Information Encryption Research Articles

Antithermal-Quenching All-Inorganic Perovskite Crystals with Green Ultralong Persistent Luminescence for Advanced Anticounterfeiting Applications.

Long persistent luminescence (PersL) materials have revolutionized many fields of optoelectronics and photonics due to their applications in anticounterfeiting, information encryption, and in vivo bioimaging. Here, we reported a novel PersL crystal prepared by the heterovalent doping of Sb3+ into perovskite tetragonal phase RbCdCl3, comparing with the pristine non-perovskite orthorhombic phase analogue without PersL property. Surprisingly, under the UV light irradiation, the title crystals concurrently exhibit green ultralong PersL (>2400 s), high photoluminescence quantum yield (49.1%), and antithermal quenching in the range from 148 to 328 K. It was revealed by experimental results and theoretical analyses that green ultralong PersL and antithermal quenching of perovskite-phase RbCdCl3/Sb3+ crystals originate from the electron transition between the 5s2 level of the dopant Sb3+ and the electronic defect-induced trap states. Enlightened by the excellent optical properties, the tetragonal perovskite-phase RbCdCl3/Sb3+ PersL materials show promising application prospects in anticounterfeiting and encryption of information.

Non-volatile and Secure Optical Storage Medium with Multilevel Information Encryption.

Non-volatile photomemory based on photomodulated luminescent materials offers unique advantages over voltage-driven memory, including low residual crosstalk and high storage speed. However, conventional materials have thus far been volatile and insecure for data storage because of low trap depth and single-level storage channels. Therefore, the development of a novel non-volatile multilevel storage medium for data encryption remains a challenge. Herein, a robust, non-volatile, multilevel optical storage medium is reported, based on a photomodulated Ba3MgSi2O8:Eu3+, which combined the merits of light-induced valence (Eu3+ → Eu2+) and photochromic phenomena using optical stimulation effects, accompanied by larger luminescent and color contrasts (>90%). These two unique features provided dual-level storage channels in a single host, significantly improving the data storage security. Notably, dual-level optical signals could be written and erased simultaneously by alternating 265 and 365 nm light stimuli. Theoretical calculations indicated that robust color centers induced by intrinsic interstitial Mg and vacancy defects with suitable trap depths enable excellent reversibility and long-term storage capability. By relying on different luminescent readout mechanisms, the encrypted dual-level information can be accurately decrypted by separately probing the Eu2+ and Eu3+ signals, thus ensuring information security. This study proposes a novel approach for constructing multilevel information storage channels for information security.

Sodium Assists Controlled Synthesis of Cubic Rare-Earth Oxyfluorides Nanocrystals for Information Encryption and Near-Infrared-IIb Bioimaging.

Rare-earth oxyfluoride (REOF) colloidal nanocrystals (NCs) suffer from a low photoluminescence efficiency due to their small size with poor crystallinity and a detrimental surface quenching effect. Herein, we introduce an innovative approach that involves doping sodium ions into REOF NCs to produce monodisperse, size-controllable, well-crystallized, and highly luminescent colloidal REOF core/shell NCs. The Na+ doping allows for successfully synthesizing the cubic REOF NCs with a tunable size from 6 to 30 nm. Further fabrication of the core/shell NCs doped with Na+ results in enhancements up to 1062 (Ho3+), 1140 (Er3+), and 2212 (Tm3+) folds in upconversion luminescence and 17.7 folds (Er3+) in downconversion luminescence compared to that of core/shell NCs without doping Na+ ions. These NCs were subsequently developed into multicolor luminescent inks, demonstrating significant potential application for information security, and used for near-infrared-IIb (NIR-IIb) (1500-1700 nm) in vivo imaging, which exhibits a high-resolution in vivo dynamic imaging capability with a signal-to-noise ratio of 5.28. These results present the way to the controlled synthesis of efficient luminescent cubic LuOF: RE3+/LuOF core/shell NCs, expanding the toolkit of rare-earth doped NCs in diverse applications such as advanced encoding encryption, varied fluorescence imaging, and biomedicine.

