Abstract
Introduction
Luminescent textiles, which emit visible light under specific excitation conditions, have attracted significant attention in material science. Their applications span diverse fields, from decorative fabrics to safety wear in dark environment.1–3 However, current luminescent textiles often suffer from limited brightness, durability as well as radioactivity and toxicity, 4 hindering their widespread use. Addressing these limitations is crucial for the advancement of luminescent textiles and their integration into various practical applications. One way to address these limitations is to explore the use of non-toxic and bright luminescent materials that can be incorporated into textiles.
ZnO is a widely used semiconductor with excellent optical and electrical properties.5,6 ZnO-based luminescent materials have gained significant attention due to their inexpensive, non-toxic and efficient nature, 7 as well as the wide range of applications in optoelectronics 8 and potential for integration into textiles.9,10 By themselves, ZnO nanomaterials, in particular, offer high luminescence efficiency and stability. 11 Nevertheless, ZnO luminescent materials still face challenges such as insufficient photocatalytic activity 12 and intensity. 13 However, embedding rare earth elements, which are known for their unique optical properties, into ZnO matrices has been proposed as a potential solution to these issues.14,15
The incorporation of rare earth elements, such as europium (Eu), into ZnO-based luminescent materials offers significant improvements.16,17 Europium’s unique electronic structure enables efficient energy transfer and emission of specific wavelengths, leading to enhanced luminescence intensity. 18 Previous studies have demonstrated that Eu-doped ZnO nanocomposites exhibit superior luminescent properties compared to undoped ZnO and ZnO doped with low concentration of Eu.5,19,20 These improvements are attributed to the energy level transitions within the Eu ions, which facilitate efficient energy transfer and emission processes. 21
However, most of the current studies that combine europium with ZnO are focused on the composite in the forms of powders, solutions or membranes. In addition, rare earth luminescent textiles are usually prepared through methods like melt spinning, solution spinning, surface coating or bonding methods. Magnetron sputtering technology, a versatile method for thin film deposition, offers significant advantages in our study. Its ability to precisely control the composition and microstructure of deposited films benefits the creation of uniform and high-quality Eu-doped ZnO composite films on textiles. 22 Furthermore, magnetron sputtering allows for the deposition of thin films with excellent adhesion to the textile substrate, ensuring durability and stability.23,24 By utilizing this technology, we aim to overcome the limitations of current luminescent textiles and develop a novel material with superior luminescent properties suitable for a wide range of applications.25,26
Experimental
Materials
The materials used in this work include cotton woven fabric (90.66 g/m2, Xinzhe Textile Industry), zinc (Zn) target (Ф 76.2 × 3 mm, 99.995%, Zhongnuo New Material (Beijing) Technology Co., LTD) and europium oxide-doped zinc oxide target that possess compositions of ZnO:Eu2O3 at a ratio of 97:3 atomic percent (Ф 76.2 × 3 mm, 99.99%, Zhongnuo New Material (Beijing) Technology Co., LTD) as well as anhydrous ethanol (Sinopharm Chemical Reagent Co., Ltd).
Preparation of rare earth Eu-doped nano ZnO composite film
The radio-frequency magnetron sputtering method was employed to deposit thin films onto cotton fabrics with ZnO:Eu2O3 target or Zn target. The study utilized Zn for reaction sputtering to form ZnO film on the fabric due to the fact that Zn targets are more robust and solid, with higher deposition rate and no oxygen deficiency issue.
Multiple cotton fabrics measuring 20 × 20 cm were cut and soaked in anhydrous ethanol for 30 min. Subsequently, they were placed in an oven at 50°C for 30 min to assure complete evaporation of the ethanol. This step aimed to eliminate any impurities or sizing agents on the cotton fabrics that could potentially influence the final experimental results. 27
The treated fabrics were then fixed onto a sample holder positioned 15 cm away from the target. Under certain conditions (argon gas flow rate = 20 mL/min, base vacuum = 1.5 × 10−3 Pa, working pressure = 0.5 Pa, sputtering duration = 1 h/3 h), differentiated ZnO:Eu3+/ZnO thin films were deposited onto the cotton fabrics by adjusting the sputtering power and the targets. In the following paper, fabric sputtered with Zn target for 1 h is named as ZnO 1, fabric sputtered with 3% Eu2O3:ZnO target for 1 h and 3 h are named as ZnO:Eu3+ 1 and ZnO:Eu3+ 3, respectively. All physical properties and spectroscopic measurements were performed using a single replicate to reduce batch to batch variations.
