wherein n is the total number of sides of the rugged structure, L i Is the length of the ith edgeA degree; preferably, the average value of the side length is less than 830nm; more preferably, the average edge length is 610.+ -.20 nm (FIG. 7).
Further, the depth average value calculation formula is as follows:
wherein m is the total number of concave-convex structural grooves, H i Is the depth of the ith groove, and the depth is the vertical distance between the highest point and the lowest point in any groove; preferably, the depth average is < 830nm; more preferably, the depth average is 660.+ -.20 nm (FIG. 8).
Further, the resistivity of the substrate 1 is less than or equal to 0.005 Ω. cm; preferably, the substrate 1 is a silicon-containing material; preferably, the substrate 1 is a doped silicon-containing material; more preferably, the substrate 1 is an n-type doped silicon wafer; preferably, the doping element in the doped silicon wafer is at least one of nitrogen (N), phosphorus (P), arsenic (As) and antimony (Sb); preferably, the doping element is arsenic (As).
Further, the central luminous wavelength of the erbium-doped silicon nanomaterial is more than or equal to 830nm; preferably, the center luminescence wavelength of the erbium-doped silicon nanomaterial is around 830nm and around 1540nm, respectively. The term "near" as used herein refers to a wavelength within + -5 nm of the central emission wavelength.
Furthermore, a protective layer 3 is also arranged on the nanomaterial layer 2; preferably, the wavelength range of the absorption spectrum of the protective layer 3 is not overlapped with the wavelength range of the luminescence spectrum of the nanomaterial layer 2; preferably, the absorption cut-off wavelength of the protective layer 3 is less than or equal to 400nm, and the absorption cut-off wavelength refers to a critical value from an absorption signal to a non-absorption signal on an absorption spectrum; preferably, the material of the protective layer 3 is a polymer; more preferably, the material of the protective layer 3 is at least one selected from polymethyl methacrylate, polyvinyl alcohol resin, polyimide; more preferably, the material of the protective layer 3 is polymethyl methacrylate.
Further, with the protective layer 3, the light emitting performance of the nanomaterial layer 2 is not significantly attenuated in air (fig. 24), in contrast to the light emitting performance of the nanomaterial layer 2 without the protective layer 3, which is significantly attenuated in air (fig. 25).
The quantity A of optical response signals generated at any point of the silicon-based optical PUF in the previous study is independently determined by the nano material layer 2, the substrate 1 only plays a supporting role and does not contribute to the improvement of the coding capacity, and in the invention, the silicon-based optical PUF is accurately regulated and controlled by accurately controlling the parameters such as the etching components of the preparation method, the addition amount of the etching components, the etching time, the type and the addition amount of the erbium-doped silicon nano material, namely the silicon-based optical PUF needs to simultaneously meet the requirement that the substrate 1 has an uneven structure, and the average value of the side length and the average value of the depth of the uneven structure are respectively smaller than the central luminous wavelength of the nano material layer 2; the material of the nano material layer 2 is erbium-doped silicon nano material, 7 different optical response signals can be generated at any point on the nano material layer 2, the erbium-doped silicon nano material comprises silicon element and erbium element, wherein the silicon element exists in the form of nano silicon, and the erbium element completely exists in the form of Er 3+ Morphology exists within the crystal lattice of the silicon nanomaterial and is optically active; the condition is not necessary, so that the quantity A of optical response signals generated by any point of the silicon-based optical PUF is determined by the nano material layer 2 and the coupling action of the specific substrate 1 and the nano material layer 2, the quantity A of the optical response signals generated by any point of the silicon-based optical PUF is improved, and the coding capacity of the silicon-based optical PUF is further improved. The method for improving the coding capacity by jointly coupling the substrate 1 and the nano material layer 2 is not reported in the prior literature, and has great innovation. Furthermore, the invention smartly utilizes the nano material layer 2 to couple with the silicon chip substrate 1, realizes high coding capacity by a preparation method which is compatible with the prior silicon-based CMOS process through an element doping material, and realizes the coding capacity of 7 of the silicon-based optical PUF under the total amount of all points of the test condition of 100 multiplied by 100 10000 Is the maximum coding capacity (shown in table 1) which can be achieved by only one element doping material and not carrying out numerical processing on an optical response signal at present, breaks through the prior artThe challenge of high encoding capacity is to dope multiple elements and/or through complex processing of the optical response signal.
Therefore, the invention still maintains high coding capacity by using a preparation method compatible with the existing silicon-based CMOS technology under the condition of doping only one element, does not need to carry out complex numerical processing on an optical response signal, greatly simplifies the process of extracting the response signal, ensures that the detection and verification process is simpler, has great innovation and practical value, and has great application prospect.
The invention provides a preparation method of the silicon-based optical PUF, which comprises the following steps:
etching the silicon wafer by using a mixed solution containing copper ions, hydrogen peroxide and hydrofluoric acid, wherein the ratio of the addition amount of the copper ions to the area of the silicon wafer is 0.0003-0.0008 mol/cm 2 The volume ratio of the hydrogen peroxide to the hydrofluoric acid is 1:1, and the ratio of the total addition amount of the hydrogen peroxide and the hydrofluoric acid relative to the area of the silicon wafer is 5-15 mL/cm 2 Etching for 0.5-2 min, cleaning and drying to obtain a substrate 1;
the invention skillfully realizes the cooperative coupling of the nano material layer (2) and the substrate (1) by controlling the cooperative effects of various parameters such as etching components, etching component proportion, adding volume, etching time, temperature, cleaning and the like, realizes that the quantity A of optical response signals generated by any point of the silicon-based optical PUF is 7 only through doping one rare earth element without complex numerical processing on the optical response signals, and realizes that the coding capacity is 7 only through the material doped by one element at present 10000 And overcomes the technical prejudice that silicon materials cannot be applied to optical PUFs because they do not emit light.
