Superior Mechanoluminescence of ZnS:Mn/ZnO Heterostructure Array Chip Boosted by Type Ⅱ Electron Transition

Superior Mechanoluminescence of ZnS:Mn/ZnO Heterostructure Array Chip Boosted by Type Ⅱ Electron Transition | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Superior Mechanoluminescence of ZnS:Mn/ZnO Heterostructure Array Chip Boosted by Type Ⅱ Electron Transition Aihua Zhong, Jiateng Fan, Yunkai Wang, Hang Yang, Zhiheng Ma, and 6 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7927301/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 22 Apr, 2026 Read the published version in Microsystems & Nanoengineering → Version 1 posted 12 You are reading this latest preprint version Abstract Mechanoluminescence (ML) has garnered considerable attention in widespread applications, including visualized stress detection, electronic signatures, and electronic skin. However, its high stress-threshold and limited emission efficiency fail to satisfy the growing application requirements. To address these challenges, we propose constructing ZnS:Mn/ZnO heterostructure with a novel type Ⅱ energy band alignment, aiming to activate the abundant electrons in the valence band for ML emission and introduce additional piezoelectric field as well as built-in electric field. The ZnS: Mn/ZnO heterostructure array chips were fabricated by standard semiconductor techniques, forming regular heterostructures and emission centers in square array. Each emission square functions as a pixel for mapping force distribution and recording dynamic forces. As anticipated, the heterostructure array exhibits a record-low threshold of 0.05 N and a 4-fold increase in ML intensity. In mechano-electro-photon combined study, pulsed electric current were simultaneously observed, directly confirming the generation of non-balanced free carriers upon the mechanical stimulus. Owing to the high electron density in the VB of ML materials, the type II electron transition proposed in this work could dramatically increase the number of non-balanced carriers participating in the ML process, thereby have a revolutionary impact on the efficiency and fundamental understanding of ML emission. Physical sciences/Optics and photonics Physical sciences/Engineering Physical sciences/Materials science type Ⅱ energy band alignment heterostructure threshold mechanoluminescence thin films Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction Mechanoluminescence (ML), an interesting light emission phenomenon that directly convert widely distributed mechanical stimuli to photon 1 , 2 , has attracted huge attention in widespread applications including visualized stress distribution 3 – 5 , electronic signatures 1 , 6 , temperature sensing 7 – 9 , health diagnosis 10 , mechanically driven light emission device 11 , and flexible electronic skin 4 , 6 , 12 – 14 . Numerous inorganic ML materials such as ZnS:Mn/Cu 6,15,16 , SrAl 2 O 4 :Eu 17,18 , CaZnOS:Cu 19 , and LiNbO 3 :Pr 20,21 , have been investigated. Nerveless, ZnS is still considered as one of the most representative ML materials, which exhibits advantages of self-recoverability 22 , stable ML emission 23 , free of pre-excitation 24 , feasibility in color-tuning 25 , high brightness, and easy fabrication. Normally, these ML materials are prepared into powder like samples and mixed with highly elastic organic materials such as polydimethylsiloxane (PDMS) 26 – 28 , epoxy resin 29 , 30 and so on, to demonstrate the ML properties by applying different forms of stress. However, these powder like samples are mainly composed of polycrystalline materials. Under macroscopic stress, the forces between microscopic crystals are very complex, involving not only the influence of crystal interfaces, but also the analysis of stress conditions 31 , which ultimately makes the analysis of ML mechanisms particularly difficult, and greatly limits the accuracy of stress sensing, causing difficulties in the practical applications. Thus, there is an imperative need to develop non-polycrystalline integrated ML materials to simultaneously study the real ML mechanism and device based stress sensing applications. Stress-threshold is an important indicator reflecting the ML accuracy and performance. Recently, researchers have conducted research on the stress-threshold of ZnS system. Jha et al. systematically studied the stress-threshold of the macrocrystal, microcrystal, and nanocrystal ZnS:Mn, 30 and 0.8 MPa for the macrocrystal and microcrystal, respectively 32 . It is revealed that the threshold is highly related to the piezoelectric field inside the ZnS:Mn crystals. Particularly, Kleckner et al. used the nanoscopy tools to precisely study the ML thresholds of single ZnS:Mn particles 33 . Great heterogeneity of the stress-thresholds was observed, ranging from 0.233 to 47.15 MPa, with the lowest threshold obtained from the particle that is abundant with stacking disorder. In 2024, Yuan et al. reported a state-of-the-art low threshold force of 0.1 N for the ZGGO:Cr by precise control of defect content and trap distribution 14 . While the defect-control strategy has significantly reduced the threshold, it remains worthwhile to explore new approaches to feasibly lower the threshold force for ML emission. Furthermore, in the previously researches, the optical properties of the ML materials have been well investigated while the electrical changes such as variations in carrier concentration and conductivity under mechanical stimuli is lacking, mainly due to the poor conductivity and complexity of the inorganic-organic composite. The deficiency of electrical properties study hinders the deep-insight understanding of the real ML mechanism. Therefore, a combined study of mechano-electro-photon behaviors is of great significance. Under the current perspective, the generation of non-balanced free carriers is a key to the ML performance. Based on the origin of non-balanced carriers, two mainstream mechanism models, piezoelectric-induced carrier detrapping model 20 , 34 , 35 and the triboelectric-induced electroluminescence model 5 , 36 , 37 , have been proposed and developed. Regarding the carrier detrapping model, it is believed that the charge carriers trapped at various defects are released to the conduction or the valance band under the mechanical stimulus, generating non-balanced carriers for ML emission. For the triboelectric-induced electroluminescence model, non-balanced carriers are generated through the carrier transfer from the counterpart triboelectric materials, and has been well confirmed by Xie et al. 16 As mentioned above, the non-balanced carriers for ML emission rely on either the detrapping of the electrons through piezoelectric effect or the electron injection by triboelectric effect, both of which result in limited non-balanced carrier generation. Conversely, the valence band (VB) of ML materials contains abundant electrons, but they are hardly activated by mechanical stimulation due to the substantial energy required for activation. For the photodetector design, researchers have integrated counterpart materials with the optoelectronic materials, forming a heterostructure in which type Ⅱ electron transition occurs 38 – 41 . Herein, type Ⅱ electron transition means the electron in the VB of one material is directly activated to the conduction band (CB) of the counterpart material, so that lower energy could be efficiently utilized. This strategy may dramatically increase the non-balanced carriers engaged in ML emission and subsequently significantly improve the ML performances, however, no relevant study has been conducted. In this work, we propose constructing a ZnS:Mn/ZnO heterostructure with a type Ⅱ energy band alignment, where the CB of ZnO (CB ZnO )is moderately higher than the VB of the ZnS:Mn film (VB ZnS ), aiming to directly activate the electrons in the VB of the ZnS for ML emission. The heterostructure design may also lower the stimulation threshold by introducing additional piezoelectric field via lattice mismatch and a built-in electric field through heterojunction formation at the ZnS:Mn/ZnO interface. Using standard photolithography, we patterned the film into a 50×50 µm² square array, forming a regular heterostructure with discrete emission centers. Each square functions as a pixel for mapping force distribution and recording dynamic forces. Remarkably, the ZnS:Mn/ZnO heterostructure exhibited a record-low threshold of 0.05 N (4 kPa). Additionally, two gold (Au) electrodes were formed on the ZnS:Mn/ZnO heterostructure to enable combined mechano-electro-photon studies. Pulsed electric current and 4-fold increasement in ML intensity were observed for the ZnS:Mn/ZnO heterostructure, suggesting the successful activation of type Ⅱ electron transition upon newton force stimulus. Compared with the limited trapped carriers by defects or the carrier transfer by triboelectric effect, the VB of ML materials contain large number of electrons that are available for activation. Therefore, the type II electron transition proposed in this work may dramatically increase the number of non-balanced free carriers involved in the ML process, thereby have a revolutionary impact on the efficiency and fundamental understanding of ML emission. Experimental Section Deposition of ZnO:Mn films : Quartz glass with the size of 25×25×1 mm 3 was selected as the substrate for ZnO film growth. Prior to deposition, the substrates were ultrasonically cleaned in acetone, methanol, and deionized water in sequence for 10 mins, respectively. ZnO films doped with Mn were deposited on quartz glass substrates by co-sputtering technique (PVD-75, Kurt J. Lesker, USA) with a thickness of 200 nm. Various powers of Mn target, 2.5, 3, 3.5, 4 and 5 W were studied, and their photoluminescence are presented in Figure S12. When the substrate was heated to 200 o C, the chamber was filled with argon at a working pressure of 4 mTorr. Two fixed radio frequency (RF) power of 100 W and 3.5 W were applied to the ZnO and Mn targets, respectively. EDS was utilized to measure the element mappings ( Figure S14), and the Mn content (3.5 W) was measured to be 0.6 at%. ZnS:Mn/ZnO heterostructure construction : To fabricate the ZnS:Mn/ZnO heterostructure, an AZ5214 photoresist