{"title":"Effects of Crystal Orientations on Oxidation of Epitaxial TiN Thin Films","authors":"Zi-Qin Wang, Wen-Wen Fan, Yu-Hong Li, Hua-Long Zhu, Yujia Wang, Yunlong Tang","doi":"10.1039/d5nr01402f","DOIUrl":"https://doi.org/10.1039/d5nr01402f","url":null,"abstract":"As an industrial-grade electrode material, TiN is widely employed as a gate electrode and capacitor material in advanced semiconductor devices. However, the inevitable oxidation plays a negative role in the TiN thin films. In this study, crystallographic orientation engineering was employed to fabricate epitaxial TiN thin films, with an investigation of the oxidation behavior and electrical conductivity. Epitaxial TiN thin films were grown on the [001]-, [110]-, and [111]-oriented SrTiO3 substrates under high vacuum. High-resolution X-ray diffraction and Transmission electron microscopy confirm the epitaxial relationship and high growth quality. The X-ray photoemission spectroscopy depth profiling directly reflects the oxidation of epitaxial TiN thin films. The oxidation level follows the order of TiN(001) < TiN(110) ≈ TiN(111). X-ray photoemission spectroscopy after Ar+ ion etching reveals the presence of TiNxOy as the oxidation product. As measured by the Current-voltage curve, the epitaxial TiN thin films still retain the electrical conductivity. Our work provides a useful reference for preparing oxidation-controlled epitaxial TiN films by crystallographic orientation engineering and guidance for the design of chemically stable TiN thin film electrodes.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"56 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144130240","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NanoscalePub Date : 2025-05-23DOI: 10.1039/d5nr01119a
Li Luo,Jialuo Ding,Yuxin Zou,Yuanyuan Lv,Sui Peng,Bo Liu,Jingjing Bian,Zhe Zhao,Zhanyi Lin,Jiaqi Yang,Jin He,Cheng Chen,Shichao Zhao,Boyu Chen,Jitao Li,Jie Li,Jianquan Yao
{"title":"Spin-multiplexed phase and amplitude manipulations of terahertz waves based on chiral metasurfaces.","authors":"Li Luo,Jialuo Ding,Yuxin Zou,Yuanyuan Lv,Sui Peng,Bo Liu,Jingjing Bian,Zhe Zhao,Zhanyi Lin,Jiaqi Yang,Jin He,Cheng Chen,Shichao Zhao,Boyu Chen,Jitao Li,Jie Li,Jianquan Yao","doi":"10.1039/d5nr01119a","DOIUrl":"https://doi.org/10.1039/d5nr01119a","url":null,"abstract":"The independent manipulation of circularly polarized electromagnetic waves is a significant topic in the field of micro-nano optics, and metasurfaces provide a convenient solution for this target. However, the design of metasurfaces is still complex, often involving both parameter space and polarization space, where the simultaneous control of amplitude and phase is quite challenging. In this paper, we propose a new scheme for the spin-multiplexed control of amplitude and phase based on chiral metasurfaces, which only consider the parameter space. By sequentially breaking the in-plane mirror symmetry and second-order rotational symmetry of meta-atoms, we demonstrate two types of metasurfaces in the terahertz band. The first one achieves spin-multiplexed phase control of co-polarized terahertz waves solely through a chiral phase, with a reflection efficiency greater than 71.7% for both components. The other one is demonstrated for the joint control of phase and amplitude of the reflected circularly polarized wave. To validate the effectiveness of the scheme, two devices were designed with wavefront profiles such as focusing and deflection for functional verification. The results illustrate that by exploring and designing the parameter space of chiral meta-atoms, we can independently control circularly polarized waves using a chiral phase and circular dichroism, thus providing a new method for designing metasurfaces for spin-multiplexed amplitude-phase manipulations.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"57 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122314","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NanoscalePub Date : 2025-05-23DOI: 10.1039/d5nr00795j