Highly Water‐Dispersible Spiropyran‐Octapeptide Supramolecules: Efficient, Multi‐processable, and Versatile Photoswitches for Time‐Dependent Dual‐Mode Encryption

AbstractWith exceptional photochromic and photoluminescent properties, spiropyrans have demonstrated significant potential for advanced information encryption and anti‐counterfeiting applications. However, its inherent water insolubility leads to incompatibility with aqueous polymers, and even more, its ease of leaching from the matrix hinders the formation of stable stimuli‐responsive platforms through direct blending with all polymers. Here, the fabrication of amphiphilic spiropyran‐octapeptide molecules is reported that can spontaneously self‐assemble into highly water‐dispersible supramolecular nanofibers in water. These assemblies exhibit universal polymer matrix compatibility while retaining the rapid photo‐responsiveness of spiropyrans. The formation of strong interactions between the supramolecular assembly and polymer chains ensures the long‐term stability of the resultant stimuli‐responsive materials in aqueous environments. These platforms fully preserve the base polymers’ processing properties, with silk fibroin as the matrix offering exceptional opportunities for constructing photo‐responsive platforms in various forms (e.g., films, gels, fibers, and coatings) with multiple functionalities using diverse solution processing techniques. Integrating distinct photochromic and photoluminescent responses within a single format without interference, combined with environmental stability and processing flexibility, enables the creation of dual‐mode, high‐security encryption devices for diverse application scenarios. The outlined strategy provides innovative concepts for developing high‐performance, versatile intelligent systems utilizing stimulus‐responsive molecules.

Combining Semi-Tensor Product Compressed Sensing and Session Keys for Low-Cost Encryption of Batch Information in WBANs

Combining Semi-Tensor Product Compressed Sensing and Session Keys for Low-Cost Encryption of Batch Information in WBANs

Flexible X-ray Imaging and Stable Information Storage of SrF2:Eu Based on Radio-Photoluminescence.

X-ray imaging has garnered widespread interest in biomedical diagnosis and nondestructive detection. The exploration of radio-photoluminescence has hastened the advancement of X-ray information storage. However, significant challenges persist in achieving the prolonged imaging of curved objects without attenuation. Here, europium-doped strontium fluoride (SrF2:Eu) is meticulously created to exhibit a linear response to an extensive range of X-ray doses (maximum dose > 5000 Gy), showcasing excellent X-ray information reading/erasing reusability properties (10 cycles). This is accompanied by a red-to-blue emission transition under UV excitation, sustaining for 150 days without attenuation. To elucidate the phenomena of irradiated photoluminescent discoloration and the reversible X-ray storage of SrF2:Eu, we propose an electron-vacancy trap (valence conversion) mechanism, information stably retained by the SrF2:Eu-based device under ambient conditions due to high energy barriers. The time-lapse readout capability is further demonstrated for three-dimensional imaging of curved objects (10 lp mm-1) based on SrF2:Eu embedded within a polydimethylsiloxane (SrF2:Eu@PDMS). The SrF2:Eu demonstrates time-lapse imaging, reversible radio-photoluminescence, and recoverable X-ray storage, offering a promising avenue for optical information encryption and anticounterfeiting applications.

Precisely Regulating Photoactivated Dynamic Room Temperature Phosphorescence by Alkyl Chain‐Induced Lattice‐Softening

AbstractDynamic response room temperature phosphorescence (RTP) is a hot topic in smart materials research due to its unique RTP‐response characteristics under external stimuli. However, its precisely control are currently challenging. Here, an alkyl chain‐induced lattice‐softening strategy is proposed to precisely regulate photoactivated dynamic RTP (PDRTP). By adjusting the alkyl chain flexibility of hybrid metal halide matrices, oxygen permeability can be adjusted, thereby achieving finely manipulate of the photoactivation equilibrium time, RTP lifetime, and RTP wavelength of the resulted host–guest doped materials within the ranges of 10–600 s, 0.05‐1.62 s, and 405–595 nm, respectively. It is also demonstrated the potential application of the PDRTP materials in afterglow oxygen sensing and multi‐level information encryption. This study not only proposes an effective method for regulating the photosensitivity of PDRTP materials, but also points out a new direction for exploring gas permeability in dense‐packed crystalline materials.