mask was used to pattern the ZnO:Mn film deposited above, and a AlN film (80 nm) was grown as a barrier layer to prevent the ZnO layer beneath from sulfidation in the following annealing process. On the other hand, porous anodic aluminum oxide template (Pore diameter 200 nm and period of 450 nm) was covered on ZnO:Mn film before sulfidation annealing, to fabricate the ZnS:Mn/ZnO-AAO heterostructure. As for the sulfidation annealing process, 3g sulfur powder was added to the quartz bottle placed in the tube furnace (OTF-1200X-III, Hefei Kejing Materials Technology Co., China), films were heated to 700 o C with a rate of 10 o C min − 1 and annealed for 60 min in the argon gas for sulfidation, followed by slowly cooling down (5 o C min − 1 ) to room temperature. The anneal process in detail is presented in Figure S13. The sulfur powder was simultaneously heated and kept at 200 o C for the whole annealing process. Characterizations : Surface morphology, crystal structure, and chemical composition of all films were characterized using SEM (APREO S, Thermoscientific, Holland), XRD (Ultima IV diffractometer, Rigaku), and XPS (Nexsa, TFS). Cross-sectional images and ZnS:Mn/ZnO interface were obtained using transmission electron microscopy (TEM, Titan Cubed Themis G201, FEI). The film thickness was measured by a surface-profile measurement system (Dektakxt, Bruker, USA). PL spectra were recorded using a FLS-1000 photo-luminescence spectrometer (Edinburgh Instruments Ltd., UK). The equipment used to obtain ML spectroscopy was a home-built measuring system consisting of a stepper motor, a digital push-pull force gauge, a linked displacement platform and the QE65pro fiber optic spectrometer (OceanInsight, UK). The UV-vis absorption spectra were carried out by using a UV-vis spectrophotometer (UV 3600 plus, Shimadzu, Japan). Electrical measurements were conducted at room temperature using an AES-4TH testing system equipped with a probe station. Results and discussion Construction and characterization of the ZnS:Mn/ZnO heterostructure A method for well-designed construction of ZnS:Mn/ZnO heterostructure was proposed and developed in Fig. 1 a-c. As shown in Fig. 1 a, ZnO:Mn film was deposited by co-sputtering technique, followed by a deposition of AlN film on the photolithography patterned ZnO:Mn film. Herein, the AlN film was utilized as a barrier layer to prevent the beneath ZnO:Mn film from sulfidation. The un-sulfidated ZnO film beneath the AlN barrier layer and the ZnS:Mn film precisely form ZnS:Mn/ZnO heterostructure at their interface, named as ZnS:Mn/ZnO-LT. Figure 1 b illustrates the detailed dimensions and structure of the heterostructure, with the AlN barrier layer having a characteristic width of 10 µm, which was arranged in a grid pattern at intervals of 50 µm. To further confirm the ZnS:Mn/ZnO heterostructure, we employed an anodized aluminum oxide (AAO) template as the barrier layer to fabricate another ZnS:Mn/ZnO heterostructure named as ZnS:Mn/ZnO-AAO in Fig. 1 c. The SEM image presented in Fig. 1 d reveals the surface morphology of the ZnS:Mn/ZnO-LT, showing a periodic array structure and porous surface (Fig. 1 e). As shown in Figure S1 b-d, this porous feature is observed in all films prepared via the sulfidation process, which is significantly different from that directly deposited using ZnS target (Fig. 1 g). The formation of this porous morphology is attributed to the sulfidation reaction from ZnO to ZnS, which is accompanied by the outward growth of ZnS 42 , 43 . During this process, internal interface reaction leads to the creation of zinc and oxygen vacancies, which subsequently diffuse to the surface of the ZnS layer via point defects of interstitial sites, sulfur vacancies, and grain boundaries. The cross-sectional image shown in Fig. 1 f verifies that this loose nature is not confined to the surface but extends throughout the whole film. The optical images of the ZnS:Mn/ZnO heterostructure array chip were recorded by an optical microscope and shown in Fig. 1 h. Under 365 nm light illumination, the ZnS:Mn film exhibits strong yellow emission while the ZnO film is free of emission, indicating successful construction of ZnS:Mn/ZnO heterostructure. It is worth to note that every ZnS square can be functioned as a pixel in the visualized detection of stress distribution, providing high resolution in remote stress detection. The size of the pixel is feasible to adjust in a wide range from nm to mm, depending on the requirement of resolution. X-ray diffraction (XRD) analyses were conducted and shown in Figure S2. The strong diffraction peak at 34.2° in the ZnO film is associated with the wurtzite (0 0 2) ZnO44. After annealing in the sulfur atmosphere, the ZnO film without AlN barrier layer was completely transformed to ZnS, which is a hexagonal ZnS with (0 0 2) orientation. For both the ZnS:Mn/ZnO-AAO and ZnS:Mn/ZnO-LT films, the ZnO (002) and (103) diffraction peaks persist after sulfidation. This confirms that a portion of ZnO remains due to the AlN barrier design or AAO mask, which is critical for constructing the ZnS:Mn/ZnO heterostructure. Transmission electron microscopy (TEM) analysis was conducted to study the interface of the ZnS/ZnO heterostructure and the defects in the ZnS:Mn film. As depicted in Fig. 2 a, the left side shows an AlN barrier layer on the top and a dense ZnO film beneath with a thickness of ~ 200 nm. On the right side, the thickness of the film is significantly larger than the left side, indicating the film expands during the sulfidation process, and a porous structure is presented, in consistent with the SEM result in Fig. 1 e. Figure 2 b focuses on the interface of the heterostructure, where a boundary between ZnO and ZnS is observed. Energy-dispersive X-ray spectroscopy (EDS) results shown in Fig. 2 c and 2 d demonstrate a pronounced enrichment of oxygen (O) and sulfur (S) in their respective domains. This indicates that the sulfidation process was effectively controlled. Notably, the heterostructure in this work was formed in the designed regions rather than randomly, suggesting that the heterostructure fabrication method is highly controllable and its density can also be feasibly adjusted. Figure 2 e presents a high-resolution transmission electron microscopy (HRTEM) image that clearly reveals the lattice structures of the two distinct phases at the interface. Figure 2 f presents the HRTEM image of the ZnO region, showing an order arrangement of atoms, and its corresponding fast fourier transform (FFT) pattern is shown in Fig. 2 i. It is seen that the FFT spots of ZnO are clear without streaks, indicating that the ZnO has a pristine wurtzite structure. The plane distances of 2.81 Å, 2.46 Å, and 2.6 Å are corresponding to the wz- ZnO \(\:\left(10\stackrel{-}{1}0\right)\) , \(\:\left(10\stackrel{-}{1}1\right)\) , and \(\:\left(0002\right)\:\) , respectively. In contrast, the HRTEM image of the ZnS in Fig. 2 g reveals that some atoms are in a disordered state, suggesting the existence of stacking fault. The observed plane distances in the FFT pattern depicted in Fig. 2 j are 2.86 Å, 2.83 Å, and 3.19 Å, corresponding to the \(\:\left(10\stackrel{-}{1}\stackrel{-}{1}\right)\) , \(\:\left(10\stackrel{-}{1}1\right)\) , and \(\:\left(0002\right)\) of wz -ZnS, respectively. Notably, the spots in Fig. 2 j appear blurred and streaks are clearly observed, further confirming the presence of stacking faults in the ZnS. In previous research, it has been discovered that the stacking faults formed in the ZnS: Mn thin film is a key to the ML emission 33 , 45 . As mentioned above, the lattice constants of the ZnO and the ZnS are different, probably resulting in a strong stress and further piezoelectric field at the ZnS:Mn/ZnO interface, which is essential for the detrapping of carriers engaged in ML emission 32 . Figure 2 h presents the high-resolution elemental mapping images of the interface of ZnS:Mn/ZnO, where a sharp transition in O and S content is observed. The interface width is determined to be 5.92 nm, confirming the well-defined formation of the ZnS:Mn/ZnO heterostructure. X-ray photoelectron spectroscopy (XPS) analysis was also conducted and studied. As shown in Figure S3a-e, it is seen that the oxygen ions (O L ) 46 within the lattice exist both in the ZnS:Mn/ZnO-AAO and in the ZnS:Mn/ZnO-LT heterostructure while no O L component is observed in the pristine ZnS film, further confirming that ZnO is preserved by the AlN barrier design or AAO mask. Optical and mechanoluminescence properties of the ZnS:Mn/ZnO-LT We systematically investigated the ML behaviors of four ZnS:Mn thin films including traditional film, porous ZnS:Mn film prepared through sulfidation, the ZnS:Mn/ZnO-LT, and the ZnS:Mn/ZnO-AAO. These films were directly grown on the quartz glasses and no pre-irradiation was conducted before ML measurement. A spectrometer in Fig. 3 f was utilized to record the ML properties. As shown in Fig. 3 a, the traditional ZnS:Mn film exhibits very weak ML emission, even when subjected to a strong force of 13 N. In sharp contrast, the sulfidated ZnS:Mn film (Fig. 3 b) and the ZnS:Mn/ZnO-LT heterostructure (Fig. 3 c) exhibit 12- and 15-fold stronger ML emission, respectively. Moreover, the ML behaviors of the ZnS:Mn/ZnO-AAO film with thicknesses of 200 and 400 nm exhibit similar improvements ( Figure S6 and S7), further confirming the key role of the heterostructure. The ML intensities at various stimuli of the ZnS and ZnS:Mn/ZnO-LT heterostructure are summarized in Fig. 3 d. It is seen that the films with heterostructure demonstrate pronouncedly higher ML than the pristine ZnS:Mn film, especially at the cases of small stimulus (< 7 N). Within the force range of 1–7 N, the emission intensity exhibits a linear relationship with the applied force. For a direct comparison, their ML spectra stimulated at 1 N are depicted in Fig. 3 g. The ML intensities of the ZnS:Mn/ZnO-LT film is about 4-fold stronger than that of the porous ZnS:Mn film. As shown in Fig. 3 e, the ML of the ZnS:Mn/ZnO-LT heterostructure films are strong that they can be directly seen by naked eyes under a small stimulus of 1 N. To study its performances at small stimulus, the ML curves of the ZnS:Mn/ZnO-LT film range from 