K. Swetha, Anushree Bhatnagar, Manikrishna Lakavathu, Poornima Penta, PRATHIKSHA Ganesh, Adithi Kamath, Srinivasa Reddy Bonam, S. Murty Srinivasula, Rajendra Kurapati
{"title":"Biological Degradation of Graphitic Carbon Nitride Sheets and Autophagy Induction in Macrophages","authors":"K. Swetha, Anushree Bhatnagar, Manikrishna Lakavathu, Poornima Penta, PRATHIKSHA Ganesh, Adithi Kamath, Srinivasa Reddy Bonam, S. Murty Srinivasula, Rajendra Kurapati","doi":"10.1039/d5nr00795j","DOIUrl":"https://doi.org/10.1039/d5nr00795j","url":null,"abstract":"Although a metal-free graphitic-C3N4 was studied for potential applications in bioimaging, cancer therapy, etc., its biodegradability and impact on immune modulation and autophagy induction have not yet been reported, which are essential for designing clinical applications. Herein, we studied the biodegradability of two types of g-C3N4 nanosheets (exfoliated and porous) using human myeloperoxidase (hMPO) from the primary immune cells (neutrophils), plant enzyme horseradish peroxidase (HRP) and photo-Fenton reaction (PF, generating hydroxy radicals). The biodegradation was followed by electron microscopy, and spectroscopic techniques such as Raman, X-ray photoelectron, UV-vis and fluorescence spectroscopy. All these results confirmed that the g-C3N4 sheets could be degraded better by hMPO over HRP, where porous g-C3N4 showed higher degradability than exfoliated due to the presence of oxygen groups. Next, the PF reaction was applied to interrogate the degradation by-products using mass spectrometry, and the cytotoxicity of degradation products was assessed in comparison with pristine g-C3N4. Further, the impact of g-C3N4 on the induction of autophagy in the RAW264.7 macrophages was confirmed by over-expression of the autophagy marker, LC3 protein, especially significantly observed for the porous sheets. Finally, the immunomodulatory function of the nanosheets and cytokine production was also evaluated in RAW macrophages following exposure to both porous and exfoliated g-C3N4. These findings demonstrated that the porous nanosheets induced a dose-dependent pro-inflammatory response.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"15 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NanoscalePub Date : 2025-05-23DOI: 10.1039/d5nr01273b
Abuzer Alp Yetisgin, Sivakumar Ponnurengam Malliappan, Sibel Cetinel
{"title":"Current state and potential of polymersomes as ocular drug delivery systems","authors":"Abuzer Alp Yetisgin, Sivakumar Ponnurengam Malliappan, Sibel Cetinel","doi":"10.1039/d5nr01273b","DOIUrl":"https://doi.org/10.1039/d5nr01273b","url":null,"abstract":"Amphiphilic copolymers can spontaneously form different structures such as micelles, worm-like micelles, and spherical and tubular polymersomes, determined by the ratio of hydrophilic and hydrophobic blocks. Among them, polymersomes are composed of an aqueous core and a hydrophobic membrane that can encapsulate hydrophilic and hydrophobic drugs. Significant effort has been dedicated to developing polymersomes for targeted delivery of drugs, particularly in cancer therapy. Nonetheless, polymersomes hold great potential for drug delivery to the ocular tissues as well. Polymersomes provide various advantages as ocular drug delivery systems due to their chemical and physical adaptability, ability to encapsulate multiple drugs, and precise control over parameters including size, shape, membrane characteristics, drug release, ability to traverse biological barriers, and responsiveness to stimuli. Despite the limited research to date, polymersomes, with their superior mobility within ocular compartments and their tunable properties, should be considered a promising option for ocular drug delivery, surpassing other vesicular systems such as liposomes and niosomes. In this review, we assessed the possibility of polymersomes as carriers for delivering drugs to ocular tissues.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"10 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122838","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NanoscalePub Date : 2025-05-23DOI: 10.1039/d5nr01676b
