Reversible Thermochromism Research Articles

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

AbstractErbium ions are commonly used to extend the photoelectric properties of metal halide perovskites from visible to near‐infrared range. However, achieving high‐efficiency multimode 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 multimode luminescence and enhance the second near‐infrared region (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 (PLQY) 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 multimode luminescence in perovskites, opening avenues for advanced applications in blue‐excitable NIR light emitting diodes (LEDs), 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.

Co-assembly-Directed Enhancement of the Thermochromic Reversibility and Solvatochromic Selectivity of Supramolecular Polydiacetylene.

The construction of functional materials via the co-assembly of multimolecular systems has recently emerged as a fascinating topic. The co-assembled multicomponent could promote the evolution of supramolecular assemblies into a high-order nanoarchitecture with improved functional properties. We report the successful preparation of a dual-functional polydiacetylene (MCPDA-Tz-CA) having thermochromic and solvatochromic properties via facile co-assembly of MCDA-Tz and cyanuric acid (MCDA-Tz-CA) followed by ultraviolet-induced polymerization. Molecular packing patterns from powder X-ray diffraction and density functional theory calculations of molecular self-assembly processes confirm highly ordered co-assembled lamellar structures. MCPDA-Tz-CA showed excellent reversible thermochromism properties when the temperature was increased from 30 to 150 °C with a reversible blue-to-red color transition that could be detected by the naked eye. Also, MCPDA-Tz-CA displayed selective blue-to-red solvatochromism against dimethylformamide and dimethyl sulfoxide. Detailed investigations revealed that the enhanced thermochromic reversibility and solvatochromic selectivity could be attributed to the hydrogen-bonding interactions and the formation of a network structure in the MCDA-Tz/cyanuric acid co-assembly. Our research opens a promising route for improving the performance of functional materials via noncovalent multicomponent arrangements at the molecular level.

An AIE-active Schiff base derivative with reversible thermochromism based on two-step isomerization in the solid state

Thermoresponsive aggregation-induced emission (AIE) luminogens, especially in the solid state, have attracted extensive attention due to their potential applications as smart materials. Herein, we report an AIE-active tetraphenylethene (TPE)-based Schiff base derivative (TPENOMe-I) that exhibits rapid and reversible thermochromism along with luminescence in the solid state. The excited-state intramolecular proton transfer-induced AIE and efficient thermochromism (rather than photochromism) are facilitated by the relatively compact crystal packing and polymorphism of TPENOMe-I, which effectively suppress cis-to-trans isomerization. Theoretical calculations demonstrated that the two-step isomerization process between the enol isomer and the cis- and twisted cis-keto isomers is responsible for the thermochromic behavior of solid-state TPENOMe-I. The chromic transitions may result from the reversible interconversion between various twisted cis-keto forms during the thermal isomerization process. Three composites containing TPENOMe-I that were simply prepared with low cost excited reversible thermochromism and were successfully demonstrated in thermochromic patterns. The findings suggest that these TPENOMe-I composites have promising applications for use in warning labels, thermochromic textiles, and thermal printing.

Nanocellulose-based cobalt(II) coordinated malonic acid hybrid aerogels exhibiting reversible thermochromism and moisture sensor properties

The emergence of sustainable polymers and technologies has led to the development of innovative materials with minimal carbon emissions which find extensive applications in wearable electronics, biomedical sensors, and Internet of Things (IoT)-based monitoring systems. Nanocellulose which can be generated from abundant biomass materials has been widely recognized as a sustainable alternative for a diverse range of applications due to its remarkable properties and eco-friendly nature. By making use of the unique and easily accessible coordination transformation property of Co(II) ions and associated visible light absorption changes, we report a novel Co(II) cation-incorporated nanocellulose/malonic acid hybrid aerogel material that exhibits reversible thermochromism induced by thermal stimulus in the presence of atmospheric moisture. This effect is accentuated by the highly porous nature of the nanocellulose aerogel material we have developed. Besides the reversible thermochromic property which Co(II) ions exhibit, the metal ions act as very efficient reinforcing units contributing significantly to the structural stability and rigidity of the hierarchical aerogels by coordinative cross-linking through carboxylate moieties present in the TEMPO-oxidized cellulose nanofibers (TCNF) and additionally adding malonic acid to provide sufficient COO− for cross-linking. Thorough characterization and detailed investigation of as-prepared hybrid aerogels was conducted to evaluate their overall properties including reversible thermochromism and moisture sensor behaviour. Further, an Android mobile-based application was developed to demonstrate the real-world application of the aerogels for atmospheric humidity sensing.