Preferably, the copper ions are from copper ion salts; preferably, the copper ions are from copper nitrate trihydrate;
preferably, the preparation temperature of the mixed solution is 45-80 ℃; more preferably, the temperature is 50 ℃;
preferably, the stirring time for preparing the mixed solution is 10-30 min; more preferably, the stirring time is 10 minutes;
preferably, the ratio of the addition amount of the copper ions to the area of the silicon wafer is 0.0006mol/cm 2 ；
Preferably, the ratio of the total addition amount of hydrogen peroxide and hydrofluoric acid to the area of the silicon wafer is 10mL/cm 2 ；
Preferably, the volume fraction of the hydrogen peroxide is more than or equal to 30%;
preferably, the volume fraction of hydrofluoric acid is more than or equal to 40%;
preferably, the etching time is 1min;
preferably, the cleaning is that the silicon wafer is put into nitric acid for ultrasonic cleaning, and the ultrasonic cleaning time is 20min;
step (2) dissolving the C7-C18 olefin modified erbium-doped silicon nanomaterial in a low-boiling nonpolar solvent to prepare a solution, coating the solution on the surface of the substrate 1, and heating to remove the low-boiling nonpolar solvent to prepare the silicon-based optical PUF with the nanomaterial layer 2 on the substrate 1, wherein the ratio of the quantity of the erbium-doped silicon nanomaterial to the area of the silicon wafer is 20-60 mu L/cm 2 The low-boiling nonpolar solvent is a solvent with a boiling point lower than 150 ℃; the olefin of C7-C18 is any one of heptene to octadecene;
preferably, the olefin modification comprises the steps of dissolving erbium-doped silicon nano material particles in a mixed solution of mesitylene and olefin, and then adding xenon difluoride mesitylene solution, wherein the olefin is C7-C18 olefin;
preferably, in the mixed solution, the volume ratio of mesitylene to olefin is 1:1-3:1;
more preferably, the olefin modification specifically comprises the steps of:
step A), erbium-doped silicon nano material particles are dissolved in methanol and fully dispersed, and then the erbium-doped silicon nano material methanol solution is prepared;
step B), adding hydrofluoric acid with the volume fraction of more than or equal to 40% into the erbium-doped silicon nanomaterial methanol solution prepared in the step A), stirring for 1-5 minutes, centrifuging for 1-5 minutes at the rotating speed of 5000-9000 rpm, pouring out supernatant, rapidly dissolving the erbium-doped silicon nanomaterial in a centrifuge tube by using mesitylene, then adding the mixed solution consisting of the mesitylene and olefin according to the volume ratio of 1:1-3:1, wherein the olefin is C7-C18 olefin, continuously adding xenon difluoride mesitylene solution, and heating for 3-5 hours at the temperature of 160-180 ℃ to prepare the erbium-doped silicon nanomaterial;
Preferably, the olefin is dodecene;
preferably, the ratio of the amount of erbium-doped silicon nanomaterial to the area of the silicon wafer is 35. Mu.L/cm 2 ；
Preferably, the low boiling nonpolar solvent is toluene;
preferably, the temperature for heating to remove the low-boiling nonpolar solvent is 160-250 ℃; more preferably the temperature is 160 ℃;
preferably, the time for heating to remove the low-boiling nonpolar solvent is 30-60 min; more preferably, the time is 30 minutes.
Further, after the step (2) of the preparation method, the method further comprises a step of preparing the protective layer 3, which specifically comprises the following steps: coating the solution of the protective layer 3 on the upper part of the nano material layer 2, wherein the rotating speed is 1000-3000 rpm, the time is 0.5-1 min, the proportion of the solution of the protective layer 3 relative to the area of the silicon wafer is 20-60 mu L/cm < 2 >, and heating to remove solvent components in the solution to prepare the silicon-based optical PUF with the protective layer 3;
preferably, the solution of the protective layer 3 is selected from polymer solutions; more preferably, the solution of the protective layer 3 is selected from anisole solution of polymethyl methacrylate, aqueous solution of polyvinyl alcohol resin, dimethylformamide solution of polyimide; more preferably, the protective layer 3 is an anisole solution of polymethyl methacrylate;
Preferably, the ratio of the amount of solution of the protective layer 3 to the area of the silicon wafer is 35. Mu.L/cm 2 ；
Preferably, the rotating speed is set to 2000 revolutions per minute and the time is set to 45 seconds;
preferably, the temperature of the solvent component in the heating removal solution is 160-250 ℃; more preferably, the temperature is 160 ℃;
preferably, the time for heating to remove the solvent component in the solution is 30-60 min; more preferably, the time is 30 minutes.
The invention controls the etching component in the step (1), the adding amount of the etching component, the etching time, the type of the erbium-doped silicon nanomaterial in the step 2, the adding amount and other parameter conditions, so that the silicon-based optical PUF is accurately regulated and controlled, the substrate 1 with a specific rugged structure is obtained, the average value of the side length and the average value of the depth of the rugged structure are respectively smaller than the central light-emitting wavelength of the nanomaterial layer 2, the material of the nanomaterial layer 2 is erbium-doped silicon nanomaterial, the erbium-doped silicon nanomaterial comprises silicon element and erbium element, the silicon element exists in the form of nano silicon, and the erbium element is Er 3+ Morphology exists within the crystal lattice of the silicon nanomaterial and is optically active; the coupling effect of the substrate 1 and the nanomaterial layer 2 with the specific structure of the invention is realized unexpectedly, namely the central luminescence wavelength of the silicon nanomaterial and the luminescence service life of the silicon nanomaterial are changed along with the change of the position of the substrate 1 (figure 18 and figure 21), the number of optical response signals A at any point on the nanomaterial layer 2 of the silicon-based optical PUF is 7, and the coding capacity of the silicon-based optical PUF is 7 under the test condition that the total quantity B of all points of the silicon-based optical PUF is 100 multiplied by 100 10000 And overcomes the technical prejudice that silicon materials cannot be applied to optical PUFs because they do not emit light.
Furthermore, the invention also provides an anti-counterfeiting label, which comprises the silicon-based optical PUF or the silicon-based optical PUF prepared by the preparation method.
Furthermore, the invention provides the silicon-based optical PUF, the silicon-based optical PUF prepared by the preparation method and the application of the anti-counterfeiting label in the anti-counterfeiting field.
The silicon-based optical PUF of the present invention is manufactured by an etching coating process, wherein the coating comprises a simple and low cost Spin-coating process (Spin-coating are simple, universal, and cost-effective substrate-up technologies to provide functional coatings, naveas N, manso-Silv N M, et al manufacturing and characterization of nanostructuredporous silicon-silver composite layers by cyclic deposition: dip-coating vs Spin-coating [ J ]. Nanotechnology,2020,31 (36)). In addition, the spin-coating process is Compatible with CMOS processes (CMOS Compatible technologies such as spin coating.vyasA, hajibaher S Z, M ndez-Romero U, et al spin-Coated Heterogenous Stacked Electrodes for Performance Enhancement in CMOS-composite On-Chip Microsupercapacitors [ J ]. ACS Applied Energy Materials,2022,5 (4): 4221-4231), so that the silicon-based optical PUF of the present invention can be directly integrated onto the existing chip preparation process line, greatly reducing the production cost.
The beneficial effects of the invention are as follows:
aiming at the defects of the prior art, the invention provides the silicon-based optical PUF which is prepared by only doping the silicon nanomaterial with the rare earth element and does not need to carry out complex data processing on an optical response signal, has high coding capacity and low cost, and the preparation method is compatible with a CMOS (complementary metal oxide semiconductor) process, has simple process and low cost, and overcomes the technical prejudice that the silicon material cannot be applied to the optical PUF because of no luminescence.
(1) The invention overcomes the technical prejudice that the coding capacity can be improved by using 2 or more elements doped materials and/or by complex numerical processing of optical response signals in the prior art, and the coupling effect of the substrate 1 and the nanomaterial layer 2 with specific structures is realized by using only one rare earth element doped silicon nanomaterial, the numerical processing of the optical response signals is not needed, the number of optical response signals A generated at any point on the nanomaterial layer 2 of the silicon-based optical PUF is 7, and the coding capacity of the silicon-based optical PUF is 7 under the test condition that the total quantity B of all points of the silicon-based optical PUF is 100 multiplied by 100 10000 。
(2) The invention overcomes the technical prejudice that the quantity A of optical response signals generated at any point of the silicon-based optical PUF in the prior art is independently determined by the nano material layer 2, and the substrate 1 only plays a supporting role and does not contribute to the improvement of the coding capacity. According to the invention, the special rugged structure is prepared on the surface of the substrate 1, so that the quantity A of optical response signals generated at any point on the nano material layer 2 of the silicon-based optical PUF is determined not only by the nano material layer 2, but also by the coupling action of the substrate 1 and the nano material layer 2, the quantity A of optical response signals generated at any point on the nano material layer 2 of the silicon-based optical PUF is improved, and the coding capacity of the silicon-based optical PUF is further improved. The method for improving the coding capacity by utilizing the joint coupling of the substrate 1 and the nano material layer 2 is not reported in the prior literature, and has great innovation.