Jinyang Bi,Huijun Lv,Hengguang Wang,Liping Du,Yan Liu,Yueqi Shen,Bo Wu,Yong Wang,Weihua Ning
{"title":"Bandgap engineering of lead-free double perovskites for efficient photocatalysis.","authors":"Jinyang Bi,Huijun Lv,Hengguang Wang,Liping Du,Yan Liu,Yueqi Shen,Bo Wu,Yong Wang,Weihua Ning","doi":"10.1039/d5nr01676b","DOIUrl":"https://doi.org/10.1039/d5nr01676b","url":null,"abstract":"Lead-free halide perovskites represent promising candidates in optoelectronics due to their excellent properties, such as high stability, mobility, defect tolerance and low-cost processes. However, their applications in photovoltaic and photocatalysis are limited by their wide bandgap nature. Here, we introduced Sb3+ and Sb5+ ions into the double perovskite Cs2AgBiCl6, successfully narrowing its bandgap and extending the absorption band edge to 1450 nm, representing the broadest near-infrared (NIR) response reported for lead-free perovskites. Remarkably, the Sb-doped perovskite catalyst exhibits a significantly enhanced photocatalytic hydrogen generation rate. Specifically, Cs2AgBiCl6:0.63% Sb5+ achieves a hydrogen generation rate of 4835.9 μmol g-1 h-1 under 420-780 nm irradiation, which is an order of magnitude improvement over that of pure Cs2AgBiCl6. This material maintains high photocatalytic performance within the NIR range and demonstrates sustained stability over a 16-hour continuous reaction. This study sets the stage for fabricating stable perovskite-based photocatalysts and breaks through the spectral absorption range of halide perovskite materials, and the proposed strategy extends light absorption to activate NIR photoactivity.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"15 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122315","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NanoscalePub Date : 2025-05-23DOI: 10.1039/d5nr00952a
Peiyuan Pang, Zhipeng Zhang, Bingzhe Wang, Tao Sheng, Guichuan Xing
{"title":"Efficient and Color Stable Blue Perovskite Light-Emitting Diodes Achieved via Dual-Additive Phase Modulation","authors":"Peiyuan Pang, Zhipeng Zhang, Bingzhe Wang, Tao Sheng, Guichuan Xing","doi":"10.1039/d5nr00952a","DOIUrl":"https://doi.org/10.1039/d5nr00952a","url":null,"abstract":"Despite remarkable progress in sky-blue perovskite light-emitting diodes (PeLEDs), achieving efficient and color stable pure-blue electroluminescence remains challenging due to halide phase segregation, low-dimensional phase-induced non-radiative recombination, and defect-related losses in mixed Cl-Br quasi-2D perovskites. Here, we propose a dual-additive strategy to regulate phase distribution and manage Cl incorporation in quasi-2D perovskites for pure-blue PeLEDs. By introducing EDACl2 to suppress high-n phases and incorporate Cl for bandgap broadening, combined with NaBr to eliminate low-n non-radiative centers and promote small-sized nanocrystals, we optimize radiative recombination toward wide-bandgap phase distribution. This approach enables spectrally stable pure-blue electroluminescence at 474 nm without compromising photoluminescence quantum yield. Further hole-transport-layer engineering yields a peak external quantum efficiency of 4.6%, with spectral stability maintained under extreme bias up to 10.4 V. Our work provides critical insights into phase and halide management for high-performance blue PeLEDs, advancing their potential in full-color displays and lighting technologies.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"18 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122839","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NanoscalePub Date : 2025-05-23DOI: 10.1039/d5nr00465a
Srinivasa Reddy Tamalampudi,Ghada Dushaq,Mahmoud S Rasras