Antimony doping towards fast digital encryption and decryption and high-efficiency WLED in zero-dimensional hybrid indium chlorides

Lead-free metal halides with thermally induced reversible fluorescence transitions are promising smart optoelectronic materials. However, it is challenging to obtain such materials with reversible and fast fluorescent thermochromism at relatively low temperatures. Herein, two series of new zero-dimensional (0-D) hybrid perovskite indium chlorides doped with Sb3+ are synthesized and characterized, namely (TAEA)InCl6·Cl·4H2O: xSb3+ (1: xSb3+) and (TETA)InCl6·Cl·H2O: xSb3+ (2: xSb3+) (TAEA = quadruply protonated tris(aminoethyl)amine; TETA = quadruply protonated triethylenetetramine; x = 0 − 15 %). Compound 1: 0.5 %Sb3+ displays green broadband emission with photoluminescence quantum yield (PLQY) of 44.4 %, while compound 2: 1 %Sb3+ produces yellow emission with PLQY of 73.46 %. A reversible transition between green and orange light emission for 1: 0.5 %Sb3+ can be triggered by thermal stimulation; such photoluminescence (PL) color switching happens with a fast response time of 20 s and a low transition temperature of 333 K. In addition, the materials combining compounds 2: 1 %Sb3+ and 1: 0.5 %Sb3+ can achieve complex digital encryption and decryption upon heating. Furthermore, due to its excellent luminous efficiency, the 2: 1 %Sb3+ is employed as yellow phosphor for white light-emitting diode (WLED). The WLED shows a CRI of 90.5 and a CCT of 5415 K, superior to most WLEDs based on hybrid metal halides. Finally, the impact of forming the self-trapped excitons state and complex PL mechanism of compound 1: 0.5 %Sb3+ are investigated through DFT calculations and femtosecond transient absorption techniques. This work provides new insights into the design of hybrid metal halides with multiple optical properties, paving the way to obtaining materials for multiple optical applications.

One-pot microwave-assisted approach of polydiacetylene/zinc oxide nanocomposite for reversible thermochromic

This study introduces a new technique to fabricate the reversible poly(PCDA/ZnO) nanocomposites thermochromism. Our preparation process is the solution-mixing method, which is supported by microwave synthesis time instead of ultrasonic bath or stirrer. The presence of ethanol molecules in aqueous media in the solution-mixing method induces dipolar polarization. In addition, the presence of Zn2+ leaking out of the ZnO can produce ionic polarization. These factors affect the shape of poly(PCDA/ZnO) nanocomposites based on their thermochromic properties. The optical properties of poly(PCDA/ZnO) nanocomposite were determined through UV-Vis absorption spectroscopy. The morphology of this nanocomposite was examined by scanning electron microscopy, and its crystallinity was investigated by X-ray diffraction. The inter-intrachain interaction was confirmed by infrared spectroscopy. In addition, the poly(PCDA/ZnO) nanocomposite embedding PVA was prepared. The reversible theromochromic properties of poly(PCDA/ZnO) nanocomposites demonstrated a higher color transition temperature with increasing microwave synthesis time. It is an important observation to understand the effect of microwave synthesis time on the morphology and reversible thermochromism of the poly(PCDA/ZnO) nanocomposite

Tunable thermoresponsive hydrogels for temperature regulation and warning in fruit and vegetables preservation

Fresh fruit and vegetables usually suffer from quality deterioration when exposed to inappropriate temperatures. Common energy-input temperature regulation is widely applied but there remain challenges of increasing energy consumption. Passive temperature management regulates the heat transfer without energy consumption, showing a sustainable strategy for food preservation. Here, thermoresponsive hydrogels were constructed by incorporating NaCl and sodium dodecyl sulfate (SDS) micelles into a poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAM-co-AM)) network. Due to the excellent mechanical properties and reversible thermochromism at 14 °C and 37 °C, Gel-8 wt%-NaCl could inhibit temperature rise and avoid sunburn damage to peppers under direct sunlight by blocking the input of solar energy and accelerating moisture evaporation. Additionally, hydrogels could act as a feasible sensor by providing real-time visual warnings for inappropriate temperatures during banana storage. Based on the self-adaptive thermoresponsive behaviour, the prepared hydrogels showed effective performance of temperature regulation and quality preservation of fruit and vegetables.