(3) The preparation method of the silicon-based optical PUF is compatible with the existing CMOS technology based on the silicon material, the technology is simple and low in cost, and the nano material layer (2) contains the silicon material capable of generating the optical response signal, so that the technical prejudice that the silicon material cannot be applied to the optical PUF because of no luminescence is overcome, the silicon-based optical PUF is directly integrated on the existing chip preparation technology line, the production cost is greatly reduced, and the industrial large-scale application is facilitated.
Therefore, the silicon-based optical PUF still maintains high coding capacity under the condition of using only one element doped material by using a preparation method compatible with the existing CMOS technology based on the silicon material, does not need to carry out complex numerical processing on an optical response signal, greatly simplifies the process of extracting the response signal, ensures that the detection and verification processes are simpler, reduces the production cost, and has great innovation, practical value and application prospect.
Drawings
Fig. 1 is a scanning electron microscope image of a cross section of a silicon-based optical PUF, wherein 1 is a substrate and 2 is a nanomaterial layer;
fig. 2 is a scanning electron microscope image of a cross section of a silicon-based optical PUF with a protective layer 3, wherein 1 is a substrate, 2 is a nanomaterial layer, and 3 is a protective layer;
Fig. 3 is a schematic cross-sectional view of a silicon-based optical PUF, wherein 1 is a substrate, 2 is a nanomaterial layer, and 3 is a protective layer;
fig. 4 is a scanning electron microscope image of a top view of the substrate 1;
fig. 5 is a schematic diagram of a top view of the substrate 1;
fig. 6 is a scanning electron microscope image of a cross section of the substrate 1;
FIG. 7 is a statistical distribution diagram of the side length of the etched silicon wafer;
FIG. 8 is a statistical distribution of the dimensions of the depth of the etched wafer;
FIG. 9 is a transmission electron microscope image of erbium doped silicon nanomaterial;
FIG. 10 is a statistical distribution plot of the dimensions of erbium-doped silicon nanomaterials;
FIG. 11 is a fluorescence spectrum of erbium-doped silicon nanomaterial;
FIG. 12Er 3+ A graph of luminescence intensity around 1540nm with excitation power;
FIG. 13 is an absorption spectrum of PMMA;
FIG. 14 is an X-ray photoelectron spectrum of erbium;
FIG. 15 is a high angle annular dark field scanning transmission electron microscope image of an erbium doped silicon nanomaterial;
FIG. 16 is a blank back bottom view;
FIG. 17 is a surface topography of a silicon-based optical PUF;
FIG. 18 is a graph of fluorescence spectra (500-1200 nm) at different positions after coupling of erbium-doped silicon nanomaterial with silicon wafer;
FIG. 19 is a graph of fluorescence spectra (1450-1620 nm) at different positions after coupling of erbium-doped silicon nanomaterial with silicon chip;
FIG. 20 is a graph of the ratio of luminous intensity at different positions after the erbium-doped silicon nanomaterial is coupled with the grooves on the surface of the silicon wafer;
FIG. 21 is a graph of luminescence lifetime at different positions after coupling of erbium-doped silicon nanomaterial with a silicon wafer surface groove;
FIG. 22 is a graph of fluorescence spectra at different positions after the erbium-doped silicon nanomaterial is dripped on the surface of a common silicon wafer;
FIG. 23 is a graph of luminescence lifetime at different positions after the erbium-doped silicon nanomaterial is dropped onto a surface of a common silicon wafer;
FIG. 24 is a graph of luminescence properties of a sample with PMMA protective layer over time;
FIG. 25 is a graph of luminescence properties of a sample without PMMA protective layer over time;
FIG. 26 is a workflow diagram of a silicon-based optical PUF;
fig. 27 is a binarized image plot of a silicon-based optical PUF;
fig. 28 shows a similarity profile of a silicon-based optical PUF.
Detailed Description
Unless defined otherwise, technical or scientific terms used in this patent document should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. As used in the present specification and claims, the terms "upper," "lower," "left," "right," "inner," "outer," and the like are used merely as relative positional relationships, which may be changed when the absolute position of the object being described is changed, merely to facilitate description of the present invention and simplify the description, and do not denote or imply that the apparatus or elements being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present invention.
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
The detection method of each performance is as follows:
1. the detection method of the silicon-based optical PUF structure comprises the following steps:
shooting a multilayer structure of the silicon-based optical PUF through a scanning electron microscope with the model of JSM-IT800, wherein the electron acceleration voltage is 5kV, and the working distance is 8mm;
2. the detection method of the average value of the side length comprises the following steps:
shooting a top view of the substrate 1 by a scanning electron microscope with the model of JSM-IT800, wherein the electron acceleration voltage is 5kV, the working distance is 8mm, and then reading the length value of the edge in the visual field range by a measuring scale tool of the scanning electron microscope, wherein the number of the read edges is more than or equal to 100; the 'side' refers to an image in a straight line shape under the imaging of a scanning electron microscope, and does not contain non-straight line images such as curves, corners and the like;
3. the detection method of the depth average value comprises the following steps:
shooting a top view of the substrate 1 by a scanning electron microscope with the model of JSM-IT800, wherein the electron acceleration voltage is 5kV, the working distance is 8mm, and then reading depth values of grooves in a visual field range by a measuring scale tool of the scanning electron microscope, wherein the number of the grooves read is more than or equal to 100; the groove refers to an image which is in a concave shape under the imaging of a scanning electron microscope;
4. The detection method of the resistivity of the substrate 1 comprises the following steps:
the resistivity of the substrate 1 is detected by a four-probe method;
5. the detection method of the doping element of the substrate 1 comprises the following steps:
detecting by an energy spectrometer (EDS) matched with a scanning electron microscope, wherein the electron acceleration voltage is 20kV, and the working distance is 15mm;
6. the detection method of the average particle size of the erbium-doped silicon nanomaterial comprises the following steps:
detecting the erbium-doped silicon nanomaterial by a transmission electron microscope, wherein the electron acceleration voltage is 200kV, and then counting the particle size of the erbium-doped silicon nanomaterial to obtain the average particle size of the erbium-doped silicon nanomaterial;
7. the detection method of the optical response signal generated at any point on the nanomaterial layer 2 comprises the following steps:
and detecting an optical response signal generated at any point on the nanomaterial layer 2 by using a fluorescence spectrometer. Wherein, the blank back refers to an optical response signal under the condition of no excitation (challenge); the excitation condition of the surface topography is white light; the excitation condition of the luminous intensity of the silicon nano material, the luminous intensity of erbium ions, the central luminous wavelength of the silicon nano material, the luminous service life of the silicon nano material and the luminous intensity ratio of the silicon nano material to the erbium ions is laser with the central luminous wavelength of 300-600 nm; preferably, the excitation condition is a laser with a central emission wavelength of 405 nm;
8. The method for detecting the luminescence life of the silicon nanomaterial comprises the following steps:
detecting a luminescence attenuation curve of the silicon nanomaterial by using a fluorescence spectrometer, wherein the excitation wavelength is 405nm, the frequency is 100Hz, fitting the luminescence attenuation curve by using the following formula (4), and finally calculating the luminescence life by using the following formula (5).
