Scalable Multistep Imprinting of Multiplexed Optical Anti-counterfeiting Patterns with Hierarchical Structures.

Multiplexed optical techniques with multichannel patterns provide powerful strategies for high-capacity anti-counterfeiting. However, it is still a big challenge to meet the demands of achieving high encryption levels, excellent readability, and simple preparation simultaneously. Herein, we use a multistep imprinting technique, leveraging surface work-hardening to massively produce multiplexed encrypted patterns with hierarchical structures. These patterns with coupled nano- and microstructures can be instantaneously decoded into different pieces of information at different view angles under white light illumination. By incorporating perpendicular nano- and microgratings, we achieve four-channel encoded patterns, enhancing anti-counterfeiting capacity. This versatile method works on various metal/polymer materials, offering high-density information storage, direct visibility, broad material compatibility, and low-cost mass production. Our high-performance anti-counterfeiting patterns show significant potential in real-world applications.

Glass Disorder Modulated Luminescence in Zero-Dimensional Antimony-Chloride Coplanar Dimers for Optical Anti-counterfeiting.

Zero-dimensional metal halides have received wide attention due to their structural diversity, strong quantum confinement, and associated excellent photoluminescence properties. A reversible and tunable luminescence would be desirable for applications such as anti-counterfeiting, information encryption, and artificial intelligence. Yet, these materials are underexplored, with little known about their luminescence tuning mechanisms. Here we report a pyramidal coplanar dimer, (TBA)Sb2Cl7 (TBA = tetrabutylammonium), showing broadband emission wavelength tuning (585-650 nm) by simple thermal treatment. We attribute the broad color change to structural disorder induced by varying the heat treatment temperatures. Increasing the heating temperature transitions the material from long-range ordered crystalline phase to highly disordered glassy phase. The latter exhibits stronger electron-phonon coupling, enhancing the self-trapped exciton emission efficiency. The work provides a new material platform for manifold optical anti-counterfeiting applications and sheds light on the emission color tuning mechanisms for further design of stimuli-responsive materials.

Luminescent Mechanism and Anti-Counterfeiting Application of Hydrophilic, Undoped Room-Temperature Phosphorescent Silicon Nanocrystals.

Silicon nanocrystals (SiNCs) have attracted extensive attention in many advanced applications due to silicon's high natural abundance, low toxicity, and impressive optical properties. However, these applications are mainly focused on fluorescent SiNCs, little attention is paid to SiNCs with room-temperature phosphorescence (RTP) and their relative applications, especially water-dispersed ones. Herein, this work presents water-dispersible RTP SiNCs (UA-SiNCs) and their optical applications. The UA-SiNCs with a uniform particle size of 2.8 nm are prepared by thermal hydrosilylation between hydrogen-terminated SiNCs (H-SiNCs) and 10-undecenoic acid (UA). Interestingly, the resultant UA-SiNCs can exhibit tunable long-lived RTP with an average lifetime of 0.85 s. The RTP feature of the UA-SiNCs is confirmed to the n-π* transitions of their surface C═O groups. Subsequently, new dual-modal emissive UA-SiNCs-based ink is fabricated by blending with sodium alginate (SA) as the binder. The customized anticounterfeiting labels are also prepared on cellulosic substrates by screen-printing technique. As expected, UA-SiNCs/SA ink exhibits excellent practicability in anticounterfeiting applications. These findings will trigger the rapid development of RTP SiNCs, envisioning enormous potential in future advanced applications such as high-level anti-counterfeiting, information encryption, and so forth.

Visible Light-Activated Ultralong-Lived Triplet Excitons of Carbon Dots for White-Light Manipulated Anti-Counterfeiting.