Structural characterization
Scanning electron microscopy (SEM)
SEM (TM4000Plus, Hitachi Corporation, Japan) was used to observe the micro-morphological characterization of cotton fabric surface prior and after coating. It was achieved by scanning the sample (0.5 × 0.5 cm) with a high-energy electron beam (acceleration voltage = 15 kV, magnification = ×4000). Prior to scanning, the sputtered sample was securely affixed to the sample stage using electron microscope tape, followed by a gold spraying process to enhance the conductivity and image quality. 28
Fourier transform infrared spectroscopy (FTIR)
The chemical bonds within the samples (0.5 × 0.5 cm) were meticulously examined using the IS50 Fourier transform infrared spectrometer manufactured by Thermo Fisher Scientific Co., Ltd. Since various molecular structures absorb infrared light in distinct patterns, the infrared spectrum can be applied as a reliable indicator for identifying the type of chemical bond present in a compound. Through this method, it was able to qualitatively assess the chemical substances within the coated fabrics. 29
Optical tests
UV absorption
The UV absorption spectroscopy analysis of the samples (∼2.6 cm in diameter) was performed by applying a calibrated double beam UV-Vis spectrophotometer (TU-1901, Beijing Puyang General Instrument Co., LTD). The experimental fabric was placed in the spectrophotometer for scanning (λ = 350-800 nm). The spectrophotometer measures the transmitted light intensity at various wavelengths, generating a UV absorption spectrum. This spectrum displayed the fabric’s absorption characteristics as a function of wavelength, allowing for the identification of any absorption peaks or troughs that might indicate the presence of specific chemical species. 30
Photoluminescence
Upon exposure to short-wavelength light, objects store energy and emit long-wavelength light, known as fluorescence. 31 Changes in fluorescence intensity across different wavelengths are reflected in the excitation spectrum while the emission spectrum characterizes the intensity and distribution of fluorescence. Emission spectra (EX = 350 nm, λ = 370–600 nm) of the samples (2.5 × 2.5 cm) were detected using a F-7100 spectrophotometer.
Photocatalysis
A UV-visible spectrophotometer was applied to evaluate the photocatalytic activity of the fabrics, thereby verifying the ability of the prepared luminescent textiles to degrade formaldehyde in the air under solar irradiation. Immersing in 10 mL of methylene blue (MB) solution, the samples (∼4 cm in diameter) were continuously irradiated for 6 h under a metal halide lamp (light gray matte). The absorbance changes of solution (λ = 554 nm) were measured every 30 min using a UV-visible spectrophotometer. As the concentration of MB solution at this wavelength being proportionate to its absorbance, by calculating the degradation rate of the MB solution and comparing the data at different time points, a photocatalytic degradation curve was plotted to visually demonstrate the degradation process.
In the degradation curves, the illumination time (t) was plotted with -ln (C/C0), and the pseudo-first-order degradation rate constant is represented by the slope k of the linear fit. Degradation rate = (C0 - C) / C × 100%, where C0 is the initial concentration of MB and C is the concentration of MB after illumination of n × 30 min (n = 1, 2, 3…, 7).
Color fastness
Color fastness to rubbing
Textiles encounter frequent friction in daily use, such as the friction among fabrics as well as between fabrics and our skin, necessitating favorable color fastness to rubbing to prevent color changes and coating transfer. To assess this property, referring to the GB/T 3920-2008 standard, samples (15 × 5 cm) were rubbed repeatedly under controlled conditions on a Y(B)571-II pre-set rubbing tester, and their color retention was visually evaluated employing a gray scale card ranging from one to five to quantify color fastness where higher grades indicate superior adhesion between the membrane and fabric, resulting in reduced membrane transfer and longer textile lifespan.