Where I (t) is the value of the intensity of the luminescence decay curve over time, A1 and A2 are the fitting coefficients, τ1 and τ2 are the fast and slow lifetimes, respectively, of the fitting, τ is the luminescence lifetime.
9. The detection method of the valence state of erbium element comprises the following steps:
detection is carried out by X-ray photoelectron spectroscopy;
10. the detection method for the erbium element existing in the lattice of the silicon nanometer material comprises the following steps:
observing the erbium-doped silicon nanomaterial by using a high-angle annular dark field scanning transmission electron microscope (HAADF-STEM);
11、Er 3+ the detection method with optical activity comprises the following steps:
detecting by a light-induced fluorescence spectrum;
12. detection method of absorption spectrum of protective layer 3:
the absorption spectrum of the protective layer 3 was measured using an ultraviolet-visible absorption spectrometer.
Example 1
The invention provides a preparation method of a silicon-based optical PUF structure, which comprises the following steps:
etching the cleaned silicon wafer with the area of 1.5cm multiplied by 1.5cm by using a mixed solution of copper nitrate trihydrate, hydrogen peroxide and hydrofluoric acid, wherein the preparation temperature of the mixed solution is 50 ℃, the stirring time is 10min, the volume fraction of dioxygen water is 30%, the volume fraction of hydrofluoric acid is 40%, and the ratio of the addition amount of copper ions to the area of the silicon wafer is 0.0006mol/cm 2 The copper ions are from copper nitrate trihydrate, the volume ratio of hydrogen peroxide to hydrofluoric acid is 1:1, and the ratio of the total addition amount of hydrogen peroxide and hydrofluoric acid to the area of the silicon wafer is 10mL/cm 2 Etching for 1min, and placing the silicon wafer into the nitrateUltrasonic cleaning in acid for 20min, and drying to obtain a substrate 1;
dissolving 50g of erbium-doped silicon nano material particles in 10mL of methanol for ultrasonic treatment for 10 min to fully disperse, preparing an erbium-doped silicon nano material methanol solution, adding 3mL of hydrofluoric acid with the volume fraction of 49% and stirring for 2 min, centrifuging at the rotating speed of 9000 r/min for 2 min, pouring out supernatant after centrifuging, rapidly dissolving the erbium-doped silicon nano material in a centrifuge tube by using 10mL of mesitylene, then adding the obtained mixture into a mixed solution composed of 15mL of mesitylene and 5mL of dodecene (the volume ratio is 3:1), and continuously adding 10mL of xenon difluoride (XeF) with the concentration of 1mg/mL 2 ) Heating the mesitylene solution for 3 hours at 180 ℃ to obtain the dodecene modified erbium-doped silicon nanomaterial; the dodecene modified erbium-doped silicon nano material is dissolved in toluene to prepare a solution, the solution is coated on the surface of a substrate 1, and then the toluene is removed by heating for 30min at 160 ℃, wherein the proportion of the erbium-doped silicon nano material relative to the area of a silicon wafer is 35 mu L/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the A silicon-based optical PUF with a nanomaterial layer 2 on a substrate 1 is produced.
Results and analysis:
embodiment 1 detection method of silicon-based optical PUF structure the detection method 1 is described above, and a scanning electron microscope image of a cross section of a silicon-based optical PUF is shown in fig. 1, and sequentially comprises a substrate 1 and a nanomaterial layer 2 from bottom to top;
example 1 a scanning electron microscope image of a top view of a substrate 1 is shown in fig. 4, and a schematic diagram of a top view of a substrate 1 is shown in fig. 5, wherein "point" and "position" of the present invention have the same meaning, i.e. "point 1" and "position 1" are equivalent, corresponding to points 1-n in fig. 5; the scanning electron microscope image of the cross section of the substrate 1 is shown in fig. 6;
example 1 method of detecting average value of side length of substrate 1 method 2 was previously described, the side length dimension distribution of the silicon-based optical PUF of example 1 is shown in fig. 7, and the average value of side length is 610nm;
example 1 method of detection of depth average value of substrate 1 method 3 was previously described, the statistics of depth size distribution of the silicon-based optical PUF of example 1 is shown in fig. 8, and the depth average value is 660nm;
example 1 method for detecting doped elements of substrate 1 as described above for detection method 5, example 1 silicon-based optical PUF doped elements are arsenic;
Method for measuring resistivity of example 1 substrate 1 the resistivity of example 1 substrate 1 was 0.003 Ω. cm as described above for method 4;
example 1 detection method of average particle size of erbium-doped silicon nanomaterial detection method 6 was described previously, and the average particle size of erbium-doped silicon nanomaterial of example 1 was 4nm; the transmission electron microscope image and the size statistical distribution of the erbium-doped silicon nanomaterial are shown in fig. 9 and 10, respectively; the fluorescence spectrum of the erbium-doped silicon nanomaterial is shown in fig. 11; er (Er) 3+ The change in emission intensity around 1540nm with excitation power is shown in FIG. 12;
the detection method of the optical response signal generated at any point on the nanomaterial layer 2 in embodiment 1 is as described in detection method 7, wherein the optical response signal is respectively a blank back, a surface morphology, a luminous intensity of the silicon nanomaterial, a luminous intensity of erbium ions, a central luminous wavelength of the silicon nanomaterial, a luminous lifetime of the silicon nanomaterial, and a luminous intensity ratio of the silicon nanomaterial to the erbium ions; the detection result of the blank back is shown in fig. 16, the surface morphology is shown in fig. 17, the luminous intensity and the central luminous wavelength are shown in fig. 18 and 19, the detection result of the luminous intensity ratio is shown in fig. 20, and the luminous life is shown in fig. 21; in addition, as a comparison, the fluorescence spectrum of the nanomaterial layer 2 prepared by coating the erbium-doped silicon nanomaterial on the substrate other than the present invention is shown in fig. 22, and the luminescence lifetime of the nanomaterial layer 2 prepared by coating the erbium-doped silicon nanomaterial on the substrate other than the present invention is shown in fig. 23;
Example 1 detection method of valence state of erbium element detection method 9 is described above, wherein the peak binding energy of X-ray photoelectron spectrum of erbium element is 169eV, and there is no other accompanying peak, which indicates that valence state of erbium element is +3 valence; the detection result is shown in fig. 14;
example 1 method of detecting the presence of erbium element in the lattice of the silicon nanomaterial the erbium-doped silicon nanomaterial was observed with a high-angle annular dark field scanning transmission electron microscope ((HAADF-STEM)) as described in the detection method 10, and the erbium element showed a higher high-angle annular dark field intensity than the silicon element at an electron acceleration voltage of 200 kV; the detection results are shown in FIG. 15.