Room temperature phosphorescence (RTP) has emerged as an interesting but rare phenomenon with multiple potential applications in anti-counterfeiting, optoelectronic devices, and biosensing. Nevertheless, the pursuit of ultralong lifetimes of RTP under visible light excitation presents a significant challenge. Here, new phosphorescent materials that can be excited by visible light with record-long lifetimes are demonstrated, realized through embedding nitrogen doped carbon dots (N-CDs) into a poly(vinyl alcohol) (PVA) film. The RTP lifetime of the N-CDs@PVA film is remarkably extended to 2.1 s excited by 420 nm, representing the highest recorded value for visible light-excited phosphorescent materials. Theoretical and experimental studies reveal that the robust hydrogen bonding interactions can effectively reduce the non-radiative decay rate and radiative transition rate of triplet excitons, thus dramatically prolong the phosphorescence lifetime. Notably, the RTP emission of N-CDs@PVA film can also be activated by easily accessible low-power white-light-emitting diode. More significantly, the practical applications of the N-CDs@PVA film in state-of-the-art anti-counterfeiting security and optical information storage domains are further demonstrated. This research offers exciting opportunities for utilizing visible light-activated ultralong-lived RTP systems in a wide range of promising applications.

Coffee-Ring Mediated Thinning and Thickness-Dependent Dewetting Modes in Printed Polymer Droplets Coupled with Assembly of Quantum Dots for Anti-Counterfeiting.

Molecular transport processes in printed polymer droplets hold enormous importance for understanding wetting phenomena and designing systems in applications such as encoding, electronics, photonics, and sensing. This paper studies thickness-dependent dewetting modes that are activated by thermal annealing and driven by interfacial interactions within microscopically confined polymeric features. The printing of poly(2-vinylpyridine) is performed in a regime where coffee-ring effects lead to strong thinning of the central region of the deposit. Thermal annealing leads to two different modes of dewetting that depend on the thickness of the central region. Mode I refers to the formation of randomly positioned small features surrounded by large hemispherical ones located along the periphery of the printed features and occurs when the central regions are thin. Observed at large central thicknesses, Mode II mediates significant molecular transport from edges toward the center of the printed droplet with thermal annealing and forms a hemispherical feature from the initial ring-like deposit. The selective adsorption of red, green, and blue emitting quantum dots over the poly(2-vinylpyridine) results in photoluminescent patterns. The selective assembly of photoluminescent quantum dots over patterned surfaces leads to deterministic and stochastic features beneficial to creating security labels for anti-counterfeiting applications.

A Novel Ion Species- and Ion Concentration-Dependent Anti-Counterfeiting Based on Ratiometric Fluorescence Sensing of CDs@MOF-Nanofibrous Films.

Traditional fluorescent anti-counterfeiting labels based on "on-off" fluorescence can be easily cloned. It is important to explore advanced anti-counterfeiting fluorescent labels with high-level security. Here, a pioneering ion species- and ion concentration-dependent anti-counterfeiting technique is developed. By successive loading Cu2+ -sensitive yellow emitted carbon dots (Y-CDs) and Cu2+ non-sensitive blue emitted carbon dots (B-CDs) into metal-organic frameworks (MOFs) and followed by electrospinning, the B&Y-CDs@MOF-nanofibrous films are prepared. The results show that the use of MOF not only avoids the fluorescence quenching of CDs but also improves the fluorescence stability. The fluorescence Cu2+ -sensitivity of the CDs@MOF-nanofibrous films can be regulated by polymer coating or lamination. The fluorescent label consisting of different Cu2+ -sensitivity films will show Cu2+ concentration-dependent decryption information. Only at a specific ion species and concentration (Cu2+ solution of 40-90 µm), the true information can be read out. Less or more concentration (<40 or >90 µm) will lead to false information. The identification of the real information depends on both the species and the concentration. After Cu2+ treatment, the fluorescence of the label can be recovered by ethylenediaminetetraacetic acid disodium (EDTA-2Na) for further recycling. This work will open up a new door for designing high-level fluorescent anti-counterfeiting labels.

Interfacing Lanthanide Metal-Organic Frameworks with ZnO Nanowires for Alternating Current Electroluminescence.

Alternating current electroluminescence (ACEL) devices are attractive candidates in cost-effective lighting, sensing, and flexible displays due to their uniform luminescence, stable performance, and outstanding deformability. However, ACEL devices have suffered from limited options for the light-emitting layer, which presents a significant constraint in the progress of utilizing ACEL. Herein, a new class of ACEL phosphors based on lanthanide metal-organic frameworks (Ln-MOFs) is devised. A synthesis of lanthanide-benzenetricarboxylate (Ln-BTC) thin film on a brass grid substrate seeded with ZnO nanowires (NWs) as anchors is developed. The as-synthesized Ln-BTC thin film is employed as the emissive layer and shows visible electroluminescence driven by alternating current (2.9 V µm-1 , 1 kHz) for the first time. Mechanistic investigations reveal that the Ln-based ACEL stems from impact excitation by accelerated electrons from ZnO NWs. Fine-tuning of the ACEL color is also demonstrated by controlling the Ln-MOF compositions and introducing an extra ZnS emitting layer. The advances in these optical materials expand the application of ACEL devices in anti-counterfeiting.