Triplet Energy Gap‐Regulated Room Temperature Phosphorescence in Host‐guest Doped Systems

The organic room temperature phosphorescence (RTP) materials via host‐guest doped method receive considerable attention in the fields of optoelectronics, bioimaging, and information encryption. Despite many host‐guest doped materials with excellent RTP properties have been developed, their luminous mechanism is still limited. Here, a series of host‐guest doped materials, using Benzophenone as the host and quinone compounds as the guests, were constructed to investigate the effect of the triplet energy gap (ΔET) between the host and guest on triplet states population. The guest’s triplet state is proposed to be a “triplet energy reservoir”, gathering the triplet excitons to emit RTP when ΔET is large and returning triplet excitons to the host when ΔET is small. By combining the results of steady‐state and delayed emission spectra, time‐resolved transient absorption, and theoretical calculations, A bidirectional energy transfer process is proved, which are triplet‐triplet energy transfer and reverse triplet‐triplet energy transfer processes. The thermal equilibrium of these two energy transfer processes can be regulated by the ΔET and temperature. The potential applications of these RTP properties are also realized in data encryption and anti‐counterfeiting. This work provides valuable insight into the design of host‐guest doped materials based on energy transfer mechanisms.

Triplet Energy Gap-Regulated Room Temperature Phosphorescence in Host-guest Doped Systems.

The organic room temperature phosphorescence (RTP) materials via host-guest doped method receive considerable attention in the fields of optoelectronics, bioimaging, and information encryption. Despite many host-guest doped materials with excellent RTP properties have been developed, their luminous mechanism is still limited. Here, a series of host-guest doped materials, using Benzophenone as the host and quinone compounds as the guests, were constructed to investigate the effect of the triplet energy gap (ΔET) between the host and guest on triplet states population. The guest's triplet state is proposed to be a "triplet energy reservoir", gathering the triplet excitons to emit RTP when ΔETis large and returning triplet excitons to the host when ΔETis small. By combining the results of steady-state and delayed emission spectra, time-resolved transient absorption, and theoretical calculations, A bidirectional energy transfer process is proved, which are triplet-triplet energy transfer and reverse triplet-triplet energy transfer processes. The thermal equilibrium of these two energy transfer processes can be regulated by the ΔETand temperature. The potential applications of these RTP properties are also realized in data encryption and anti-counterfeiting. This work provides valuable insight into the design of host-guest doped materials based on energy transfer mechanisms.

Subtraction-based DNA Origami Cryptography by using Structural Defects for Information Encryption.

Conventional cryptographic methods rely on increased computational complexity to counteract the threat posed by growing computing power for sustainable protection. DNA cryptography circumvents this threat by leveraging complex DNA recognition to maintain information security. Specifically, DNA origami has been repurposed for cryptography, using programmable folding of the long scaffold strand carrying additional tagged strands for information encryption. Herein, a subtraction-based cryptographic strategy is presented that uses structural defects on DNA origami to contain encrypted information. Designated staple strands are removed from the staple pool with "hook" strands to create active defect sites on DNA origami for information encryption. These defects can be filled by incubating the structures with the intact pool of biotinylated staple strands, resulting in biotin patterns that can be used for protein-binding steganography. The yields of individual protein pixels reached over 91%, and self-correction codes are implemented to aid the information recovery. Furthermore, the encrypted organization of defective DNA origami structures is investigated to explore the potential of this method for scalable information storage. This method uses DNA origami to encrypt information in hidden structural features, utilizing subtraction for robust cryptography while ensuring the safety and recovery of data.