Er of example 1 3+ Detection method with optical Activity As described above for detection method 11, er in the erbium-doped silicon nanomaterial 3+ The luminescence intensity of (a) increases linearly with increasing excitation light power (fig. 12), indicating Er in the erbium-doped silicon nanomaterial 3+ Are optically active. If Er 3+ Only part of the light is optically active, and the luminous intensity thereof tends to be saturated with the increase of the excitation light power (see FIG. 3,Fujii M,Yoshida M,Kanzawa Y,et al.1.54 μm m Photoluminescence of Er of the document 3+ Doped into SiO 2 Films Containing Si Nanocrystals:Evidence for Energy Transfer from Si Nanocrystals to Er 3+ [J].Applied Physics Letters,1997,71(9):1198–1200.)。
The silicon-based optical PUF of embodiment 1 comprises a substrate 1 and a nanomaterial layer 2 on the substrate 1, wherein: the substrate 1 is used for providing an uneven structure, the average value of the side length and the average value of the depth of the uneven structure are respectively smaller than the central light-emitting wavelength of the nano material layer 2, and the resistivity of the substrate 1 is less than or equal to 0.005 Ω cm; the material of the nanomaterial layer 2 is erbium-doped silicon nanomaterial, and 7 different optical response signals can be generated at any point on the nanomaterial layer 2, which are respectively: blank back, surface morphology, luminous intensity of the silicon nanomaterial, luminous intensity of erbium ions, central luminous wavelength of the silicon nanomaterial, luminous life of the silicon nanomaterial, and luminous intensity ratio of the silicon nanomaterial to the erbium ions; the 7 different optical response signals are generated from the erbium-doped silicon nanomaterial; the erbium-doped silicon nanomaterial comprises silicon element and erbium element, wherein the silicon element exists in the form of nano silicon, and the erbium element completely exists in the form of Er 3+ Morphology exists within the crystal lattice of the silicon nanomaterial and is optically active; preferably, the average grain diameter of the erbium-doped silicon nano material is 3-5 nm; the 7 different optical response signals except for the blank back, the rest 6 optical response signalsThe response signal changes with the position of the arbitrary point on the substrate;
the calculation formula of the coding capacity is as follows:
coding capacity=a B
Wherein a is the number of optical response signals generated at any point on the nanomaterial layer 2 in the silicon-based optical PUF, a=7, B is the total amount of all points in the silicon-based optical PUF, B is 100×100, and the encoding capacity of the silicon-based optical PUF prepared in example 1 is 7 10000 。
Example 2
On the basis of example 1, example 2 also includes a step of preparing the protective layer 3, which comprises the following specific steps: the anisole solution of polymethyl methacrylate is coated on the upper part of the nano material layer 2, wherein the rotating speed is 2000 r/min, the time is 45s, and the ratio of the anisole solution of polymethyl methacrylate to the area of the silicon wafer is 35 mu L/cm 2 And heating at 160 ℃ for 30min to remove solvent components in the solution, so as to obtain the silicon-based optical PUF structure with the protective layer 3.
The detection method of the silicon-based optical PUF structure is as described in detection method 1, the image of the silicon-based optical PUF scanning electron microscope containing the protective layer 3 in embodiment 2 is shown in fig. 2, the substrate 1, the nano material layer 2 and the protective layer 3 are sequentially contained from bottom to top, and the schematic cross section of the PUF structure is shown in fig. 3.
The detection method of the absorption spectrum of the protective layer 3 is as described in the detection method 12, and the absorption spectrum is shown in fig. 13.
The change of the luminescence property of the silicon-based optical PUF with the protective layer 3 with time in example 2 is shown in fig. 24, which illustrates that the luminescence property of the nanomaterial layer 2 is not significantly attenuated in air (fig. 24), the silicon-based optical PUF without the protective layer 3 in example 1, and the luminescence property of the nanomaterial layer 2 is significantly attenuated in air (fig. 25).
The silicon-based optical PUF of the invention works as follows:
firstly, using a fluorescence spectrometer as detection equipment, and using a laser or white light as excitation (challenge) signals to obtain optical response (response) signals of specified positions of the silicon-based optical PUF, wherein the optical response (response) signals of each position are one pixel point of an optical image of the silicon-based optical PUF. Then, the optical image of the silicon-based optical PUF is subjected to Gabor filtering to convert the optical image into a binary image with 0/1 binary information, the image pixel size being 100 x 100 (fig. 27). Next, the binary image is compressed into a binary key (key), and the binary keys (keys) of the different silicon-based optical PUFs are analyzed and compared by Matlab, thereby obtaining a similarity distribution of the different silicon-based optical PUFs (fig. 28). Using the same method we can obtain a similarity profile for the same silicon-based optical PUF (fig. 28). Finally, a threshold value for distinguishing true/false is determined according to the similarity distribution of different silicon-based optical PUFs and the similarity distribution of the same silicon-based optical PUF, then binary keys of the different silicon-based optical PUFs are stored in a cloud, and a user can compare the silicon-based optical PUFs on the chip with corresponding silicon-based optical PUF information on the cloud, so that the product is verified to be true/false.
Example 3
Referring to the preparation method of example 2, the preparation method parameters are shown in table 2.
Results and analysis: example 3 the addition of copper nitrate trihydrate, hydrogen peroxide and hydrofluoric acid was reduced within the scope of the present invention, the substrate 1 of the silicon-based optical PUF structure obtained by example 3 had smaller side length average value and depth average value, so that the coupling effect of the substrate 1 and the nanomaterial layer 2 was slightly weaker, and further the difficulty of reading the optical response signal was slightly increased, the optical response signal of the silicon-based optical PUF structure obtained by example 3 was 7, and the encoding capacity was 7 10000 The method is also suitable for anti-counterfeiting. The detection method of each performance is the same as that of example 2, and each performance is shown in table 3.
Example 4
Referring to the preparation method of example 2, the preparation method parameters are shown in table 2.
Results and analysis: example 4 the addition of copper nitrate trihydrate, hydrogen peroxide and hydrofluoric acid was increased within the scope of the invention, the substrate 1 of the silicon-based optical PUF structure obtained by example 4 having a larger sizeThe average value of the side length and the average value of the depth make the coupling effect of the substrate 1 and the nano material layer 2 weaker, and further make the difficulty of reading the optical response signal slightly increased, the optical response signal of the silicon-based optical PUF structure prepared in embodiment 4 is 7, and the encoding capacity is 7 10000 The method is also suitable for anti-counterfeiting. The detection method of each performance is the same as that of example 2, and each performance is shown in table 3.
Example 5
Referring to the preparation method of example 2, the preparation method parameters are shown in table 2.
Results and analysis: example 5 the etching time was reduced within the scope of the present invention, the substrate 1 doping element was nitrogen, and since the substrate 1 of the silicon-based optical PUF structure obtained in example 5 with a reduced etching time had a slightly smaller average value of the side length and average value of the depth, the change of doping element slightly increased the resistivity of the substrate 1, but all within the scope of the present invention, the optical response signal of the silicon-based optical PUF structure obtained in example 5 was 7, the encoding capacity was 7 10000 The method is also suitable for anti-counterfeiting. The detection method of each performance is the same as that of example 2, and each performance is shown in table 3.
Example 6
Referring to the preparation method of example 2, the preparation method parameters are shown in table 2.
Results and analysis: example 6 an etching time was increased within the scope of the present invention, the doping element of the substrate 1 was nitrogen, the increase of the etching time enabled the substrate 1 of the silicon-based optical PUF structure obtained in example 5 to have a larger average value of the side length and average value of the depth, the resistivity of the substrate 1 was larger, and although the coupling effect of the substrate 1 and the nanomaterial layer 2 was slightly weak, it was within the scope of the present invention that the optical response signal of the silicon-based optical PUF structure obtained in example 6 was 7, and the encoding capacity was 7 10000 The method is also suitable for anti-counterfeiting. The detection method of each performance is the same as that of example 2, and each performance is shown in table 3.