A Disposable Thermally Triggered Photonic Crystal Anti-Counterfeiting Tag with Irreversible Response and Multi-Step Color Changes.

Thermochromic photonic crystal (PC) is a promising material for anti-counterfeiting applications, but there are still challenges to further improve the anti-counterfeiting performance and the practicability in usage. Here, a disposable thermally triggered PC anti-counterfeiting tag with irreversible response and multi-step color changes is developed based on the thermochromic Silica/(Polyethylene glycol-Ethoxylated trimethylolpropane triacrylate) (SiO2/(PEG-ETPTA)) double-layer film. The fast and irreversible thermal response come from the quick melting and infiltration of PEG-ETPTA into the PCs upon heating. The multi-step color change at different temperatures originated from the regioselective control of the UV curing degree of the PEG-ETPTA layer and the resulting thermochromic temperature of the double-layer film. Therefore, the invisible PC pattern on the tag can be revealed part by part upon heating and became invisible again after overheating, which offered diversified visual effects and enhanced anti-counterfeiting performances.

Exploring Carbon Dots: Green Nanomaterials for Unconventional Lasing.

In recent years, the progress toward lighting miniaturization is focused on luminescent nanomaterials. Among them, fluorescent carbon dots (CDs) are receiving increasing attention thanks to their astonishing optical properties complemented by their intrinsic biocompatibility and low toxicity. The CDs can be easily dispersed in water, organic solvents or incorporated in polymeric matrices, preserving their emission properties. However, the relationship between their structural and optical properties is still not fully elucidated, motivating a consistent research effort for the comprehension of their features. Nevertheless, CDs demonstrate to be efficient gain materials for lasing, thanks to their high quantum yield (QY), emission tunability in the visible and near infrared (NIR) range, short lifetimes, and high absorption cross section, even if the synthetic reproducibility, the low reaction yield and the spectral width of the emission may limit their effective exploitation. This review summarizes the latest advancements in the investigation of the characteristic properties of CDs that make laser action possible, illustrating optical geometries for lasing and random lasing, both in solution and solid state, and the few currently demonstrated breakthroughs. While the journey toward their effective application is still long, the potential of CD-based laser sources is promising in various technological fields and futuristic perspectives will be discussed.

Conformation-Driven Responsive 1D and 2D Lanthanide-Metal-Organic Framework Heterostructures for High-Security Photonic Barcodes.

Development of luminescent segmented heterostructures featuring multiple spatial-responsive blocks is important to achieve miniaturized photonic barcodes toward anti-counterfeit applications. Unfortunately, dynamic manipulation of the spatial color at micro/nanoscale still remains a formidable challenge. Here, a straightforward strategy is proposed to construct spatially varied heterostructures through amplifying the conformation-driven response in flexible lanthanide-metal-organic frameworks (Ln-MOFs), where the thermally induced minor conformational changes in organic donors dramatically modulate the photoluminescence of Ln acceptors. Notably, compositionally and structurally distinct heterostructures (1D and 2D) are further constructed through epitaxial growth of multiple responsive MOF blocks benefiting from the isomorphous Ln-MOF structures. The thermally controlled emissive colors with distinguishable spectra carry the fingerprint information of a specific heterostructure, thus allowing for the effective construction of smart photonic barcodes with spatially responsive characteristics. The results will deepen the understanding of the conformation-driven responsive mechanism and also provide guidance to fabricate complex stimuli-responsive hierarchical microstructures for advanced optical recording and high-security labels.

Hour-Level Persistent Multicolor Phosphorescence Enabled by Carbon Dot-Based Nanocomposites Through a Multi-Confinement-Based Approach.