Enhancement of NIR‐II Emission of Er3+ by Doping Fe3+ in Double Perovskites: Multimode Luminescence for Versatile Optoelectronic Applications

Erbium ions are commonly used to extend the photoelectric properties of metal halide perovskites from visible to near‐infrared (NIR) range. However, achieving high‐efficiency multi‐mode luminescence in a single system is difficult due to the weak absorption associated with forbidden 4f‐4f transitions. In this study, a unique strategy is proposed to adjust multi‐mode luminescence and enhance NIR‐II emission in Cs2NaBiCl6 by incorporating Fe3+ ions. The as‐prepared material demonstrates reversible thermochromism, driven by strong electron‐phonon coupling effect, and exhibits tunable luminescence that can be adjusted by altering excitation energy and temperature. Notably, benefitting from the charge transfer transition of Fe3+‐Cl‐ along with the influence of Fe3+ doping on the geometrical and electronic structures, the blue‐excitable (450 nm) NIR‐II emission around 1541 nm from Er3+ is realized for the first time, achieving an intensity 16.7 times higher and a maximum photoluminescence quantum yield of 22.5%. This enhancement enables innovative applications such as two‐dimensional information encryption by the multi‐channel cooperative responses and improved NIR imaging. The study highlights the potential of Fe3+ doping in optimizing absorption and multi‐mode luminescence in perovskites, opening avenues for advanced applications in blue‐excitable NIR light emitting diodes, thermometer, anti‐counterfeiting, and NIR imaging.

Enhancement of NIR-II Emission of Er3+ by Doping Fe3+ in Double Perovskites: Multimode Luminescence for Versatile Optoelectronic Applications.

Erbium ions are commonly used to extend the photoelectric properties of metal halide perovskites from visible to near-infrared (NIR) range. However, achieving high-efficiency multi-mode luminescence in a single system is difficult due to the weak absorption associated with forbidden 4f-4f transitions. In this study, a unique strategy is proposed to adjust multi-mode luminescence and enhance NIR-II emission in Cs2NaBiCl6 by incorporating Fe3+ ions. The as-prepared material demonstrates reversible thermochromism, driven by strong electron-phonon coupling effect, and exhibits tunable luminescence that can be adjusted by altering excitation energy and temperature. Notably, benefitting from the charge transfer transition of Fe3+-Cl- along with the influence of Fe3+ doping on the geometrical and electronic structures, the blue-excitable (450 nm) NIR-II emission around 1541 nm from Er3+ is realized for the first time, achieving an intensity 16.7 times higher and a maximum photoluminescence quantum yield of 22.5%. This enhancement enables innovative applications such as two-dimensional information encryption by the multi-channel cooperative responses and improved NIR imaging. The study highlights the potential of Fe3+ doping in optimizing absorption and multi-mode luminescence in perovskites, opening avenues for advanced applications in blue-excitable NIR light emitting diodes, thermometer, anti-counterfeiting, and NIR imaging.

A chiral supramolecular liquid crystal based on pillararene and its application in information encryption.

A chiral supramolecular liquid crystal based on a pillararene mesogen was constructed. The regulation of liquid crystal behavior was achieved through the host-guest interactions between the pillararene-based mesogen and a tetraphenylethylene-containing guest. In addition, this supramolecular liquid crystal system, showing pH-responsive fluorescence emission character, was applied as an information encryption material capable of storing multiple levels of distinct information, thereby enriching the application of liquid crystal materials in the field of information security.