Dimethyl Amine Detection using Polydiacetylene Functionalized Cellulose Paper

AbstractThis work demonstrates our effort to develop stimuli responsive cellulose films for the detection of dimethyl amines, a biogenic amine, released during food decomposition. Herein, we demonstrate that thin layer deposition of polydiacetylene‐zinc oxide nanosheets (PDA‐ZnO) on cellulose (CE) paper yields a stimuli responsive strip exhibiting strong thermochromism and solvatochromism against dimethyl amine. The incorporation of Zn nanoclusters within the composite plays an essential role in achieving reversible thermochromism while strong intermolecular interactions promote adsorption of PDA‐ZnO on cellulose paper. X‐ray diffraction and infrared spectroscopy reveal that the Zn2+ ions intercalate with PDA bilayer and strongly interact with the carboxylate headgroup of PDA. Furthermore, the reversible thermochromism persist when the nanosheets are deposited on cellulose (CE) paper when assembling PDA‐ZnO−CE paper. In addition, PDA‐ZnO−CE displayed selective solvatochromism allowing the utilization of the paper in the detection of dimethyl amine as it displayed a distinct and remarkable purple to orange colour transition. In particular, the response of the PDA‐ZnO−CE paper in several other organic solvents was poor as no transitions were observed hence its selectivity towards dimethylamine. In conclusion, the incorporation of PDA‐ZnO on cellulose paper is a step forward towards designing of a stimuli responsive packaging material that can detect biogenic amines released during food decomposition thereby preventing food poisoning.

Thermally Induced Lattice-Defective Oxygen Breathing in Perovskite-Structure Stannates with High-Contrast Reversible Thermochromism.

Inorganic thermochromic materials exhibit a tunable color gamut and a wide chromatic temperature range, indicating their potential for intelligent adaptive applications in thermal warning, temperature indication, thermal regulation, and interactive light-to-thermal energy conversion. However, most metal-oxide-based thermochromic materials show weak chromaticity adaption with the change of temperature, which needs further understanding of the microscopic principle to clarify the potential route to improve the contrast and identifiability for fabricating better thermochromic materials. Using perovskite-structure (AMO3) alkaline earth metal stannate (Ba1-xSrxSnO3, 0.0 ≤ x ≤ 1.0) as a model system, this paper reports for the first time the mechanism of the properties of thermally induced defect-enhanced charge transfer-type (CTT) thermochromic materials and the strategy for regulating their thermochromic properties by A-site cations. BaSnO3 exhibits continuously reversible thermochromic properties with high contrast from weak light yellow (b* = 11) to strong bright yellow (b* = 58) between room temperature and 550 °C. In-situ high-temperature X-ray diffraction (in-situ XRD), in-situ UV-vis absorption spectroscopy (in-situ UV-vis), thermogravimetric (TG), and electron paramagnetic resonance (EPR) spectra indicate that this excellent thermochromic phenomenon is attributed to the weakening of Sn-O bond hybridization at high temperatures, as well as the formation of a large number of oxygen vacancies at the top of the valence band, and the enhanced charge transfer resulting from the generation of impurity levels in the Sn2+ 5s2 intermediate. Replacing Ba2+ by Sr2+ in Ba1-xSrxSnO3 successfully tuned the thermochromic properties, which is attributed to the Sr2+ doping level-directed oxygen defect concentration and deoxygenation rate. The demonstrated defect-enhanced charge transfer behavior promotes a feasible route for lattice oxygen-mediated thermochromic materials and provides a fundamental relationship between thermally induced defects and colorimetry.

Towards Room Temperature Thermochromic Coatings with controllable NIR-IR modulation for solar heat management & smart windows applications

Solar heat management & green air-conditioning are among the major technologies that could mitigate heat islands phenomenon while minimizing significantly the CO2 global foot-print within the building & automotive sectors. Chromogenic materials in general, and thermochromic smart coatings especially are promising candidates that consent a noteworthy dynamic solar radiation Infrared (NIR-IR) regulation and hence an efficient solar heat management especially with the expected increase of the global seasonal temperature. Within this contribution, two major challenging bottlenecks in vanadium oxide based smart coatings were addressed. It is validated for the first time that the NIR-IR modulation of the optical transmission (∆TTRANS = T(T〈TMIT) − T(T〉TMIT) of Vanadium oxide based smart coatings can be controlled & tuned. This upmost challenging bottle-neck controllability/tunability is confirmed via a genuine approach alongside to a simultaneous drastic reduction of the phase transition temperature TMIT from 68.8 °C to nearly room temperature. More precisely, a substantial thermochromism in multilayered V2O5/V/V2O5 stacks equivalent to that of standard pure VO2 thin films but with a far lower transition temperature, is reported. Such a multilayered V2O5/V/V2O5 thermochromic system exhibited a net control & tunability of the optical transmission modulation in the NIR-IR (∆TTRANS) via the nano-scaled thickness’ control of the intermediate Vanadium layer. In addition, the control of ∆TTRANS is accompanied by a tremendous diminution of the thermochromic transition temperature from the elevated bulk value of 68.8 °C to the range of 27.5–37.5 ºC. The observed remarkable and reversible thermochromism in such multilayered nano-scaled system of V2O5/V/V2O5 is likely to be ascribed to a noteworthy interfacial diffusion, and an indirect doping by alkaline ions diffusing from the borosilicate substrate. It is hoped that the current findings would contribute in advancing thermochromic smart window technology and their applications for solar heat management in glass windows in general, skyscraper especially & in the automotive industry. If so, this would open a path to a sustainable green air-conditioning with zero-energy input.