Color fastness to soaping
Soap fastness measures a fabric’s resistance to color fading when washed with soapy water on SW-12AII washing fastness tester which is graded on a scale of five levels using a gray scale card according to GB/T 3921-2008. For nano ZnO:Eu3+ doped thin-film fabrics (15 × 5 cm), soap fastness reflects the film’s adhesion to the substrate and reveals the fabric’s structural color, luminescence, and photocatalysis. Samples were cut, sewn with white cloth and washed in soapy water on a heat-collecting stirrer. After drying, their fading and staining levels were observed.
Results and discussion
Structural characterization
Scanning electron microscopy (SEM)
In Figure 1(a), the scanning electron microscopy (SEM) image of the untreated cotton fabric at ×5 k magnification clearly revealed the microstructure of the cotton fiber, exhibiting a smooth and flat surface. In contrast, Figure 1(b) displayed the ZnO-doped fabric, which exhibited a dense, uniform distribution of ZnO particles on the surface. Figure 1(c) and (d) demonstrate that the ZnO:Eu3+-doped fibers exhibit a more angular ridge structure compared to the original fibers, with particle aggregations evident on the fabric surface, corresponding to the formation of ZnO:Eu3+ composite films. Additionally, the fabric sputtered with ZnO:Eu2O3 targets for 3 h exhibits a rougher surface compared to that sputtered for 1 hour, as anticipated. Collectively, these observations indicate the successful coating of films onto the cotton fabric via the radio-frequency magnetron sputtering technique. SEM images (magnification ×5000) of original cotton fabric (a), ZnO 1 (b), ZnO:Eu3+ 1 (c) and ZnO:Eu3+ 3 (d).
Fourier transform infrared spectroscopy (FTIR)
The FTIR peaks and spectrum serve as a unique fingerprint for a particular molecular structure and its chemical bonding patterns, thereby facilitating the identification of a molecule’s fundamental backbone along with its associated functional groups. 32
As seen in Figure 2, a prominent characteristic peak at 1096 cm−1 was observed, indicating the presence of Eu-O bonds.
33
Furthermore, the absorption in the range of 400-600 cm−1 primarily revealed the stretching vibrations of Zn-O and Eu-O, reflecting the vibrational modes of these bonds (the Zn-O symmetric stretch is typically at 443 cm-1; Eu2O3 shows characteristic vibration modes at 446 cm−1 and 586 cm−1).34,35 Additionally, the appearance of characteristic peaks at 720 cm−1 suggested a potential association with the cellulose component in the cotton fiber.
36
This comprehensive FTIR analysis aligns with the anticipated chemical composition and vibrational characteristics of the samples, providing validation of our experimental observations. FTIR spectra of fabrics coated with ZnO:Eu3+ (sputtering time = 1 h or 3 h) and ZnO (sputtering time = 1 h).
Optical properties tests
UV absorption
The UV-visible absorption spectra of three fabric samples coated with ZnO 1, ZnO:Eu3+ 1 and ZnO:Eu3+ 3 are presented in Figure 3. All samples exhibited a characteristic ZnO absorbance peak at ∼360 nm.
37
A comparative analysis revealed that the UV absorbance peak at ∼350 nm decreased significantly in the ZnO:Eu3+ sample sputtered for 1 h compared to the ZnO sample sputtered for the same duration. This attenuation was further exacerbated in the ZnO:Eu3+ sample sputtered for 3 h. This effect mainly contributes to the increase in the thickness of the coated fabric, causing reduction in transmittance of UV light/may be attributed to variations in particle sizes of ZnO caused by the differentiated nucleation and condensation process in different samples.
38
UV-visible spectra of fabrics coated with ZnO:Eu3+ (sputtering time = 1 h or 3 h) and ZnO (sputtering time = 1 h).