Example 7
Referring to the preparation method of example 2, the preparation method parameters are shown in table 2.
Results and analysis: example 7 in the present inventionThe olefin ligand of the erbium-doped silicon nanomaterial is changed within the clear range, the doping element of the substrate 1 is phosphorus, the resistivity of the substrate 1 of the silicon-based optical PUF structure obtained by the embodiment 7 is larger, the particle size of the erbium-doped silicon nanomaterial is slightly reduced, but the optical response signal of the silicon-based optical PUF structure obtained by the embodiment 7 is 7 and the coding capacity is 7 10000 The method is also suitable for anti-counterfeiting. The detection method of each performance is the same as that of example 2, and each performance is shown in table 3.
Example 8
Referring to the preparation method of example 2, the preparation method parameters are shown in table 2.
Results and analysis: example 8 an olefin ligand of erbium-doped silicon nanomaterial was changed within the scope of the present invention, the doping element of the substrate 1 was phosphorus, the resistivity of the substrate 1 of the silicon-based optical PUF structure obtained by example 8 was larger, the particle size of the erbium-doped silicon nanomaterial was increased, but all of them were within the scope of the present invention, the optical response signal of the silicon-based optical PUF structure obtained by example 8 was 7, and the encoding capacity was 7 10000 The method is also suitable for anti-counterfeiting. The detection method of each performance is the same as that of example 2, and each performance is shown in table 3.
Example 9
Referring to the preparation method of example 2, the preparation method parameters are shown in table 2.
Results and analysis: example 9 the amount of erbium-doped silicon nanomaterial added to the substrate 1 was small, the doping element of the substrate 1 was antimony, and the resistivity of the substrate 1 of the silicon-based optical PUF structure obtained in example 9 was larger, but all were within the scope of the invention, the optical response signal of the silicon-based optical PUF structure obtained in example 9 was 7, and the encoding capacity was 7 10000 The method is also suitable for anti-counterfeiting. The detection method of each performance is the same as that of example 2, and each performance is shown in table 3.
Example 10
Referring to the preparation method of example 2, the preparation method parameters are shown in table 2.
Results and analysis: example 10 adds more than example 2 within the scope of the inventionThe substrate 1 has a doping element of antimony, and the substrate 1 of the silicon-based optical PUF structure obtained in example 10 has a resistivity greater than that of the substrate 1 of the erbium-doped silicon nanomaterial, but all the silicon-based optical PUF structure obtained in example 10 has an optical response signal of 7 and a coding capacity of 7 within the scope of the present invention 10000 The method is also suitable for anti-counterfeiting. The detection method of each performance is the same as that of example 2, and each performance is shown in table 3.
Example 11
Referring to the preparation method of example 2, the preparation method parameters are shown in table 2.
Results and analysis: example 11 compared with example 2, the low boiling point nonpolar solvent is changed within the scope of the invention, the average value of the side length and the average value of the depth of the prepared silicon-based optical PUF structure substrate 1 are consistent, the particle size of erbium-doped silicon nanomaterial is equal to that of example 2, which shows that the change of the low boiling point solvent within the scope of the invention does not influence the performance of the silicon-based optical PUF, the optical response signal of the silicon-based optical PUF structure of example 11 is 7, and the coding capacity is 7 10000 The method is also suitable for anti-counterfeiting. The detection method of each performance is the same as that of example 2, and each performance is shown in table 3.
Comparative example 1 the same preparation as example 2, except that the substrate 1 was a planar structure.
Results and analysis: the silicon-based optical PUF structure obtained in comparative example 1 has the advantages of reduced number of optical response signals generated at any point, reduced coding capacity and poorer anti-counterfeiting performance. The substrate 1 was not etched in the preparation method, so that the substrate 1 of comparative example 1 had a planar structure, resulting in a lower encoding capacity than in example 2, indicating that if the structure of the substrate 1 was changed beyond the range described in the present invention, a silicon-based optical PUF structure satisfying the present invention could not be obtained. The detection method of each performance of the silicon-based optical PUF structure is the same as that of the embodiment 2, and each performance is shown in table 3.
Comparative example 2 the same preparation method as example 2 was carried out, except that the average value of the side lengths of the substrate 1 was controlled > the central light emission wavelength of the nanomaterial layer 2.
Results and analysis: by comparison of examples2, the number of optical response signals generated at any point of the obtained silicon-based optical PUF structure is less, the coding capacity is lower, and the anti-counterfeiting performance is poorer. In the preparation process step (1), the etching time (2 min) and the total addition amount (20 mL/cm) of hydrogen peroxide and hydrofluoric acid are increased 2 ) The average value of the side length of the substrate 1 of comparative example 2 is increased, resulting in lower encoding capacity than in example 2, which means that if the average value of the side length of the substrate 1 is out of the range described in the present invention, the specific rugged structure of the substrate 1 of the present invention cannot be obtained, and thus the silicon-based optical PUF structure of the present invention cannot be obtained. The detection method of each performance of the silicon-based optical PUF structure is the same as that of the embodiment 2, and each performance is shown in table 3.
Comparative example 3 the same preparation method as example 2 was carried out, except that the average value of the depth of the substrate 1 was controlled > the central light emission wavelength of the nanomaterial layer 2.
Results and analysis: the silicon-based optical PUF structure obtained in comparative example 3 has the advantages of less quantity of optical response signals generated at any point, lower coding capacity and poorer anti-counterfeiting performance. In the preparation process step (1), the etching time (3 min) and the total addition amount (15 mL/cm) of hydrogen peroxide and hydrofluoric acid are increased 2 ) The average value of the depth of the substrate 1 of comparative example 3 is increased, resulting in lower encoding capacity than in example 2, which means that if the average value of the depth of the substrate 1 is out of the range described in the present invention, the specific rugged structure of the substrate 1 of the present invention cannot be obtained, and thus the silicon-based optical PUF structure of the present invention cannot be obtained. The detection method of each performance of the silicon-based optical PUF structure is the same as that of the embodiment 2, and each performance is shown in table 3.
Comparative example 4 the same preparation method as example 2, the only difference being that nanomaterial layer 2 is a simple mixed erbium-silicon nanomaterial.
Results and analysis: the silicon-based optical PUF structure obtained in comparative example 4 has the advantages of less quantity of optical response signals generated at any point, lower coding capacity and poorer anti-counterfeiting performance. Comparative example 4 changes nanomaterial layer 2 to a simple mixed erbium-silicon nanomaterial, i.e., elemental erbium is mixed with a silicon nanomaterial, so that the number of optical response signals becomes smaller, resulting in a lower encoding capacity than in example 2, indicating that if nanomaterial layer 2 does not belong to the erbium-doped silicon nanomaterial, then a silicon-based optical PUF structure according to the present invention cannot be obtained. The detection method of each performance of the silicon-based optical PUF structure is the same as that of the embodiment 2, and each performance is shown in table 3.
Comparative example 5 was prepared in the same manner as example 2, except that the erbium element was not all Er 3+ Morphology exists in the lattice of the silicon nanomaterial.