Versatile Nanolights From Silicon, Carbon and Oxygen Hybrid System for Optical Applications

AbstractSilicon, carbon and oxygen hybrid nanomaterials (i.e., SiCOHNs) have recently drawn extensive attention as versatile photoluminescence (PL) nanosystems. The collective advantages of silicon‐ and carbon‐based nanostructures have resulted in SiCOHNs with tunable and photostable PL properties, abundant possibilities for surface modification, and low biotoxicity. Although SiCOHNs have shown great potential in diverse applications, such as bioimaging, biosensing, drug delivery and information encryption, discovering novel SiCOHNs with explicit nanostructures and elucidating the fundamental mechanisms of their PL properties for bioapplications are highly desirable. In this review, on the preparation of SiCOHNs on the basis of the synthesis conditions and precursors are first focused. Next, the manipulation of the emission wavelength, quantum yield and RTP of SiCOHNs is discussed. On the basis of previous reports and the recent experimental/theoretical results, the primary structure of SiCOHNs is clarified and deduced their possible PL mechanism. SiCOHNs possess bacterial uptake efficiency and/or anticancer capacity, promoting various biomedical applications and proof‐of‐concept applications in anti‐counterfeiting. Finally, current challenges and future trends are summarized as a roadmap for the development of SiCOHNs‐based optical applications.

Chiral Co-assembly Based on a Stimuli-Responsive Polymer towards Amplified Full-Color Circularly Polarized Luminescence.

Stimuli-responsive circularly polarized luminescence (CPL) materials have been attaching wide attention in the field of optical information storage and encryption, while still facing the challenge of the realization of highluminescence dissymmetryfactors (glum). This work presents a pair of stimuli-responsive chiral co-assemblies P7R3 and P7S3 by combining polymer PFIQ containing iso-quinoline units with chiral inducers. The obtained chiral co-assemblies can reversibly undergo significant modification in CPL behavior under trifluoroacetic acid (TFA) fumigation and annealing treatment, with the |glum| values exhibiting a reversible shift between 0.2 and 0.3. Moreover, the chiral co-assemblies before TFA fumigating can effectively induce achiral emitters to generate intense full-color CPL signals through CPL energy transfer (CPL-ET), with the corresponding |glum| values larger than 0.2. Moreover, information encryption and decryption as well as a multi-level logic gates application are achieved by leveraging the reversible stimuli-responsive CPL activity of the chiral co-assembly. This work provides a new perspective for the construction of stimuli-responsive chiral luminescent materials with large |glum| values and the activation of CPL behavior in achiral emitters.

Excitation-wavelength-dependent persistent luminescence from single-component nonstoichiometric CaGaxO4:Bi for dynamic anti-counterfeiting

Materials capable of dynamic persistent luminescence (PersL) within the visible spectrum are highly sought after for applications in display, biosensing, and information security. However, PersL materials with eye-detectable and excitation-wavelength-dependent characteristics are rarely achieved. Herein, a nonstoichiometric compound CaGaxO4:Bi (x < 2) is present, which demonstrates ultra-long, color-tunable PersL. The persistent emission wavelength can be tuned by varying the excitation wavelength, enabling dynamic color modulation from the green to the orange region within the visible spectrum. Theoretical calculations, in conjunction with experimental observations, are utilized to elucidate the thermodynamic charge transitions of various defect states, thereby providing insights into the relationship between Bi3+ emitters, traps, and multicolored PersL. Furthermore, the utility of color-tunable PersL materials and flexible devices is showcased for use in visual sensing of invisible ultraviolet light, multicolor display, information encryption, and anti-counterfeiting. These discoveries create new opportunities to develop smart photoelectric materials with dynamically controlled PersL for various applications.

Spatial momentum separation for optical vortex via phase-assembled metasurfaces

Expanding the spatial degrees of freedom is regarded to be the most innovative and effective solution for optical vortex encoding/decoding technology. A phase-assembled metasurface is proposed here to separate the momentum of the optical vortex into different spatial locations, and the incident high-order optical vortex is encoded in 18 channels. By combining both the propagation phase and the Pancharatnam-Berry (PB) phase, the fundamental Gaussian mode (solid spot) positions and other higher-order orbital angular momentum modes (hollow mode spots) positions at different channels are used to achieve the encryption of all-optical information. The scheme of grouping the mode spots on different channels into solid and hollow points greatly reduces the difficulty of encoding/decoding a high-order optical vortex. In this way, the combination of 2 incident high-order optical vortexes can represent 256 hexadecimal numbers from 00 to FF. We envision this work will open avenues for information encryption, multidimensional data storage, wavefront manipulation, and advanced orbital angular momentum detection technologies.