Moreover, the ZnO:Eu3+ sample sputtered for 3 h exhibited a broadened absorbance peak compared to the other two samples, accompanied by an observable red shift. The possible reason is that the increased internal stress within the film resulting from the extended sputtering time of 3 h likely altered the band structure and enhanced the overlap of electron wave functions, ultimately leading to a broadened band gap. 39 These findings suggest that the embedding of the rare earth metal Eu and the prolongation of sputtering time negatively impact the fabric’s ultraviolet absorption capability.
Photoluminescence
To identify the luminescence performance of ZnO:Eu3+ coated fabrics, the photo fluorescence spectra with an excitation wavelength of 350 nm are plotted in Figure 4. Emission peaks at 400-550 nm were presented in all three samples, which is contributed to the intrinsic defect emission of ZnO host.
18
It can be seen that the introduction of Eu barely effected the position of the luminescent peak since no emission from the Eu3+ in ZnO:Eu3+ could be observed under an excitation wavelength lower than 385 nm21, though distinctive changes in intensity were exhibited in the spectra. PL spectra of fabrics coated with ZnO:Eu3+ (sputtering time = 1 h or 3 h) and ZnO (sputtering time = 1 h).
As expected, a significant enhancement in intensity was observed by incorporating Eu into the system when comparing ZnO and ZnO:Eu3+ samples that were sputtered for a same time period of 1 h. However, after extending the sputtering time to 3 h, the PL intensity of ZnO:Eu3+ sample dropped dramatically which is likely due to the inhibition of luminescence property caused by growth in the thickness of the prepared film/ can be understood by the reduction of the energy transfer due to the non-radiation processes in ZnO. 40
Photocatalysis
The photocatalysis of treated fabrics was studied over its capability of degrading MB as shown in Figure 5. Under ultraviolet irradiation, ZnO produces electron-hole pairs that react with water and oxygen to generate free radicals with strong oxidizing property, which can react with methylene blue molecules to break their chemical bonds, and thus degrade them into small molecules. The absorbance of MB visually decreased with the presence of all three samples under illumination, illustrating the degradation of MB is positively correlated with illumination time, indicating the potential use of the materials for degrading formaldehyde in the air for purification purpose. Relationship between -ln(C/C0) and illumination time of fabrics coated with ZnO:Eu3+ (sputtering time = 1 h or 3 h) and ZnO (sputtering time = 1 h).
Drawn from the linear fitting results, the degradation rate constants of fabrics coated with ZnO (sputtering time = 1 h), ZnO:Eu3+ (sputtering time = 1 h) and ZnO:Eu3+ (sputtering time = 3 h) were 0.124, 0.187, and 0.211, respectively. Fabrics coated with ZnO:Eu3+ resulted in effective degradation of MB of up to 55%–56% after 3.5 h of illumination while ZnO coated fabric exhibited a milder degradation rate of 42%, which corresponds with what was revealed by previous studies41,42 where the addition of Eu can enhance the photocatalytic property of ZnO under visible light irradiation. As a result, it can be concluded that the fabrics coated with ZnO:Eu3+ exhibited the faster and higher photocatalytic degradation rate.
Color fastness
Color fastness results of the samples.
Conclusions
The study successfully prepared rare earth Eu-doped nano-ZnO composite films on textiles, comprehensively analyzed their structural and luminescent properties. To the best of our knowledge, this represents the first time that Eu-doped ZnO with a substrate as textile through magnetron sputtering for luminescent and photocatalytic applications. SEM observations confirmed the uniform deposition of ZnO:Eu3+ films on cotton fabric, and FTIR spectra validated the characteristic Zn-O/Eu-O bonds. ZnO:Eu3+ samples exhibited decreased UV absorption with longer sputtering, while the 1 h-sputtered sample displayed significantly enhanced photoluminescence. The ZnO:Eu3+ coated fabrics more effectively degraded MB up to 56% after 3.5 hours of illumination. Samples achieved high color fastness grades while further improvements are necessary to improve their resistance to rubbing. Collectively, these findings demonstrate the successful preparation of luminescent and photocatalytic-active Eu-doped ZnO films on textiles, with the 1 h sputtered sample exhibiting optimal overall properties, opening avenues for further studies and potential diverse applications.