Results and analysis: the silicon-based optical PUF structure obtained in comparative example 5 has the advantages of less quantity of optical response signals generated at any point, lower coding capacity and poorer anti-counterfeiting performance. In the preparation method step (2), the erbium element in the lattice of the erbium-doped silicon nanomaterial in comparative example 5 is not Er by selecting erbium with the valence of +2 as an erbium source 3+ The morphology exists, which in turn causes the silicon nanomaterial to emit no light or to decrease in intensity of light, which reduces the number of optical response signals, resulting in a lower encoding capacity than in example 2, indicating that if the erbium element in the erbium-doped silicon nanomaterial is not fully Er-doped 3+ The morphology exists in the lattice of the silicon nanomaterial, and the silicon-based optical PUF structure cannot be obtained. The detection method of each performance of the silicon-based optical PUF structure is the same as that of the embodiment 2, and each performance is shown in table 3.
Comparative example 6 was identical to the preparation method of example 2, except that the erbium element present in the lattice of the silicon nanomaterial was not optically active.
Results and analysis: the silicon-based optical PUF structure obtained in comparative example 6 has the advantages of less quantity of optical response signals generated at any point, lower coding capacity and poorer anti-counterfeiting performance. In the preparation method step (2), by selecting elemental erbium as an erbium source, the erbium element in the lattice of the erbium-doped silicon nanomaterial in comparative example 6 is present but has no optical activity, so that the number of optical response signals is reduced, resulting in lower coding capacity than in example 2, which means that the silicon-based optical PUF structure of the present invention cannot be obtained if the lattice of the silicon nanomaterial is doped with erbium element but has no optical activity. The detection method of each performance of the silicon-based optical PUF structure is the same as that of the embodiment 2, and each performance is shown in table 3.
Table 1 comparison of optical PUF encoding capacity
Table 2 silicon-based optical PUF preparation parameter table
Table 3 silicon-based optical PUF performance parameter table
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Summary and analysis: as can be seen from analysis of examples 1 to 11 and comparative examples 1 to 6, the silicon-based optical PUF must be precisely controlled by controlling various parameters such as etching components, etching component ratio, addition volume, etching time, temperature, cleaning, etc., that is, the silicon-based optical PUF needs to simultaneously satisfy that the substrate 1 has an uneven structure, and the average value of the side length and the average value of the depth of the uneven structure are respectively smaller than the central light-emitting wavelength of the nanomaterial layer 2; the material of the nano material layer 2 is erbium-doped silicon nano material, 7 different optical response signals can be generated at any point on the nano material layer 2, the erbium-doped silicon nano material comprises silicon element and erbium element, wherein the silicon element exists in the form of nano silicon, and the erbium element completely exists in the form of Er 3+ Morphology exists within the crystal lattice of the silicon nanomaterial and is optically active; the nano material can be obtained only by doping one element under the condition that the condition is inexhaustibleThe material characteristics of the layer 2 and the synergistic effect of the coupling of the nano material layer 2 and the substrate 1 with the specific structure of the invention do not need to carry out complex numerical processing on optical response signals, the number of optical response signals A at any point on the nano material layer 2 of the silicon-based optical PUF is 7, and the coding capacity of the silicon-based optical PUF is 7 under the test condition that the total quantity B of all points of the silicon-based optical PUF is 100 multiplied by 100 10000 Is the only one that realizes the coding capacity of 7 by only doping one element material at present 10000 And overcomes the technical prejudice that silicon materials cannot be applied to optical PUFs because they do not emit light. If one of the conditions is changed beyond the range described in the present invention, a silicon-based optical PUF satisfying the properties described in the present invention cannot be obtained.
The above-described embodiments are only for illustrating the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.

Claims (57)

1. A silicon-based optical PUF, characterized by: the silicon-based optical PUF comprises a substrate (1) and a nanomaterial layer (2) located on the substrate (1), wherein:
the substrate (1) is used for providing an uneven structure, and the average value of the side length and the average value of the depth of the uneven structure are respectively smaller than the central luminous wavelength of the nano material layer (2);
the material of the nano material layer (2) is erbium-doped silicon nano material, 7 different optical response signals can be generated at any point on the nano material layer (2), and the optical response signals are respectively as follows: blank back, surface morphology, luminous intensity of the silicon nanomaterial, luminous intensity of erbium ions, central luminous wavelength of the silicon nanomaterial, luminous life of the silicon nanomaterial, and luminous intensity ratio of the silicon nanomaterial to the erbium ions;
The 7 different optical response signals are generated from the erbium-doped silicon nanomaterial;
the erbium-doped silicon nanomaterial comprises silicon element and erbium element, wherein the silicon element exists in the form of nano silicon, and the erbium element completely exists in the form of Er 3+ Morphology exists within the crystal lattice of the silicon nanomaterial and is optically active;
the 7 different optical response signals, except for the blank back, and the rest 6 optical response signals are changed along with the change of the position of any point on the substrate;
the calculation formula of the coding capacity of the silicon-based optical PUF is as follows:
wherein a is the number of optical response signals generated at any point on the nanomaterial layer (2) in the silicon-based optical PUF, a=7, and B is the total amount of all points in the silicon-based optical PUF.
2. A silicon-based optical PUF according to claim 1, characterized in that: the resistivity of the substrate (1) is less than or equal to 0.005 omega cm.
3. A silicon-based optical PUF according to claim 1, characterized in that: the average grain diameter of the erbium-doped silicon nano material is 3-5 nm.
4. A silicon-based optical PUF according to claim 1, characterized in that: the side length average value has the following calculation formula:
wherein n is the total number of sides of the rugged structure, +. >Is the length of the ith edge.
5. A silicon-based optical PUF as defined in claim 4, wherein: the side length average value is less than 830 and nm.
6. A silicon-based optical PUF as defined in claim 4, wherein: the average value of the side length is 610+/-20 nm.
7. A silicon-based optical PUF according to claim 1, characterized in that: the depth average value calculation formula is as follows:
wherein m is the total number of structural grooves with irregularities, < >>Is the depth of the ith groove, which is the vertical distance between the highest point and the lowest point in any groove.
8. A silicon-based optical PUF according to claim 7, characterized in that: the depth average is < 830 nm.
9. A silicon-based optical PUF according to claim 7, characterized in that: the depth average was 660±20 nm.
10. A silicon-based optical PUF according to claim 1, characterized in that: the substrate (1) is a silicon-containing material.
11. A silicon-based optical PUF according to claim 1, characterized in that: the substrate (1) is made of doped silicon-containing material.
12. A silicon-based optical PUF according to claim 1, characterized in that: the substrate (1) is an n-type doped silicon wafer.
13. A silicon-based optical PUF according to claim 12, characterized in that: the doping element in the doped silicon wafer is at least one of nitrogen (N), phosphorus (P), arsenic (As) and antimony (Sb).
14. A silicon-based optical PUF according to claim 13, characterized in that: the doping element is arsenic (As).
15. A silicon-based optical PUF according to claim 1, characterized in that: the center luminescence wavelength of the erbium-doped silicon nano material is more than or equal to 830nm.
16. A silicon-based optical PUF according to claim 1, characterized in that: the center luminescence wavelength of the erbium-doped silicon nanomaterial is near 830nm and near 1540 nm, respectively.
17. A silicon-based optical PUF according to any one of claims 1-16, characterized in that: a protective layer (3) is also present on the nanomaterial layer (2).
18. A silicon-based optical PUF according to claim 17, characterized in that: the wavelength range of the absorption spectrum of the protective layer (3) is not overlapped with the wavelength range of the luminescence spectrum of the nano material layer (2).