0.05 to 0.8 N were recorded and shown in Fig. 3 h. Interestingly, the ZnS:Mn/ZnO heterostructure exhibits clear ML behavior under these small stimuli. To our knowledge, 0.05 N is the record-low stress threshold of the reported ML materials. Low stress-threshold is of great importance for the development of next-generation stress sensors, the electronic skin, and the humanoid robots since it can expand the detection to rather small stress together with much higher resolution. The ZnS:Mn/ZnO heterostructure almost has no stress-threshold, together with the linear relationship between the ML intensity and the stimulus force in Fig. 3 i, making it considerable attractive for widespread practical applications. Furthermore, the ML performances under stimulus with frequency of 500 Hz were also studied. As depicted in Figure S8, the ML peaks observed in the near-infrared spectrum are centered at 754, 775, 852, and 970 nm, which can be attributed to the formation of (Mn) n clusters 47 . The application of high-frequency stimulation enhances the likelihood of (Mn) n cluster formation and promotes the energy transfer from the excited Mn 2+ ions to the (Mn) n clusters, consequently resulting in the emergence and intensification of the near-infrared emission band. As depicted in Figure S4a, the transmittance of the ZnS:Mn/ZnO-LT film is smaller than both the ZnO and the ZnS film, suggesting enhanced light absorption because of the ZnS:Mn/ZnO heterostructure. Figure S4b demonstrates that the optical bandgap of the ZnO is approximately 3.28 eV, and the bandgap of the ZnS is around 3.64 eV. Figure S4c and 4d depicts the PL spectra of the ZnS:Mn/ZnO-LT films excited by 330 nm light and the PLE spectra at 585 nm. Figure S4e shows that the time-resolved decay curve of the traditional ZnS:Mn film is consisting of two exponential decay components. Differently, the porous ZnS:Mn film and the ZnS:Mn/ZnO-LT in Figure S4f exhibits three exponential decay components. The values of the decay curve in detail are summarized in Table S1. Compared to porous ZnS film in Figure S4f, the ZnS:Mn/ZnO-LT exhibits a higher proportion of 𝜏 2 occupancy, A 2 . This suggests that the heterostructure introduces more defects 5 . Moreover, thermoluminescence test was also conducted, as shown in Figure S5, but no thermoluminescence was observed both for the porous ZnS:Mn film and the ZnS:Mn/ZnO-LT with various thicknesses. Mechano-electro-photon combined study and ML mechanism of the ZnS:Mn/ZnO heterostructure To characterize the coupled mechano-electro-photon behaviors of the ZnS:Mn/ZnO-LT heterostructure, two Au electrodes were deposited on the film surface to simultaneously collect electrical responses, while ML emission was recorded under the same mechanical stimulus. Figure S9 shows the I-V curves of the porous ZnS:Mn film and the ZnS:Mn/ZnO-LT film. As ZnS is a wide-bandgap semiconductor and highly resistive, the current is rather small. In contrast, the I-V curve of the ZnS:Mn/ZnO-LT heterostructure device exhibits rectifying characteristic of diode, suggesting formation of heterojunction, and the conductivity of the ZnS:Mn/ZnO-LT is much larger, ~ 40 nA, due to the higher conductivity of the ZnO. Figure 4 d shows the current responses of the ZnS:Mn/ZnO-LT heterostructure to force stimuli varied from 0.2 to 7 N. Interestingly, pulsed currents are clearly observed once the ZnS:Mn/ZnO-LT is applied to a force through Al needle, and recovers to the original value when the friction is stop. The larger the force is, the higher the pulsed current △I is. As shown in Fig. 4 e, the current increases rapidly upon stimulation, with a current increase of △I = 9.5 µA at 3 N. In sharp contrast, there is no pulsed current both for the ZnO and the ZnS:Mn film in Fig. 4 a and 4 b, even at a larger stimulus of 13 N. For a given semiconductor, the carrier mobility is unlikely to change; thus, it can be deduced that free carriers are generated in the ZnS:Mn/ZnO heterostructure upon force stimulus. In contrast, neither the pristine ZnO nor the ZnS:Mn film generates free carriers, or the number of free carriers generated is smaller. The difference in the free carrier generation between the heterostructure and the pristine film is of great interest, since it implies new mechanism of free carrier generation in the ZnS:Mn/ZnO-LT heterostructure. Moreover, the ML behaviors of the ZnS:Mn/ZnO-LT heterostructure were simultaneously recorded upon the same stimuli in electrical signal collection and shown in Fig. 4 c and 4 f. Figure 4 g shows the plots of ML intensity as a function of newton force, suggesting excellent linearity between them. The magnitude of the pulsed current △I upon newton force are depicted in Fig. 4 h. It is seen that the △I gradually increase with the force within 5 N and sharply increases to 20 µA at 7 N. In Fig. 4 i, it is observed that the higher the pulsed current generated upon the force stimulus, the stronger the ML intensity is. Besides the process (i), it is deduced from Fig. 4 d that the electrons in the VB ZnS are directly activated to the CB ZnO upon force stimulus. This process is denoted as process (ii) in Fig. 5 b, resulting in the additional non-balanced holes in the ZnS. For the photodetector research, the phenomenon of electrons transition from the VB of one material to the CB of the adjacent material has been well recognized, and named it as type Ⅱ electron transition 40 , 41 . Herein, it is the first time to propose and confirm the electron transition from the VB of one material to the CB of adjacent material in the ML study. To distinguish the electron transition within one material, we also named it as type Ⅱ electron transition. Since the conductivity of ZnO is better than the ZnS, the conductive channel of the ZnS:Mn/ZnO heterostructure is mainly ZnO. The type Ⅱ electron transition from VB ZnS to CB ZnO results in the increase of free electrons in ZnO and thus the improved conductivity of the heterostructure, well explaining the pulsed current observed in Fig. 4 d. Moreover, the non-balanced holes in ZnS generated by type Ⅱ electron transition also pronouncedly enhance the electron-hole pairs’ non-radiation combination, resulting in a significantly improvement in ML emission as shown in Fig. 3 d. In Figure S11, the type Ⅱ electron transition is further confirmed by 520 nm photon irradiation. Compared with the limited trapped carriers by defects or the carrier transfer by triboelectric effect, the VB of ML materials contain large number of electrons that are available for activation. Thus, the type II electron transition in the ML behavior observed herein may significantly increase the number of non-balanced free carriers, thereby have a revolutionary impact on the efficiency and intensity of ML emission. This discovery provides a novel and general strategy for improving ML performance and advances the understanding of the ML mechanism. Considering the integration advantages of ZnS:Mn/ZnO heterostructure and the innovative carrier generation mode, this study further designed a pixel-array ML integrated application mode. Under the dynamic stress application, the ZnS:Mn/ZnO heterostructure array realizes the pixelated trajectory recording of scratching and handwriting by converting mechanical stress into luminescence through the ML process. As shown in Fig. 6 a, the scratching trajectory is visualized in real-time via image acquisition. A complementary metal oxide semiconductor (CMOS) image sensor is employed to capture the luminescence of the ZnS:Mn/ZnO heterostructure array under the stress. Using a 20x20 pixel array, the handwriting of “SZU” was successfully recorded in Fig. 6 d. The ML intensity is derived by extracting the gray values of the captured image, and further calibrated to the value of force using the relationship shown in Fig. 4 g. In this way, the approximate magnitude of the force applied during the “SZU” writing process was capable to record and present in in Fig. 6 d. Notably, the ZnS:Mn/ZnO heterostructure array was fabricated via standard semiconductor processes on a wafer scale, enabling the integration of a photodetector array with the heterostructure array chip as depicted in Fig. 6 c, directly converting the stimulus to the force/stress values, may providing dual-modes sensing of force or stress in the future. Owing to its extremely low stress-threshold, the heterostructure array-based system holds potential for applications in ethology research in Fig. 6 c and the development of high-precision force-recognition mechanical hands in Fig. 6 b. This design is the first time to transform the application mode of ML materials from polycrystalline powder to integrated array, result in the widespread promotion to develop the ML chips by utilizing the mechano-optical conversion. Due to its high efficiency and passive characteristics, it will have a significant impact on the current electrical stress sensing mode. Conclusion In summary, we have successfully constructed a ZnS:Mn/ZnO heterostructure with type Ⅱ energy band alignment. Standard semiconductor technique was utilized to fabricate the ZnS:Mn/ZnO heterostructure array chips, forming regular heterostructures and emission centers in square array. Each emission square functions as a pixel for mapping force distribution and recording dynamic forces, realizing the chip-based stress sensing applications. Pulsed electric current of 20 µA was simultaneously observed with bright ML emission, confirming the successful activation of type Ⅱ electron transition upon force stimulus. Notably, a record-low threshold of 0.05 N is achieved by introducing piezoelectric field at the heterostructure interface through lattice mismatch and a build-in electric field, providing a novel approach for lowering the ML stress-threshold. Compared with the limited trapped carriers by defects or the carrier transfer by triboelectric effect, the VB of ML materials contain large number of electrons that are available for activation. Thus, the type II electron transition in the ML behavior observed herein may significantly increase the number of non-balanced free carriers involved in the ML process, thereby have a revolutionary impact on the efficiency and intensity of ML emission. Declarations