Modulating Near-Infrared Persistent Luminescence via Diverse Preparation Approaches.

Near-infrared (NIR) persistent luminescence (PersL) materials have attracted extensive attention due to their great promise in medical diagnostics, bio-imaging, night vision surveillance, multi-level anticounterfeiting, and information encryption. To achieve NIR PersL (micro/nano-) materials with the desired properties, a variety of synthesis methods have been employed, including solid-phase reaction and liquid-phase synthesis. Different synthesis methods have different but important effects on the micro/nano-structure, luminescence, and PersL properties of the materials. Moreover, the influence of various synthesis methods on the properties of NIR PersL materials determines the selection of preparation approaches for other new material systems. Taking the representative NIR PersL ZnGa2O4:Cr3+ material as an example, four synthesis procedures are applied, namely, high-temperature solid-state reaction (SSR), high-temperature molten salt method (MSM), hydrothermal method (HM), and microwave-assisted solid-state (MASS) method. The structural and luminescent properties of samples made by SSR, MSM, HM, and MASS are compared. Notably, it is revealed that the MASS method can create additional trapping energy levels, which is of great significance for emerging applications. This work demonstrates the different effects of synthesis methods on PersL performance and provides a good guideline for the rapid and reasonable selection of preparation methods for diverse applications.

Promoting WLED-Excited High Temperature Long Afterglow by Orthogonally Anchoring Chromophores into 0D Metal-Organic Cages.

Afterglow materials have garnered significant interest due to distinct photophysical characteristics. However, it is still difficult to achieve long afterglow phosphorescence from organic molecules due to aggregation-caused quenching (ACQ) and energy dissipation. In addition, most materials reported so far have long afterglow emission only at room or even low temperatures, and mainly use UV light as an excitation source. In this work, we report a strategy to achieve high temperature long afterglow emission through the assembly of isolated 0D metal-organic cages (MOCs). In which, both ACQ and phosphorescence quenching effects are effectively mitigated by altering the stacking mode of organic chromophores through orthogonally anchoring into the edges of cubic MOCs. Furthermore, improvement in molecular rigidity, promotion of spin-orbit coupling and broadening of the absorption range are achieved through the MOC- engineering strategy. As a result, we successfully synthesized MOCs that can produce afterglow emission even after excitation by WLEDs at high temperatures (380 K). Moreover, the MOCs are capable of generating afterglow emissions when excited by mobile phone flashlight at room temperature. Given these features, the potential applications of MOCs in the visual identification of explosives, information encryption and multicolor display are explored.

Realizing Tunable Long Persistent Luminescent in Novel Cu2+‐Doped NaGaO2 for Multi‐Level Information Storage and Encryption

AbstractAnti‐counterfeiting and encryption are key technologies for information transmission in modern society. However, most optical materials offer only a single fixed response mode, limiting their security level in advanced anti‐counterfeiting applications. Exploring efficient and tunable long persistent luminescent (LPL) phosphors is urgently demanded and highly meaningful. In this work, a dual‐site occupancy strategy is innovatively reported via Li+ doped NaGaO2: Cu2+ (NGO: Cu2+/Li+) phosphors for enhancing LPL properties. To be specific, Cu2+ initially occupies both Na and Ga sites in NaGaO2, producing orange–yellow LPL at 585 nm and near‐infrared (NIR) emission at 712 nm, respectively. Furthermore, the introduction of Li+ will occupy the Na+ sites, attenuating the NIR emission and increasing the defect density of the oxygen‐deficient states, which results in enhanced LPL intensity and prolonged afterglow time. Significantly, the obtained NGO:Cu2+/Li+ exhibits multi‐emission modes with dynamic change of LPL time (10–20 min). More importantly, the NGO: Cu2+/Li+ has great potential applications in multi‐level information storage and encryption.