Hour-level persistent room temperature phosphorescence (RTP) phenomena based on multi-confinement carbon dots (CDs) are reported. The CDs-based system reported here (named Si-CDs@B2O3) can be efficiently synthesized by a simple pyrolysis method compared to the established persistent RTP systems. The binding modes of CDs, silica (SiO2), and boron oxide (B2O3) are deduced from a series of characterizations including XRD, FT-IR, and TEM characterization. Further studies show that the formation of covalent bonds between B2O3, SiO2, and CDs play a key role in activating the persistent RTP and preventing its quenching. This is a rare example of a persistent RTP system that exhibits hourly persistent RTP under environmental conditions. Finally, the applications of Si-CDs@B2O3 are demonstrated for anti-counterfeiting, long-duration phosphorescence imaging, and fingerprinting. This synthetic strategy is expected to provide strong technical support for the preparation of persistent RTP CDs and pave the way for the synthesis of persistent RTP CDs in the future.

Visual Sensor with Host-Guest Specific Recognition and Light-Electrical Co-Controlled Switch.

Perception of UV radiation has important applications in medical health, industrial production, electronic communication, etc. In numerous application scenarios, there is an increasing demand for the intuitive and low-cost detection of UV radiation through colorimetric visual behavior, as well as the efficient and multi-functional utilization of UV radiation. However, photodetectors based on photoconductive modes or photosensitive colorimetric materials are not conducive to portable or multi-scene applications owing to their complex and expensive photosensitive components, potential photobleaching, and single-stimulus response behavior. Here, a multifunctional visual sensor based on the "host-guest photo-controlled permutation" strategy and the "lock and key" model is developed. The host-guest specific molecular recognition and electrochromic sensing platform is integrated at the micro-molecular scale, enabling multi-functional and multi-scene applications in the convenient and fast perception of UV radiation, military camouflage, and information erasure at the macro level of human-computer interaction through light-electrical co-controlled visual switching characteristics. This light-electrical co-controlled visual sensor based on an optoelectronic multi-mode sensing system is expected to provide new ideas and paradigms for healthcare, microelectronics manufacturing, and wearable electronic devices owing to its advantages of signal visualization, low energy consumption, low cost, and versatility.

Remarkable Off-On Tunable Solid-State Luminescence by the Regulation of Pyrene Dimer.

It is always a challenge to achieve "off-on" luminescent switch by regulating non-covalent interactions. Herein, we report a unique strategy for constructing high performance "off-on" tunable luminescent materials utilizing a novel molecule (TFPA) consist of pyrene and cyanostilbene. The pristine crystal of TFPA is almost non-emissive. Upon grinding/UV irradiation, an obvious luminescence enhancement is observed. Theoretical and experimental results revealed the underlying mechanism of this intriguing "off-on" switching behavior. The non-emissive crystal consists of ordered H-aggregates, with adjacent two molecules stacked in an anti-parallel manner and no overlapped area in pyrene moieties. When external force is applied by grinding or internal force is introduced through the photoisomerization, the dimer structures are facilitated with shorter intermolecular distances and better overlapping of pyrene moieties. In addition, the "on" state can recover to "off" state under thermal annealing, showing good reversibility and applicability in intelligence material. The present results promote an in-depth insight between packing structure and photophysical property, and offer an effective strategy for the construction of luminescence "off-on" switching materials, toward the development of stimuli-responsive luminescent materials for anti-counterfeiting.

Dual Aliovalent Dopants Cu, Mn Engineered Eco-Friendly QDs for Ultra-Stable Anti-Counterfeiting.