Acknowledgements This work was supported by the National Natural Science Foundation of China (Grant No. 62071307 and 52372160), and Guangdong Basic and Applied Basic Research Foundation (Grant No. 2025A1515011910). The authors wish to acknowledge the assistance of TEM (Titan Cubed Themis G201, FEI) received from the Electron Microscope Center and Photonics Research Centre of Shenzhen University. Author details 1 State Key Laboratory of Radio Frequency Heterogeneous Integration, College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, P.R. China 2 Faculty of Materials Science and Chemistry, China University of Geosciences, 388 Lumo Road, Wuhan 430074, China 3 Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, China 4 New Industry Creation Hatchery Center, Tohoku University, Sendai, 980-8579, Japan Author contributions J. Fan and Y. Wang contributed equally to this work. A. Zhong and D. Tu conceived the project. J. Fan, Y. Wang, and A. Zhong designed the experiments. J. Fan, Y. Wang, H. Yang, D. Peng and S. Xue were primarily responsible for the experiment setup and data collection. A. Zhong and D. Tu supervised the research. J. Fan, A. Zhong, K. Hane, and D. Tu wrote and revised the manuscript. J. Fan, Y. Wang, L. Huang, and Z. Ma prepared the figures. A. Zhong, J. Luo, K. Hane, and D. Tu proposed the ML emission mechanism. All authors contributed to data analysis, discussions and manuscript preparation. Conflict of Interest The authors declare no conflict of interest. Supporting I nformation Supporting Information is available for this paper at : References Zhuang Y, Tu D, Chen C, Wang L, Zhang H, Xue H et al. Force-induced charge carrier storage: a new route for stress recording. Light Sci Appl 2020; 9 : 182. Xie Z, Mao Z, Wang H, Xiao Y, Zhang X, Yu T et al. Dual-channel mechano-phosphorescence: a combined locking effect with twisted molecular structures and robust interactions. Light Sci Appl 2024; 13 : 85. Wang WX, Matsubara T, Takao Y, Imai Y, Xu CN. 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15:33:49","extension":"html","order_by":17,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":139478,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-7927301/v1/46b5d8cbef3d67a784a204f7.html"},{"id":95849851,"identity":"30683525-dba2-4cc5-b282-3c8a71086f16","added_by":"auto","created_at":"2025-11-13 15:33:49","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":355362,"visible":true,"origin":"","legend":"\u003cp\u003ea) The fabrication process of the ZnS:Mn/ZnO-LT heterostructure. b) Illustration and dimensions of the ZnS:Mn/ZnO-LT and c) ZnS:Mn/ZnO-AAO. d) SEM image of the ZnS:Mn/ZnO-LT array. e) SEM image of the ZnS:Mn film, exhibiting porous surface. f) Cross-sectional image of the ZnS:Mn/ZnO-LT heterostructure. g) SEM image of the traditional ZnS thin film deposited by ZnS target, showing compact surface. h) Optical images of the ZnS:Mn/ZnO-LT heterostructure array chip with and without ultraviolet irradiation.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-7927301/v1/dfa289e5a0fe4a14f1c46d8c.png"},{"id":96240658,"identity":"b03b1a9d-935e-4dad-964f-6a8aeaa73b55","added_by":"auto","created_at":"2025-11-19 07:09:19","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":504970,"visible":true,"origin":"","legend":"\u003cp\u003ea) Cross-sectional image of the ZnS:Mn/ZnO-LT film. b) TEM image of the ZnS:Mn/ZnO interface. c) O element mapping and d) S element mapping of the ZnS:Mn/ZnO interface.\u003cstrong\u003e e\u003c/strong\u003e) HRTEM image of the ZnS/ZnO interface. HRTEM images of the f) ZnO and g) ZnS. h) Elemental mapping of O and S in the interface, indicating clear interface of the ZnO and ZnS. FFT patterns of the i) ZnO and j) ZnS.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-7927301/v1/db88adaeeeddf286fcd9ea06.png"},{"id":96241587,"identity":"3575350a-d08b-4787-883d-7339b6de5205","added_by":"auto","created_at":"2025-11-19 07:11:03","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":336735,"visible":true,"origin":"","legend":"\u003cp\u003eML spectra of the ZnS:Mn thin films with thickness of ~200 nm: a) traditional ZnS:Mn film, b) the ZnS:Mn film prepared by sulfidation, and c) the ZnS:Mn/ZnO-LT film. d) Comparison of the ML intensity between the sulfidated ZnS film and the ZnS:Mn/ZnO-LT film. e) Optical images of the ML phenomenon. f) Illustration of the ML test instrument. g) ML spectra of ZnS:Mn/ZnO-LT film and the sulfidated ZnS film at 1 N. h) ML spectra of ZnS:Mn/ZnO-LT film upon small forces of 0.05 to 0.8 N, i) Plots of the ML intensity as a function of newton force.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-7927301/v1/e8b8e01acb4fb432ac89712e.png"},{"id":96241137,"identity":"e82c1876-ec7d-4223-9e28-64e4d6e1a421","added_by":"auto","created_at":"2025-11-19 07:10:16","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":259517,"visible":true,"origin":"","legend":"\u003cp\u003eElectrical current change of (a) the ZnO, and (b) the ZnS: Mn film under a 13 N stimulus. (c) ML spectra of the ZnS:Mn film simultaneously measured with the same stimuli of the electrical responses shown in (b). (d) Electrical current change of the ZnS:Mn/ZnO-LT heterostructure upon newton force stimuli. (e) Focused current response of the ZnS:Mn/ZnO-LT to 3 N st imulus; (f) ML spectra of the ZnS:Mn/ZnO-LT heterostructure simultaneously measured with the same stimuli of the electrical responses shown in (d). (g) Plots of ML intensity of the ZnS:Mn/ZnO-LT heterostructure as a function of newton force; (h) Current increasement △I of the ZnS:Mn/ZnO-LT heterostructure device under various newton force; and (i) Plots of ML intensity \u003cem\u003eversus\u003c/em\u003e △I\u003cem\u003e.\u003c/em\u003e\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-7927301/v1/c0474e4eef1472c1e4592ea9.png"},{"id":95849854,"identity":"ddafb8a7-618e-49d5-98af-02dba6bda377","added_by":"auto","created_at":"2025-11-13 15:33:49","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":127041,"visible":true,"origin":"","legend":"\u003cp\u003eEnergy band diagram of the ZnS:Mn/ZnO heterostructure, (a) before contact, and (b) after contact with a stimulus.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-7927301/v1/a326c813d91493a0fa6a5f14.png"},{"id":95849862,"identity":"f7c770c0-a831-4bfb-864c-26f76357ae80","added_by":"auto","created_at":"2025-11-13 15:33:49","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":151031,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Optical image of the scratching trajectory; (b) Application illustration of the ZnS:Mn/ZnO heterostructure array for the high-precision force-recognition mechanical hands; (c) Illustration of the integration of ZnS:Mn/ZnO heterostructure array with the photodetector array, enabling dual-mode stress/force detection for ethology research; (d) Force mapping of the “SZU” writing process.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-7927301/v1/33ca33019977dfd763f4499d.png"},{"id":107604023,"identity":"eb126a2e-889e-49b5-8484-947e808380bb","added_by":"auto","created_at":"2026-04-23 07:16:41","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2226266,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7927301/v1/1c4dda07-f56d-47ad-b145-bea6114fbaee.pdf"},{"id":95849853,"identity":"7de24c7b-3bef-44e7-a858-9cc3b78344b2","added_by":"auto","created_at":"2025-11-13 15:33:49","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":1817883,"visible":true,"origin":"","legend":"Supporting file","description":"","filename":"AAAsupportingfileR.docx","url":"https://assets-eu.researchsquare.com/files/rs-7927301/v1/51872058b75b63671700809d.docx"}],"financialInterests":"There is no conflict of interest","formattedTitle":"Superior Mechanoluminescence of ZnS:Mn/ZnO Heterostructure Array Chip Boosted by Type Ⅱ Electron Transition","fulltext":[{"header":"Introduction","content":"\u003cp\u003eMechanoluminescence (ML), an interesting light emission phenomenon that directly convert widely distributed mechanical stimuli to photon\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e,\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, has attracted huge attention in widespread applications including visualized stress distribution\u003csup\u003e\u003cb\u003e\u003cspan additionalcitationids=\"CR4\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, electronic signatures\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e,\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, temperature sensing\u003csup\u003e\u003cb\u003e\u003cspan additionalcitationids=\"CR8\" citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, health diagnosis\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, mechanically driven light emission device\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, and flexible electronic skin\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e,\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e,\u003cspan additionalcitationids=\"CR13\" citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e. Numerous inorganic ML materials such as ZnS:Mn/Cu\u003csup\u003e\u003cb\u003e6,15,16\u003c/b\u003e\u003c/sup\u003e, SrAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e:Eu\u003csup\u003e\u003cb\u003e17,18\u003c/b\u003e\u003c/sup\u003e, CaZnOS:Cu\u003csup\u003e\u003cb\u003e19\u003c/b\u003e\u003c/sup\u003e, and LiNbO\u003csub\u003e3\u003c/sub\u003e:Pr\u003csup\u003e\u003cb\u003e20,21\u003c/b\u003e\u003c/sup\u003e, have been investigated. Nerveless, ZnS is still considered as one of the most representative ML materials, which exhibits advantages of self-recoverability\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, stable ML emission\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, free of pre-excitation\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, feasibility in color-tuning\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, high brightness, and easy fabrication.