Reversible thermochromism of CsPbBr3-doped tellurite glass

Perovskite quantum dots (PQDs) have emerged as a promising research field and dynamic modulation of PQDs could induce reversible color alterations of PQD-doped glass.

A novel guanidine-containing polyoxotantalate with reversible thermochromism property

A novel guanidine-containing polyoxotantalate (POTa), H12[CN3H6]12Na2(H2O)6[Cu(en)2(H2O)]3[Ta6O19]4·32H2O (1) has been synthesized by adding the CH6N3+ as counter cations. The [Ta6O19]8− clusters in compound 1 are connected by sodium ions to form a 2-D layered structure, which is further connected through [Cu(en)2(H2O)]2+ to form a 3-D supramolecular framework structure. Moreover, it is demonstrated that compound 1 exhibits reversible thermochromism behavior, changing from purple to dark blue upon heating and dehydration, which endows it with potential application in the field of anti-counterfeiting functional materials.

Remarkable Thermochromism in the Double Perovskite Cs2NaFeCl6

AbstractLead‐free halide double perovskites (HDPs) have emerged as a new generation of thermochromic materials. However, further materials development and mechanistic understanding are required. Here, a highly stable HDP Cs2NaFeCl6 single crystal is synthesized, and its remarkable and fully reversible thermochromism with a wide color variation from light‐yellow to black over a temperature range of 10 to 423 K is investigated. First‐principles, density functional theory (DFT)‐based calculations indicate that the thermochromism in Cs2NaFeCl6 is an effect of electron–phonon coupling. The temperature sensitivity of the bandgap in Cs2NaFeCl6 is up to 2.52 meVK−1 based on the Varshni equation, which is significantly higher than that of lead halide perovskites and many conventional group‐IV, III–V semiconductors. Meanwhile, this material shows excellent environmental, thermal, and thermochromic cycle stability. This work provides valuable insights into HDPs' thermochromism and sheds new light on developing efficient thermochromic materials.

In situ optical and structural properties of the thermochromic material Nd2MoO6

The reversible thermochromic inorganic material of rare earth neodymium molybdate Nd2MoO6 was synthesized by solid state reaction. In the temperature range of 30–300 ℃, the color of the sample changed reversibly from light blue to green. In-situ UV/Vis diffuse reflectance spectroscopy (UV/Vis DRS), in-situ powder X-ray diffraction (XRD) and in-situ Raman spectroscopy were used to study the mechanism of the reversible thermochromism of the materials. In-situ XRD shows that there is no phase transition during heating and cooling. With the increase in temperature, the lattice of the sample expands anisotropically. The lattice extension leads to a change in the ligand field environment around the Nd-O polyhedra, which affects the absorption intensity of the UV/Vis diffuse reflectance spectrum, leading to a change in color. The distorted lattice returns to its initial state after cooling to room temperature.

Combined experimental and DFT study on high‐temperature thermochromism of Co‐doped LaCrO3 coating for thermal indicator

AbstractNoncontact temperature measurement using thermochromic materials is vital in the field of temperature indication, but the related mechanisms behind thermochromic behavior are diverse and high complexity, and the color‐temperature correspondence is poorly explored. This paper systematically studied the thermochromic mechanisms and color‐temperature correspondence in the cobalt‐doped LaCrO3 coatings via experiment and density functional theory study. The coatings appear reversible thermochromism from green to black with temperature and composition, functions from room temperature to 700°C. This thermochromism is attributed to the lattice expansion and bandgap reduction as the temperature increase, and a model of temperature effect bandgap was proposed. Meanwhile, the coating temperature can be inferred from the color change because the CIE chromaticity coordinate of the coating varies linearly with temperature, and the mean relative error of thermochromic measurements is 8.28%. Furthermore, the cobalt doped introduces impurity energy levels and enhances the interaction between photons and carriers, which reduce the bandgap and increase the absorption in the visible spectrum resulting in darker colors. This work provides a stable and efficient high‐temperature thermochromic coating that has a wide thermochromic temperature range and clear color‐temperature correspondence, which shows broad application prospects in the field of thermal indication at high temperatures.