Doping in semiconductor quantum dots (QDs) using optically active dopants tailors their optical, electronic, and magnetic properties beyond what is achieved by controlling size, shape, and composition. Herein, we synergistically modulated the optical properties of eco-friendly ZnInSe2/ZnSe core/shell QDs by incorporating Cu-doping and Mn-alloying into their core and shell to investigate their use in anti-counterfeiting and information encryption. The engineered "Cu:ZnInSe2/Mn:ZnSe" core/shell QDs exhibit an intense bright orange photoluminescence (PL) emission centered at 606 nm, with better color purity than the undoped and individually doped core/shell QDs. The average PL lifetime is significantly extended to 201 ns, making it relevant for complex encryption and anti-counterfeiting. PL studies reveal that in Cu:ZnInSe2/Mn:ZnSe, the photophysical emission arises from the Cu state via radiative transition from the Mn 4T1 state. Integration of Cu:ZnInSe2/Mn:ZnSe core/shell QDs into poly(methyl methacrylate) (PMMA) serves as versatile smart concealed luminescent inks for both writing and printing patterns. The features of these printed patterns using Cu:ZnInSe2/Mn:ZnSe core/shell QDs persisted after 10 weeks of water-soaking and retained 70 % of PL emission intensity at 170 °C, demonstrating excellent thermal stability. This work provides an efficient approach to enhance both the emission and the stability of eco-friendly QDs via dopant engineering for fluorescence anti-counterfeiting applications.

Spatially Resolved Multicolor Luminescence Tuning on the Single 1D Heterogeneous Microrod.

The spatially resolvable multicolored microrods have potential applications in many fields. However, achieving spatially resolved multicolor luminescence tuning on the microrod with a fixed composition remains a daunting challenge. Herein, a strategy is proposed that allows for the tuning of spatially resolved, multicolored upconversion (UC) luminescence (UCL) along a 1D heterogeneous microrod by modifying the pulse width of an external laser. NaYbF4:1 % Ho is identified as an UCL color-adjustable material, exhibiting pulse width-dependent multicolored UCL, resulting in a significant regulation of the red/green (R/G) ratio from 0.1 to 10.3 as the pulse width is varied from 0.1 to 10 ms. Such variability can be ascribed to differences in the number of photons incident upon the microrod throughout the period necessary for the UC process to occur. Additionally, NaYbF4:1 %Tm and NaYF4:20 %Yb,1 %Ho are employed as materials that emit blue and green light, respectively, with their UCL colors largely unaffected by changes in the pulse width. Subsequently, a tip-modified epitaxial growth method is utilized to integrate both UCL color-adjustable and non-adjustable segments within the same microrod. Comparing with single-color or fixed multicolor microrods, our developed multisegmented emissive color adjustable 1D heterogeneous microrods have unique optical characteristics and can carry more optical information.

Multi Stimuli Responsive Dual Aggregation-Induced Emission and Photochromic Behavior of a Tetraphenyl Substituted Triphenylamine Derivative and its Application as Anti-counterfeiting Agent.

A multi-stimuli responsive tetraphenyl substituted tripehnylamine-based aggregation induced emissive (AIE) material coupled with spiropyran was prepared. Owing to the presence of AIE and photochromic moiety, the molecule exhibits emissive aggregates, photochromism, and acidochromism. The multiple stimuli sensitive behavior of the molecule was explored for anti-counterfeiting behavior on TLC plate and commercial banknotes. The fluorogenic and photogenic response under UV and visible light established the potential of the candidate as a new generation encryption material.

Carbon dot-loaded Fe3O4as photonic pigments for multilevel anti-counterfeiting.

Amorphous arrays assembled from colloidal microspheres are a way that obtains angle-independent structural colors. In order to obtain additional properties, colloidal microspheres, which are constituent units, can be modified with other materials. Here, we utilized the silane-functionalized carbon quantum dots (SiCDs) by incorporating them into the Stöber reaction to fabricate Fe3O4@SiO2/SiCDs nanospheres with a core-shell structure. Amorphous colloidal arrays (ACAs) were constructed on commercial printing paper using Fe3O4@SiO2/SiCDs nanoparticles as structural units by a simple permeation assembly. Macroscopically, the prepared ACAs exhibit the magnetic properties of Fe3O4, while under sunlight, they display bright, angle-independent structural colors. Under ultraviolet light, the array shows significant fluorescence. This enables the presentation of multidimensional information under varying magnetic and lighting conditions. By adjusting the thickness of the outer SiO2/SiCDs composite layer, the optical properties and magnetism can be controlled easily. Moreover, due to the strong light absorption capability and high refractive index of Fe3O4, the digital patterns constructed with Fe3O4@SiO2/SiCDs nanospheres demonstrate excellent multi-level anti-counterfeiting characteristics, even under water exposure. The magnetic properties of Fe3O4@SiO2/SiCDs nanospheres, along with their distinct display characteristics under different optical environments, suggest their wide applicability in the fields of multifunctional anti-counterfeiting pigments, bioimaging, and sensing displays.