\u003c/p\u003e\u003cp\u003eNormally, these ML materials are prepared into powder like samples and mixed with highly elastic organic materials such as polydimethylsiloxane (PDMS)\u003csup\u003e\u003cb\u003e\u003cspan additionalcitationids=\"CR27\" citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, epoxy resin\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e,\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e and so on, to demonstrate the ML properties by applying different forms of stress. However, these powder like samples are mainly composed of polycrystalline materials. Under macroscopic stress, the forces between microscopic crystals are very complex, involving not only the influence of crystal interfaces, but also the analysis of stress conditions\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, which ultimately makes the analysis of ML mechanisms particularly difficult, and greatly limits the accuracy of stress sensing, causing difficulties in the practical applications. Thus, there is an imperative need to develop non-polycrystalline integrated ML materials to simultaneously study the real ML mechanism and device based stress sensing applications.\u003c/p\u003e\u003cp\u003eStress-threshold is an important indicator reflecting the ML accuracy and performance. Recently, researchers have conducted research on the stress-threshold of ZnS system. Jha et al. systematically studied the stress-threshold of the macrocrystal, microcrystal, and nanocrystal ZnS:Mn, 30 and 0.8 MPa for the macrocrystal and microcrystal, respectively\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e. It is revealed that the threshold is highly related to the piezoelectric field inside the ZnS:Mn crystals. Particularly, Kleckner et al. used the nanoscopy tools to precisely study the ML thresholds of single ZnS:Mn particles\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e. Great heterogeneity of the stress-thresholds was observed, ranging from 0.233 to 47.15 MPa, with the lowest threshold obtained from the particle that is abundant with stacking disorder. In 2024, Yuan et al. reported a state-of-the-art low threshold force of 0.1 N for the ZGGO:Cr by precise control of defect content and trap distribution\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e. While the defect-control strategy has significantly reduced the threshold, it remains worthwhile to explore new approaches to feasibly lower the threshold force for ML emission. Furthermore, in the previously researches, the optical properties of the ML materials have been well investigated while the electrical changes such as variations in carrier concentration and conductivity under mechanical stimuli is lacking, mainly due to the poor conductivity and complexity of the inorganic-organic composite. The deficiency of electrical properties study hinders the deep-insight understanding of the real ML mechanism. Therefore, a combined study of mechano-electro-photon behaviors is of great significance.\u003c/p\u003e\u003cp\u003eUnder the current perspective, the generation of non-balanced free carriers is a key to the ML performance. Based on the origin of non-balanced carriers, two mainstream mechanism models, piezoelectric-induced carrier detrapping model\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e,\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e,\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e and the triboelectric-induced electroluminescence model\u003csup\u003e\u003cb\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e,\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e,\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e, have been proposed and developed. Regarding the carrier detrapping model, it is believed that the charge carriers trapped at various defects are released to the conduction or the valance band under the mechanical stimulus, generating non-balanced carriers for ML emission. For the triboelectric-induced electroluminescence model, non-balanced carriers are generated through the carrier transfer from the counterpart triboelectric materials, and has been well confirmed by Xie et al.\u003csup\u003e\u003cb\u003e16\u003c/b\u003e\u003c/sup\u003e As mentioned above, the non-balanced carriers for ML emission rely on either the detrapping of the electrons through piezoelectric effect or the electron injection by triboelectric effect, both of which result in limited non-balanced carrier generation. Conversely, the valence band (VB) of ML materials contains abundant electrons, but they are hardly activated by mechanical stimulation due to the substantial energy required for activation. For the photodetector design, researchers have integrated counterpart materials with the optoelectronic materials, forming a heterostructure in which type Ⅱ electron transition occurs\u003csup\u003e\u003cb\u003e\u003cspan additionalcitationids=\"CR39 CR40\" citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/b\u003e\u003c/sup\u003e. Herein, type Ⅱ electron transition means the electron in the VB of one material is directly activated to the conduction band (CB) of the counterpart material, so that lower energy could be efficiently utilized. This strategy may dramatically increase the non-balanced carriers engaged in ML emission and subsequently significantly improve the ML performances, however, no relevant study has been conducted.\u003c/p\u003e\u003cp\u003eIn this work, we propose constructing a ZnS:Mn/ZnO heterostructure with a type Ⅱ energy band alignment, where the CB of ZnO (CB\u003csub\u003eZnO\u003c/sub\u003e)is moderately higher than the VB of the ZnS:Mn film (VB\u003csub\u003eZnS\u003c/sub\u003e), aiming to directly activate the electrons in the VB of the ZnS for ML emission. The heterostructure design may also lower the stimulation threshold by introducing additional piezoelectric field via lattice mismatch and a built-in electric field through heterojunction formation at the ZnS:Mn/ZnO interface. Using standard photolithography, we patterned the film into a 50\u0026times;50 \u0026micro;m\u0026sup2; square array, forming a regular heterostructure with discrete emission centers. Each square functions as a pixel for mapping force distribution and recording dynamic forces. Remarkably, the ZnS:Mn/ZnO heterostructure exhibited a record-low threshold of 0.05 N (4 kPa). Additionally, two gold (Au) electrodes were formed on the ZnS:Mn/ZnO heterostructure to enable combined mechano-electro-photon studies. Pulsed electric current and 4-fold increasement in ML intensity were observed for the ZnS:Mn/ZnO heterostructure, suggesting the successful activation of type Ⅱ electron transition upon newton force stimulus. Compared with the limited trapped carriers by defects or the carrier transfer by triboelectric effect, the VB of ML materials contain large number of electrons that are available for activation. Therefore, the type II electron transition proposed in this work may dramatically increase the number of non-balanced free carriers involved in the ML process, thereby have a revolutionary impact on the efficiency and fundamental understanding of ML emission.\u003c/p\u003e"},{"header":"Experimental Section","content":"\u003cp\u003e\u003cb\u003eDeposition of ZnO:Mn films\u003c/b\u003e: Quartz glass with the size of 25\u0026times;25\u0026times;1 mm\u003csup\u003e3\u003c/sup\u003e was selected as the substrate for ZnO film growth. Prior to deposition, the substrates were ultrasonically cleaned in acetone, methanol, and deionized water in sequence for 10 mins, respectively. ZnO films doped with Mn were deposited on quartz glass substrates by co-sputtering technique (PVD-75, Kurt J. Lesker, USA) with a thickness of 200 nm. Various powers of Mn target, 2.5, 3, 3.5, 4 and 5 W were studied, and their photoluminescence are presented in \u003cb\u003eFigure\u003c/b\u003e S12. When the substrate was heated to 200\u003csup\u003eo\u003c/sup\u003eC, the chamber was filled with argon at a working pressure of 4 mTorr. Two fixed radio frequency (RF) power of 100 W and 3.5 W were applied to the ZnO and Mn targets, respectively. EDS was utilized to measure the element mappings (\u003cb\u003eFigure\u003c/b\u003e S14), and the Mn content (3.5 W) was measured to be 0.6 at%.\u003c/p\u003e\u003cp\u003e\u003cb\u003eZnS:Mn/ZnO heterostructure construction\u003c/b\u003e: To fabricate the ZnS:Mn/ZnO heterostructure, an AZ5214 photoresist mask was used to pattern the ZnO:Mn film deposited above, and a AlN film (80 nm) was grown as a barrier layer to prevent the ZnO layer beneath from sulfidation in the following annealing process. On the other hand, porous anodic aluminum oxide template (Pore diameter 200 nm and period of 450 nm) was covered on ZnO:Mn film before sulfidation annealing, to fabricate the ZnS:Mn/ZnO-AAO heterostructure. As for the sulfidation annealing process, 3g sulfur powder was added to the quartz bottle placed in the tube furnace (OTF-1200X-III, Hefei Kejing Materials Technology Co., China), films were heated to 700\u003csup\u003eo\u003c/sup\u003eC with a rate of 10\u003csup\u003eo\u003c/sup\u003eC min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and annealed for 60 min in the argon gas for sulfidation, followed by slowly cooling down (5\u003csup\u003eo\u003c/sup\u003eC min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) to room temperature. The anneal process in detail is presented in \u003cb\u003eFigure\u003c/b\u003e S13. The sulfur powder was simultaneously heated and kept at 200\u003csup\u003eo\u003c/sup\u003eC for the whole annealing process.\u003c/p\u003e\u003cp\u003e\u003cb\u003eCharacterizations\u003c/b\u003e: Surface morphology, crystal structure, and chemical composition of all films were characterized using SEM (APREO S, Thermoscientific, Holland), XRD (Ultima IV diffractometer, Rigaku), and XPS (Nexsa, TFS). Cross-sectional images and ZnS:Mn/ZnO interface were obtained using transmission electron microscopy (TEM, Titan Cubed Themis G201, FEI). The film thickness was measured by a surface-profile measurement system (Dektakxt, Bruker, USA). PL spectra were recorded using a FLS-1000 photo-luminescence spectrometer (Edinburgh Instruments Ltd., UK). The equipment used to obtain ML spectroscopy was a home-built measuring system consisting of a stepper motor, a digital push-pull force gauge, a linked displacement platform and the QE65pro fiber optic spectrometer (OceanInsight, UK). The UV-vis absorption spectra were carried out by using a UV-vis spectrophotometer (UV 3600 plus, Shimadzu, Japan). Electrical measurements were conducted at room temperature using an AES-4TH testing system equipped with a probe station.