Reversible Thermochromic Bismuth Iodide Enabled by Self‐Adjustment

AbstractLight‐harvesting materials with dynamical management of light transmittance hold great promise in smart photovoltaics (PV). Here, a novel organic–inorganic halide, MVBi2I8 (MV = methyl viologen cation), exhibiting reversible thermochromism and constant bandgap of ≈1.65 eV over a wide temperature range of 77–453 K, is presented as a candidate. The compound consists of 0D (Bi4I16)4– clusters and MV2+ cations. And the adjacent (Bi4I16)4– clusters are in touch with each other, forming a 3D interaction for the inorganic part. The experimental and theoretical studies reveal that the ionic and covalent interactions in the crystal undergo a self‐adjusting process in response to temperature changes. The self‐adjustment and electron transfer between inorganic clusters and organic cations enable excellent reversible thermochromism and constant narrow bandgaps over a wide temperature range, which is expected for smart PV windows integrated with information displays and potentially other technologies.

Polyoxometalate-Viologen Thermochromic Hybrids for Organic Amine Detectors and Memristors with Temperature-Regulating Resistance Switching Characteristics.

There are relatively few reports on the combination of viologen and polyoxometalates (POMs). Herein, we successfully synthesized three viologen-POM-based compounds by in situ transformation of ligands under hydrothermal conditions, namely, {MII(1,4-cby)2[H2(γ-Mo8O26)]}·nH2O (1: M = Ni, n = 4; 2: M = Co, n = 6), and [NiII(1,3-cby)(H2O)4(β-Mo8O26)0.5]·2H2O (3) (1,4-cby·Cl = 1-(4-carboxy-benzyl)-[4,4']bipyridinyl-1-ium, 1,3-cby·Cl = 1-(3-carboxy-benzyl)-[4,4']bipyridinyl-1-ium). Isostructural compounds 1 and 2 exhibit two-dimensional (2D) layer structures with POMs as linking nodes, while compound 3 shows a one-dimensional (1D) metal-organic chain with dissociative POM anions. When the temperature increases, compounds 1-3 show good reversible thermochromism properties and also have a fluorescence quenching effect. Moreover, compounds 1-3 can also be used as detectors for organic amines, especially in the atmosphere of ammonia, ethylenediamine, and diethylamine with an obvious discoloration effect. In addition, compound 1 was used as a material for the preparation of memristors with superior properties (distinct temperature-adjusted resistive switching properties). It shows bipolar resistive switching (RS) behavior at different temperatures of 20, 50, and 100 °C. The results show that the 1-based memristor has good thermal stability, which is important for high-temperature environment applications. It also shows that crystalline viologen-POM-based compounds are ideal candidates for making memristors.

Dynamic CPL switching realized in chiral Mn-based metal halides with reversible thermochromism

(R-/S-Br-MBA)3MnBr5shows reversible conversion of CPL emission in wavelength and direction during heating and cooling.

Polyvinyl alcohol/propylene glycol facilitates reversible thermochromism of passive energy-saving flexible wood films at low (brightness) to high (depth) temperatures.

Reversible thermochromism presents depth at low temperatures and brightness at high temperatures, which is not conducive to the application of the passive energy-saving and shading effect. Here, we propose an innovative strategy for unconventional reversible thermochromic energy-storage flexible wood films (FT-PCMs-2) by the contribution of polyvinyl alcohol/propylene glycol (PVA/PG). Upon heating, the FT-PCMs-2 changes from light red/green to dark red/green, in contrast to the color change of the non-flexible composites without PVA/PG. The FT-PCMs-2 has good flexibility, mechanical strength and thermal stability. Among them, MSR-DEW-6PVA and MSG-DEW-6PVA have better comprehensive properties, including suitable phase change temperatures (38.6 °C and 37.2 °C), high latent heat values (59.79 J g-1 and 73.02 J g-1), and low supercooling degrees (2 °C and 0.6 °C). FTIR, XRD and SEM analysis show that the binary fatty acid eutectics were successfully loaded into the eucalyptus fibre skeleton with physical interaction with PVA/PG. In addition, MSR-DEW-6PVA and MSG-DEW-6PVA have photothermal conversion rates of 48.3% and 36%, good cycling stability and anti-leakage performance after 50 cycles, and have promising applications in the fields of building energy saving, intelligent windows and decoration.