Preparation and Application of a Sulfur-Doped Fluorescent Carbon Dots with Aggregation-Induced Emission Character.

As a new type of zero-dimensional nanomaterial, carbon dots are widely applied in various fields. However, most of the carbon dots have aggregation fluorescence quenching properties, which limited their practical applications. In this study, a novel sulfur-doped carbon dots (S-CDs) was prepared by solvothermal method. The properties of the S-CDs in ethanol solution and in solid state were investigated respectively. The results showed that the S-CDs have an excited wavelength dependent emission of blue fluorescence in ethanol solution, and have orange fluorescence emission in solid state and composite films, indicating the prepared S-CDs has aggregation-induced emission (AIE) performance. The main reason was that the presence of S-S bonds and the intramolecular rotation of aromatic rings were limited in solid state, resulting in its emission of orange fluorescence. Furthermore, the S-CDs could be applied to identify fingerprints, anti-counterfeiting.

Preparation of Fluorescent "on-off-on" Carbon Quantum Dots and Their Application to the Detection of Fe3+ and Ascorbic Acid and Information Encryption.

Carbon quantum dots are a new type of fluorescent carbon-based nanomaterials, and their excellent properties have provoked a strong research interest. Herein, blue-fluorescent carbon quantum dots (k-CQDs) were successfully synthesized by a simple one-step hydrothermal method using chitosan and ethylenediaminetetraacetic acid as precursors. It was found that Fe3+ could quench the fluorescence of k-CQDs by a dynamic quenching mechanism that increased the positive charge in solution. Due to ascorbic acid (AA) can reduce Fe3+ to Fe2+, the positive charge in solution was reduced and the fluorescence of k-CQDs was restored. Based on the mechanism of the fluorescence "on-off-on", k-CQDs were used for the detection of Fe3+ and AA with strong antijamming capability. The LOD for Fe3+ concentrations in the ranges of 0 to 30 µM and 30 to 100 µM were 0.3 µM and 0.76 µM, respectively. The LOD for AA concentrations in the ranges of 0 to 82.5 µM and 82.5 to 172.5 µM were 3.93 µM and 1.63 µM, respectively. Spiking recoveries of Fe3+ in tap water, AA in orange juice and tomato juice were 87.93 ∼ 101.13%, 86.77 ∼ 105.15% and 86.43 ∼ 103.80%, respectively. Meanwhile, k-CQDs also showed good potential for anti-counterfeiting encryption.

Electrospinning of photochromic poly(ethylene terephthalate) nanofibers toward information authentication.

The use of photochromism to enhance the anti-counterfeiting of a wide range of economic goods is an intriguing prospect. Creating a translucent anti-counterfeiting nanocomposite is critical to improving the engineering procedures of the encoding materials. Herein, we use electrospinning to produce anti-counterfeiting nanofibrous films from nanoparticles of rare-earth aluminate (NREA) and recycled poly(ethylene terephthalate) (PET). Different nanofiber films with distinct emission properties were created using different ratios of NREA. The ultraviolet (UV)-induced photochromism of the NREA@PET nanofibers was proved. Immobilizing NREA at the nanoscale ensures better dispersion without agglomeration in the PET nanofibrous matrix, which is essential for the development of transparent NREA@PET films. Diameters of 4-13 nm for NREA were shown using transmission electron microscopy. X-ray fluorescence spectroscopy, energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy, elemental mapping, and other techniques were used to investigate the photochromic nanofibers' morphology, elemental contents, optical transmittance, and mechanical performance. It was observed that the nanofiber diameter in NREA@PET was between 150 and 250 nm. Excitation and emission bands of electrospun NREA@PET nanofibrous films were monitored at 365 and 518 nm, respectively. The superhydrophobicity of NREA@PET increased with increasing NREA concentration. The transparent nanofibers exhibited fast and reversible dual-mode fluorescent photochromism to green emission without fatigue when stimulated beneath a UV source. Using the present anti-counterfeiting films can be regarded as a simple technique to develop flexible materials to launch an ideal marketplace with affordable societal and economic advantages.