\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\u003ch2\u003eConstruction and characterization of the ZnS:Mn/ZnO heterostructure\u003c/h2\u003e\u003cp\u003eA method for well-designed construction of ZnS:Mn/ZnO heterostructure was proposed and developed in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea-c. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, ZnO:Mn film was deposited by co-sputtering technique, followed by a deposition of AlN film on the photolithography patterned ZnO:Mn film. Herein, the AlN film was utilized as a barrier layer to prevent the beneath ZnO:Mn film from sulfidation. The un-sulfidated ZnO film beneath the AlN barrier layer and the ZnS:Mn film precisely form ZnS:Mn/ZnO heterostructure at their interface, named as ZnS:Mn/ZnO-LT. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb illustrates the detailed dimensions and structure of the heterostructure, with the AlN barrier layer having a characteristic width of 10 \u0026micro;m, which was arranged in a grid pattern at intervals of 50 \u0026micro;m. To further confirm the ZnS:Mn/ZnO heterostructure, we employed an anodized aluminum oxide (AAO) template as the barrier layer to fabricate another ZnS:Mn/ZnO heterostructure named as ZnS:Mn/ZnO-AAO in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec.\u003c/p\u003e\u003cp\u003eThe SEM image presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed reveals the surface morphology of the ZnS:Mn/ZnO-LT, showing a periodic array structure and porous surface (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ee). As shown in \u003cb\u003eFigure\u003c/b\u003e S1 b-d, this porous feature is observed in all films prepared via the sulfidation process, which is significantly different from that directly deposited using ZnS target (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eg). The formation of this porous morphology is attributed to the sulfidation reaction from ZnO to ZnS, which is accompanied by the outward growth of ZnS\u003csup\u003e\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e,\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e. During this process, internal interface reaction leads to the creation of zinc and oxygen vacancies, which subsequently diffuse to the surface of the ZnS layer via point defects of interstitial sites, sulfur vacancies, and grain boundaries. The cross-sectional image shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ef verifies that this loose nature is not confined to the surface but extends throughout the whole film.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe optical images of the ZnS:Mn/ZnO heterostructure array chip were recorded by an optical microscope and shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eh. Under 365 nm light illumination, the ZnS:Mn film exhibits strong yellow emission while the ZnO film is free of emission, indicating successful construction of ZnS:Mn/ZnO heterostructure. It is worth to note that every ZnS square can be functioned as a pixel in the visualized detection of stress distribution, providing high resolution in remote stress detection. The size of the pixel is feasible to adjust in a wide range from nm to mm, depending on the requirement of resolution. X-ray diffraction (XRD) analyses were conducted and shown in Figure S2. The strong diffraction peak at 34.2\u0026deg; in the ZnO film is associated with the wurtzite (0 0 2) ZnO44. After annealing in the sulfur atmosphere, the ZnO film without AlN barrier layer was completely transformed to ZnS, which is a hexagonal ZnS with (0 0 2) orientation. For both the ZnS:Mn/ZnO-AAO and ZnS:Mn/ZnO-LT films, the ZnO (002) and (103) diffraction peaks persist after sulfidation. This confirms that a portion of ZnO remains due to the AlN barrier design or AAO mask, which is critical for constructing the ZnS:Mn/ZnO heterostructure.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eTransmission electron microscopy (TEM) analysis was conducted to study the interface of the ZnS/ZnO heterostructure and the defects in the ZnS:Mn film. As depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea, the left side shows an AlN barrier layer on the top and a dense ZnO film beneath with a thickness of ~\u0026thinsp;200 nm. On the right side, the thickness of the film is significantly larger than the left side, indicating the film expands during the sulfidation process, and a porous structure is presented, in consistent with the SEM result in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ee. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb focuses on the interface of the heterostructure, where a boundary between ZnO and ZnS is observed. Energy-dispersive X-ray spectroscopy (EDS) results shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec and \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed demonstrate a pronounced enrichment of oxygen (O) and sulfur (S) in their respective domains. This indicates that the sulfidation process was effectively controlled. Notably, the heterostructure in this work was formed in the designed regions rather than randomly, suggesting that the heterostructure fabrication method is highly controllable and its density can also be feasibly adjusted.\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ee presents a high-resolution transmission electron microscopy (HRTEM) image that clearly reveals the lattice structures of the two distinct phases at the interface. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ef presents the HRTEM image of the ZnO region, showing an order arrangement of atoms, and its corresponding fast fourier transform (FFT) pattern is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ei. It is seen that the FFT spots of ZnO are clear without streaks, indicating that the ZnO has a pristine wurtzite structure. The plane distances of 2.81 \u0026Aring;, 2.46 \u0026Aring;, and 2.6 \u0026Aring; are corresponding to the \u003cem\u003ewz-\u003c/em\u003eZnO \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\left(10\\stackrel{-}{1}0\\right)\\)\u003c/span\u003e\u003c/span\u003e, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\left(10\\stackrel{-}{1}1\\right)\\)\u003c/span\u003e\u003c/span\u003e, and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\left(0002\\right)\\:\\)\u003c/span\u003e\u003c/span\u003e, respectively. In contrast, the HRTEM image of the ZnS in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eg reveals that some atoms are in a disordered state, suggesting the existence of stacking fault. The observed plane distances in the FFT pattern depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ej are 2.86 \u0026Aring;, 2.83 \u0026Aring;, and 3.19 \u0026Aring;, corresponding to the \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\left(10\\stackrel{-}{1}\\stackrel{-}{1}\\right)\\)\u003c/span\u003e\u003c/span\u003e, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\left(10\\stackrel{-}{1}1\\right)\\)\u003c/span\u003e\u003c/span\u003e, and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\left(0002\\right)\\)\u003c/span\u003e\u003c/span\u003e of \u003cem\u003ewz\u003c/em\u003e-ZnS, respectively. Notably, the spots in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ej appear blurred and streaks are clearly observed, further confirming the presence of stacking faults in the ZnS. In previous research, it has been discovered that the stacking faults formed in the ZnS: Mn thin film is a key to the ML emission\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e,\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e. As mentioned above, the lattice constants of the ZnO and the ZnS are different, probably resulting in a strong stress and further piezoelectric field at the ZnS:Mn/ZnO interface, which is essential for the detrapping of carriers engaged in ML emission\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eh presents the high-resolution elemental mapping images of the interface of ZnS:Mn/ZnO, where a sharp transition in O and S content is observed. The interface width is determined to be 5.92 nm, confirming the well-defined formation of the ZnS:Mn/ZnO heterostructure. X-ray photoelectron spectroscopy (XPS) analysis was also conducted and studied. As shown in \u003cb\u003eFigure\u003c/b\u003e S3a-e, it is seen that the oxygen ions (O\u003csub\u003eL\u003c/sub\u003e)\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e within the lattice exist both in the ZnS:Mn/ZnO-AAO and in the ZnS:Mn/ZnO-LT heterostructure while no O\u003csub\u003eL\u003c/sub\u003e component is observed in the pristine ZnS film, further confirming that ZnO is preserved by the AlN barrier design or AAO mask.\u003c/p\u003e\u003c/div\u003e\n\u003ch3\u003eOptical and mechanoluminescence properties of the ZnS:Mn/ZnO-LT\u003c/h3\u003e\n\u003cp\u003eWe systematically investigated the ML behaviors of four ZnS:Mn thin films including traditional film, porous ZnS:Mn film prepared through sulfidation, the ZnS:Mn/ZnO-LT, and the ZnS:Mn/ZnO-AAO. These films were directly grown on the quartz glasses and no pre-irradiation was conducted before ML measurement. A spectrometer in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ef was utilized to record the ML properties. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea, the traditional ZnS:Mn film exhibits very weak ML emission, even when subjected to a strong force of 13 N. In sharp contrast, the sulfidated ZnS:Mn film (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb) and the ZnS:Mn/ZnO-LT heterostructure (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec) exhibit 12- and 15-fold stronger ML emission, respectively. Moreover, the ML behaviors of the ZnS:Mn/ZnO-AAO film with thicknesses of 200 and 400 nm exhibit similar improvements (\u003cb\u003eFigure\u003c/b\u003e S6 and S7), further confirming the key role of the heterostructure.