19. A silicon-based optical PUF according to claim 17, characterized in that: the absorption cut-off wavelength of the protective layer (3) is less than or equal to 400 and nm, and the absorption cut-off wavelength refers to a critical value from an absorption signal to a non-absorption signal on an absorption spectrum.
20. A silicon-based optical PUF according to claim 17, characterized in that: the material of the protective layer (3) is polymer.
21. A silicon-based optical PUF according to claim 17, characterized in that: the material of the protective layer (3) is at least one selected from polymethyl methacrylate, polyvinyl alcohol resin and polyimide.
22. A silicon-based optical PUF according to claim 17, characterized in that: the material of the protective layer (3) is polymethyl methacrylate.
23. A method of manufacturing a silicon-based optical PUF as in claim 1, characterized by: the preparation method comprises the following steps:
etching the silicon wafer by using a mixed solution containing copper ions, hydrogen peroxide and hydrofluoric acid, wherein the ratio of the addition amount of the copper ions to the area of the silicon wafer is 0.0003-0.0008 mol/cm 2 The volume ratio of the hydrogen peroxide to the hydrofluoric acid is 1:1, and the ratio of the total addition amount of the hydrogen peroxide and the hydrofluoric acid relative to the area of the silicon wafer is 5-15 mL/cm 2 Etching for 0.5-2 min, cleaning and drying to obtain a substrate (1);
step (2) dissolving the C7-C18 olefin modified erbium-doped silicon nanomaterial in a low-boiling nonpolar solvent to prepare a solution, coating the solution on the surface of a substrate (1), and heating to remove the low-boiling nonpolar solvent to prepare the silicon-based optical PUF with the nanomaterial layer (2) on the substrate (1), wherein the ratio of the quantity of the erbium-doped silicon nanomaterial to the area of a silicon wafer is 20-60 mu L/cm 2 The low-boiling nonpolar solvent is a solvent with a boiling point lower than 150 ℃.
24. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in step (1), the copper ions are derived from a copper ion salt.
25. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in step (1), the copper ions are derived from copper nitrate trihydrate.
26. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (1), the preparation temperature of the mixed solution is 45-80 ℃.
27. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (1), the preparation temperature of the mixed solution is 50 ℃.
28. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (1), the stirring time for preparing the mixed solution is 10-30 min.
29. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (1), the stirring time for preparing the mixed solution is 10min.
30. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (1), the ratio of the addition amount of the copper ions to the area of the silicon wafer is 0.0006 mol/cm 2 。
31. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (1), the ratio of the total addition amount of hydrogen peroxide and hydrofluoric acid to the area of the silicon wafer is 10mL/cm 2 。
32. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (1), the volume fraction of the hydrogen peroxide is more than or equal to 30 percent.
33. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (1), the volume fraction of hydrofluoric acid is more than or equal to 40 percent.
34. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (1), the etching time is 1min.
35. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (1), the cleaning is to put the silicon wafer into nitric acid for ultrasonic cleaning, and the ultrasonic cleaning time is 20min.
36. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (2), the olefin modification comprises the steps of dissolving erbium-doped silicon nano material particles in a mixed solution of mesitylene and olefin, and then adding xenon difluoride mesitylene solution, wherein the olefin is C7-C18 olefin.
37. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (2), the volume ratio of mesitylene to olefin in the mixed solution is 1:1-3:1.
38. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (2), the olefin modification specifically comprises the following steps:
step A), erbium-doped silicon nano material particles are dissolved in methanol and fully dispersed, and then the erbium-doped silicon nano material methanol solution is prepared;
and B), adding hydrofluoric acid with the volume fraction of more than or equal to 40% into the erbium-doped silicon nanomaterial methanol solution prepared in the step A), stirring for 1-5 minutes, centrifuging at a rotating speed of 5000-9000 rpm for 1-5 minutes, pouring out supernatant, rapidly dissolving the erbium-doped silicon nanomaterial in a centrifuge tube by using mesitylene, then adding the mixed solution consisting of the mesitylene and olefin in the volume ratio of 1:1-3:1, wherein the olefin is C7-C18 olefin, continuously adding xenon difluoride mesitylene solution, and heating at the temperature of 160-180 ℃ for 3-5 hours to prepare the erbium-doped silicon nanomaterial.
39. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in step (2), the olefin is dodecene.
40. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (2), the ratio of the amount of the erbium-doped silicon nano material to the area of the silicon wafer is 35 mu L/cm 2 。
41. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (2), the low boiling point nonpolar solvent is toluene.
42. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (2), the temperature for heating and removing the low-boiling nonpolar solvent is 160-250 ℃.
43. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in step (2), the temperature at which the low boiling point nonpolar solvent is removed by heating is 160 ℃.
44. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (2), the time for heating to remove the low-boiling nonpolar solvent is 30-60 min.
45. A method of preparing a silicon-based optical PUF as defined in claim 23, wherein: in the step (2), the time for heating to remove the low boiling point nonpolar solvent is 30min.
46. A method of manufacturing a silicon-based optical PUF according to any one of claims 23-45, characterized in that: after step (2) of the production method according to any one of claims 23 to 45, further comprising a step of producing a protective layer (3), the specific steps being: spin-coating the solution of the protective layer (3) on the nano material layer (2), wherein the rotating speed is 1000-3000 r/min, the time is 0.5-1 min, and the proportion of the solution of the protective layer (3) relative to the area of the silicon wafer is 20-60 mu L/cm 2 And heating to remove solvent components in the solution, so as to obtain the silicon-based optical PUF with the protective layer (3).
47. A method of preparing a silicon-based optical PUF as recited in claim 46, wherein: the solution of the protective layer (3) is selected from polymer solutions.
48. A method of preparing a silicon-based optical PUF as recited in claim 46, wherein: the solution of the protective layer (3) is selected from anisole solution of polymethyl methacrylate, aqueous solution of polyvinyl alcohol resin and dimethylformamide solution of polyimide.
49. A method of preparing a silicon-based optical PUF as recited in claim 46, wherein: and the protective layer (3) is an anisole solution of polymethyl methacrylate.
50. A method of preparing a silicon-based optical PUF as recited in claim 46, wherein: the ratio of the amount of the solution of the protective layer (3) to the silicon wafer area is 35 mu L/cm 2 。
51. A method of preparing a silicon-based optical PUF as recited in claim 46, wherein: the rotational speed was set at 2000 revolutions per minute for 45 seconds.
52. A method of preparing a silicon-based optical PUF as recited in claim 46, wherein: the temperature of the solvent component in the heating and removing solution is 160-250 ℃.
53. A method of preparing a silicon-based optical PUF as recited in claim 46, wherein: the temperature of the solvent component in the heated removal solution was 160 ℃.
54. A method of preparing a silicon-based optical PUF as recited in claim 46, wherein: the time for heating to remove the solvent component in the solution is 30-60 min.
55. A method of preparing a silicon-based optical PUF as recited in claim 46, wherein: the time for heating to remove the solvent component in the solution is 30min.
56. An anti-counterfeit label, characterized in that: the security tag comprises a silicon-based optical PUF according to any one of claims 1-22 or a silicon-based optical PUF produced by a method of production according to any one of claims 23-55.
57. Use of a silicon-based optical PUF according to claims 1-22, a silicon-based optical PUF according to claims 23-55, and a security label according to claim 56 in the field of security.
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