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe ML intensities at various stimuli of the ZnS and ZnS:Mn/ZnO-LT heterostructure are summarized in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed. It is seen that the films with heterostructure demonstrate pronouncedly higher ML than the pristine ZnS:Mn film, especially at the cases of small stimulus (\u0026lt;\u0026thinsp;7 N). Within the force range of 1\u0026ndash;7 N, the emission intensity exhibits a linear relationship with the applied force. For a direct comparison, their ML spectra stimulated at 1 N are depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eg. The ML intensities of the ZnS:Mn/ZnO-LT film is about 4-fold stronger than that of the porous ZnS:Mn film. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ee, the ML of the ZnS:Mn/ZnO-LT heterostructure films are strong that they can be directly seen by naked eyes under a small stimulus of 1 N. To study its performances at small stimulus, the ML curves of the ZnS:Mn/ZnO-LT film range from 0.05 to 0.8 N were recorded and shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eh. Interestingly, the ZnS:Mn/ZnO heterostructure exhibits clear ML behavior under these small stimuli. To our knowledge, 0.05 N is the record-low stress threshold of the reported ML materials. Low stress-threshold is of great importance for the development of next-generation stress sensors, the electronic skin, and the humanoid robots since it can expand the detection to rather small stress together with much higher resolution. The ZnS:Mn/ZnO heterostructure almost has no stress-threshold, together with the linear relationship between the ML intensity and the stimulus force in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ei, making it considerable attractive for widespread practical applications. Furthermore, the ML performances under stimulus with frequency of 500 Hz were also studied. As depicted in Figure S8, the ML peaks observed in the near-infrared spectrum are centered at 754, 775, 852, and 970 nm, which can be attributed to the formation of (Mn)\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e clusters\u003csup\u003e\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e. The application of high-frequency stimulation enhances the likelihood of (Mn) \u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e cluster formation and promotes the energy transfer from the excited Mn\u003csup\u003e2+\u003c/sup\u003e ions to the (Mn)\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e clusters, consequently resulting in the emergence and intensification of the near-infrared emission band.\u003c/p\u003e\u003cp\u003eAs depicted in \u003cb\u003eFigure\u003c/b\u003e S4a, the transmittance of the ZnS:Mn/ZnO-LT film is smaller than both the ZnO and the ZnS film, suggesting enhanced light absorption because of the ZnS:Mn/ZnO heterostructure. \u003cb\u003eFigure\u003c/b\u003e S4b demonstrates that the optical bandgap of the ZnO is approximately 3.28 eV, and the bandgap of the ZnS is around 3.64 eV. \u003cb\u003eFigure\u003c/b\u003e S4c and 4d depicts the PL spectra of the ZnS:Mn/ZnO-LT films excited by 330 nm light and the PLE spectra at 585 nm. \u003cb\u003eFigure\u003c/b\u003e S4e shows that the time-resolved decay curve of the traditional ZnS:Mn film is consisting of two exponential decay components. Differently, the porous ZnS:Mn film and the ZnS:Mn/ZnO-LT in \u003cb\u003eFigure\u003c/b\u003e S4f exhibits three exponential decay components. The values of the decay curve in detail are summarized in \u003cb\u003eTable\u003c/b\u003e S1. Compared to porous ZnS film in \u003cb\u003eFigure\u003c/b\u003e S4f, the ZnS:Mn/ZnO-LT exhibits a higher proportion of \u0026#120591;\u003csub\u003e2\u003c/sub\u003e occupancy, A\u003csub\u003e2\u003c/sub\u003e. This suggests that the heterostructure introduces more defects\u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e. Moreover, thermoluminescence test was also conducted, as shown in \u003cb\u003eFigure\u003c/b\u003e S5, but no thermoluminescence was observed both for the porous ZnS:Mn film and the ZnS:Mn/ZnO-LT with various thicknesses.\u003c/p\u003e\n\u003ch3\u003eMechano-electro-photon combined study and ML mechanism of the ZnS:Mn/ZnO heterostructure\u003c/h3\u003e\n\u003cp\u003eTo characterize the coupled mechano-electro-photon behaviors of the ZnS:Mn/ZnO-LT heterostructure, two Au electrodes were deposited on the film surface to simultaneously collect electrical responses, while ML emission was recorded under the same mechanical stimulus. \u003cb\u003eFigure\u003c/b\u003e S9 shows the \u003cem\u003eI-V\u003c/em\u003e curves of the porous ZnS:Mn film and the ZnS:Mn/ZnO-LT film. As ZnS is a wide-bandgap semiconductor and highly resistive, the current is rather small. In contrast, the \u003cem\u003eI-V\u003c/em\u003e curve of the ZnS:Mn/ZnO-LT heterostructure device exhibits rectifying characteristic of diode, suggesting formation of heterojunction, and the conductivity of the ZnS:Mn/ZnO-LT is much larger, ~\u0026thinsp;40 nA, due to the higher conductivity of the ZnO.\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed shows the current responses of the ZnS:Mn/ZnO-LT heterostructure to force stimuli varied from 0.2 to 7 N. Interestingly, pulsed currents are clearly observed once the ZnS:Mn/ZnO-LT is applied to a force through Al needle, and recovers to the original value when the friction is stop. The larger the force is, the higher the pulsed current △I is. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ee, the current increases rapidly upon stimulation, with a current increase of △I\u0026thinsp;=\u0026thinsp;9.5 \u0026micro;A at 3 N. In sharp contrast, there is no pulsed current both for the ZnO and the ZnS:Mn film in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea and \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb, even at a larger stimulus of 13 N. For a given semiconductor, the carrier mobility is unlikely to change; thus, it can be deduced that free carriers are generated in the ZnS:Mn/ZnO heterostructure upon force stimulus. In contrast, neither the pristine ZnO nor the ZnS:Mn film generates free carriers, or the number of free carriers generated is smaller. The difference in the free carrier generation between the heterostructure and the pristine film is of great interest, since it implies new mechanism of free carrier generation in the ZnS:Mn/ZnO-LT heterostructure. Moreover, the ML behaviors of the ZnS:Mn/ZnO-LT heterostructure were simultaneously recorded upon the same stimuli in electrical signal collection and shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec and \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ef. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eg shows the plots of ML intensity as a function of newton force, suggesting excellent linearity between them. The magnitude of the pulsed current △I upon newton force are depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eh. It is seen that the △I gradually increase with the force within 5 N and sharply increases to 20 \u0026micro;A at 7 N. In Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ei, it is observed that the higher the pulsed current generated upon the force stimulus, the stronger the ML intensity is.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eBesides the process (i), it is deduced from Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed that the electrons in the VB\u003csub\u003eZnS\u003c/sub\u003e are directly activated to the CB\u003csub\u003eZnO\u003c/sub\u003e upon force stimulus. This process is denoted as process (ii) in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb, resulting in the additional non-balanced holes in the ZnS. For the photodetector research, the phenomenon of electrons transition from the VB of one material to the CB of the adjacent material has been well recognized, and named it as type Ⅱ electron transition\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e,\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e. Herein, it is the first time to propose and confirm the electron transition from the VB of one material to the CB of adjacent material in the ML study. To distinguish the electron transition within one material, we also named it as type Ⅱ electron transition. Since the conductivity of ZnO is better than the ZnS, the conductive channel of the ZnS:Mn/ZnO heterostructure is mainly ZnO. The type Ⅱ electron transition from VB\u003csub\u003eZnS\u003c/sub\u003e to CB\u003csub\u003eZnO\u003c/sub\u003e results in the increase of free electrons in ZnO and thus the improved conductivity of the heterostructure, well explaining the pulsed current observed in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed. Moreover, the non-balanced holes in ZnS generated by type Ⅱ electron transition also pronouncedly enhance the electron-hole pairs\u0026rsquo; non-radiation combination, resulting in a significantly improvement in ML emission as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed. In \u003cb\u003eFigure\u003c/b\u003e S11, the type Ⅱ electron transition is further confirmed by 520 nm photon irradiation. Compared with the limited trapped carriers by defects or the carrier transfer by triboelectric effect, the VB of ML materials contain large number of electrons that are available for activation. Thus, the type II electron transition in the ML behavior observed herein may significantly increase the number of non-balanced free carriers, thereby have a revolutionary impact on the efficiency and intensity of ML emission. This discovery provides a novel and general strategy for improving ML performance and advances the understanding of the ML mechanism.\u003c/p\u003e\u003cp\u003eConsidering the integration advantages of ZnS:Mn/ZnO heterostructure and the innovative carrier generation mode, this study further designed a pixel-array ML integrated application mode. Under the dynamic stress application, the ZnS:Mn/ZnO heterostructure array realizes the pixelated trajectory recording of scratching and handwriting by converting mechanical stress into luminescence through the ML process. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea, the scratching trajectory is visualized in real-time via image acquisition. A complementary metal oxide semiconductor (CMOS) image sensor is employed to capture the luminescence of the ZnS:Mn/ZnO heterostructure array under the stress. Using a 20x20 pixel array, the handwriting of \u0026ldquo;SZU\u0026rdquo; was successfully recorded in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ed. The ML intensity is derived by extracting the gray values of the captured image, and further calibrated to the value of force using the relationship shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eg. In this way, the approximate magnitude of the force applied during the \u0026ldquo;SZU\u0026rdquo; writing process was capable to record and present in in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ed. Notably, the ZnS:Mn/ZnO heterostructure array was fabricated via standard semiconductor processes on a wafer scale, enabling the integration of a photodetector array with the heterostructure array chip as depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec, directly converting the stimulus to the force/stress values, may providing dual-modes sensing of force or stress in the future. Owing to its extremely low stress-threshold, the heterostructure array-based system holds potential for applications in ethology research in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec and the development of high-precision force-recognition mechanical hands in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb. This design is the first time to transform the application mode of ML materials from polycrystalline powder to integrated array, result in the widespread promotion to develop the ML chips by utilizing the mechano-optical conversion. Due to its high efficiency and passive characteristics, it will have a significant impact on the current electrical stress sensing mode.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn summary, we have successfully constructed a ZnS:Mn/ZnO heterostructure with type Ⅱ energy band alignment. Standard semiconductor technique was utilized to fabricate the ZnS:Mn/ZnO heterostructure array chips, forming regular heterostructures and emission centers in square array. Each emission square functions as a pixel for mapping force distribution and recording dynamic forces, realizing the chip-based stress sensing applications. Pulsed electric current of 20 \u0026micro;A was simultaneously observed with bright ML emission, confirming the successful activation of type Ⅱ electron transition upon force stimulus. Notably, a record-low threshold of 0.05 N is achieved by introducing piezoelectric field at the heterostructure interface through lattice mismatch and a build-in electric field, providing a novel approach for lowering the ML stress-threshold. Compared with the limited trapped carriers by defects or the carrier transfer by triboelectric effect, the VB of ML materials contain large number of electrons that are available for activation. Thus, the type II electron transition in the ML behavior observed herein may significantly increase the number of non-balanced free carriers involved in the ML process, thereby have a revolutionary impact on the efficiency and intensity of ML emission.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003eAcknowledgements\u003c/p\u003e\n\u003cp\u003eThis work was supported by the National Natural Science Foundation of China (Grant No. 62071307 and 52372160), and Guangdong Basic and Applied Basic Research Foundation (Grant No. 2025A1515011910). The authors wish to acknowledge the assistance of TEM (Titan Cubed Themis G201, FEI) received from the Electron Microscope Center and Photonics Research Centre of Shenzhen University.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor details\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eState Key Laboratory of Radio Frequency Heterogeneous Integration, College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, P.R. China\u003c/p\u003e\n\u003cp\u003e\u003csup\u003e2\u003c/sup\u003eFaculty of Materials Science and Chemistry, China University of Geosciences, 388 Lumo Road, Wuhan 430074, China\u003c/p\u003e\n\u003cp\u003e\u003csup\u003e3\u003c/sup\u003eKey Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, China\u003c/p\u003e\n\u003cp\u003e\u003csup\u003e4\u003c/sup\u003eNew Industry Creation Hatchery Center, Tohoku University, Sendai, 980-8579, Japan\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eJ. Fan and Y. Wang contributed equally to this work. A. Zhong and D. Tu conceived the project. J. Fan, Y. Wang, and A. Zhong designed the experiments. J. Fan, Y. Wang, H. Yang, D. Peng and S. Xue were primarily responsible for the experiment setup and data collection. A. Zhong and D. Tu supervised the research. J. Fan, A. Zhong, K. Hane, and D. Tu wrote and revised the manuscript. J. Fan, Y. Wang, L. Huang, and Z. Ma prepared the figures. A. Zhong, J. Luo, K. Hane, and D. Tu proposed the ML emission mechanism. All authors contributed to data analysis, discussions and manuscript preparation.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eConflict of Interest\u003c/p\u003e\n\u003cp\u003eThe authors declare no conflict of interest.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupporting\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eI\u003c/strong\u003e\u003cstrong\u003enformation\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSupporting Information is available for this paper at :\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eZhuang Y, Tu D, Chen C, Wang L, Zhang H, Xue H \u003cem\u003eet al.\u003c/em\u003e Force-induced charge carrier storage: a new route for stress recording. \u003cem\u003eLight Sci Appl\u003c/em\u003e 2020; \u003cstrong\u003e9\u003c/strong\u003e: 182.\u003c/li\u003e\n\u003cli\u003eXie Z, Mao Z, Wang H, Xiao Y, Zhang X, Yu T \u003cem\u003eet al.\u003c/em\u003e Dual-channel mechano-phosphorescence: a combined locking effect with twisted molecular structures and robust interactions. \u003cem\u003eLight Sci Appl\u003c/em\u003e 2024; \u003cstrong\u003e13\u003c/strong\u003e: 85.\u003c/li\u003e\n\u003cli\u003eWang WX, Matsubara T, Takao Y, Imai Y, Xu CN. 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However, its high stress-threshold and limited emission efficiency fail to satisfy the growing application requirements. To address these challenges, we propose constructing ZnS:Mn/ZnO heterostructure with a novel type Ⅱ energy band alignment, aiming to activate the abundant electrons in the valence band for ML emission and introduce additional piezoelectric field as well as built-in electric field. The ZnS: Mn/ZnO heterostructure array chips were fabricated by standard semiconductor techniques, forming regular heterostructures and emission centers in square array. Each emission square functions as a pixel for mapping force distribution and recording dynamic forces. As anticipated, the heterostructure array exhibits a record-low threshold of 0.05 N and a 4-fold increase in ML intensity. In mechano-electro-photon combined study, pulsed electric current were simultaneously observed, directly confirming the generation of non-balanced free carriers upon the mechanical stimulus. Owing to the high electron density in the VB of ML materials, the type II electron transition proposed in this work could dramatically increase the number of non-balanced carriers participating in the ML process, thereby have a revolutionary impact on the efficiency and fundamental understanding of ML emission.\u003c/p\u003e","manuscriptTitle":"Superior Mechanoluminescence of ZnS:Mn/ZnO Heterostructure Array Chip Boosted by Type Ⅱ Electron Transition","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-11-13 15:33:44","doi":"10.21203/rs.3.rs-7927301/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"revise","date":"2026-03-05T00:24:57+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"This content is not available.","date":"2026-01-28T13:25:18+00:00","index":4,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2026-01-28T09:55:37+00:00","index":4,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2025-12-14T08:09:25+00:00","index":3,"fulltext":"This content is not available."},{"type":"editorInvitedReview","content":"This content is not available.","date":"2025-11-07T11:18:07+00:00","index":2,"fulltext":"This content is not available."},{"type":"editorInvitedReview","content":"This content is not available.","date":"2025-11-06T08:01:02+00:00","index":1,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2025-11-04T07:57:59+00:00","index":2,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2025-11-04T06:33:31+00:00","index":1,"fulltext":"This content is not available."},{"type":"reviewersInvited","content":"","date":"2025-11-04T06:12:41+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-10-24T02:25:02+00:00","index":"","fulltext":""},{"type":"submitted","content":"Microsystems \u0026 Nanoengineering","date":"2025-10-23T01:44:05+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-10-23T01:44:05+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"microsystems-and-nanoengineering","isNatureJournal":false,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"micronano","sideBox":"Learn more about [Microsystems \u0026 Nanoengineering](http://www.nature.com/micronano/)","snPcode":"41378","submissionUrl":"https://mts-micronano.nature.com/","title":"Microsystems \u0026 Nanoengineering","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature AJ","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"763cdbbe-80d2-4358-ab72-ed6c5f3fa4b4","owner":[],"postedDate":"November 13th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":57386715,"name":"Physical sciences/Optics and photonics"},{"id":57386716,"name":"Physical sciences/Engineering"},{"id":57386717,"name":"Physical sciences/Materials science"}],"tags":[],"updatedAt":"2026-04-23T07:16:35+00:00","versionOfRecord":{"articleIdentity":"rs-7927301","link":"https://doi.org/10.1038/s41378-026-01284-3","journal":{"identity":"microsystems-and-nanoengineering","isVorOnly":false,"title":"Microsystems \u0026 Nanoengineering"},"publishedOn":"2026-04-22 04:00:00","publishedOnDateReadable":"April 22nd, 2026"},"versionCreatedAt":"2025-11-13 15:33:44","video":"","vorDoi":"10.1038/s41378-026-01284-3","vorDoiUrl":"https://doi.org/10.1038/s41378-026-01284-3","workflowStages":[]},"version":"v1","identity":"rs-7927301","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7927301","identity":"rs-7927301","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}