{"title":"An ultra-high-speed vertically illuminated self-driven lateral asymmetric InSe photodetector.","authors":"Srinivasa Reddy Tamalampudi,Ghada Dushaq,Mahmoud S Rasras","doi":"10.1039/d5nr00465a","DOIUrl":"https://doi.org/10.1039/d5nr00465a","url":null,"abstract":"Two-dimensional (2D) materials have emerged as a promising platform for next-generation optoelectronic devices due to their unique electronic, optical, and mechanical properties, offering unprecedented opportunities for high-performance, low-power photodetection. We demonstrate a high-speed, zero-bias Au-InSe-multilayered graphene photodetector with an ultra-low dark current of 0.1 nA and photovoltaic-effect-driven photocurrent generation. The device exhibits a responsivity of 57.15 mA W-1 and a detectivity of 1.58 × 109 Jones at a wavelength of 785 nm. The device achieves an RF 3 dB bandwidth of 2.5 MHz, corresponding to an ultrafast response time of 140 ns, establishing a new benchmark for zero-bias InSe photodetectors. The exceptional performance is attributed to using asymmetric electrodes, which establish a built-in electric field within the depletion region. This field facilitates the rapid separation of photogenerated electron-hole pairs, which reduces carrier lifetime and minimizes recombination effects, thereby significantly boosting the response speed. Our results underscore the potential of InSe photodetectors with asymmetric contacts for achieving low dark current, high-speed operation, and low power consumption, offering a promising pathway for the development of next-generation optoelectronic devices based on 2D materials.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"10 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NanoscalePub Date : 2025-05-23DOI: 10.1039/D5NR90092A
Nicholas A. Kotov, Jeanne Crassous, David B. Amabilino and Pengfei Duan
{"title":"Chiral nanomaterials: theory, synthesis, applications and challenges","authors":"Nicholas A. Kotov, Jeanne Crassous, David B. Amabilino and Pengfei Duan","doi":"10.1039/D5NR90092A","DOIUrl":"10.1039/D5NR90092A","url":null,"abstract":"<p >A graphical abstract is available for this content</p>","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":" 22","pages":" 13526-13530"},"PeriodicalIF":5.8,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NanoscalePub Date : 2025-05-23DOI: 10.1039/d5nr00752f
Subhrajeet Banerjee,Saptarshi Mandal,Sneha Singh,Abhik Sen,Prolay Das
{"title":"Machine learning-guided fabrication of carbon dot-pepsin nano-conjugates for enhanced bioimaging, synergistic drug delivery, and visible light-induced photosensitization.","authors":"Subhrajeet Banerjee,Saptarshi Mandal,Sneha Singh,Abhik Sen,Prolay Das","doi":"10.1039/d5nr00752f","DOIUrl":"https://doi.org/10.1039/d5nr00752f","url":null,"abstract":"Carbon dots (CDs) are emerging as next-generation bioimaging agents due to their strong fluorescence, photobleaching resistance, and biocompatibility. However, their small size often limits efficient cell internalization, leading to unspecified cellular targets and high endosomal escape. Herein, we showcase the potential of pepsin, a simple proteolytic enzyme, to address the limitations of CDs through its covalent conjugation and subsequent creation of CD-pepsin nanoparticles (NPs). Interestingly, repeated failures in achieving CD-pepsin NPs prompted us to explore machine learning (ML), which, in a novel approach, successfully predicted the most favourable conditions for their formation. These nanoparticles unlocked two critical functionalities beyond enhanced imaging: visible light-induced reactive oxygen species (ROS) generation and sustained drug delivery, highlighting their potential for chemo-photodynamic combination therapy. The photophysical properties of the green-emissive CDs, synthesized from 3-hydroxy-2-naphthoic acid, were significantly enhanced through covalent conjugation with pepsin. This enhancement was evident in the efficient confocal imaging of human macrophage cells (THP1 cells) using both the CD-pepsin covalent conjugate and CD-pepsin NPs. Beyond enhancing the imaging potential of CDs by stabilizing their surface states through covalent conjugation with pepsin, this modification also significantly increased ROS generation, surpassing conventional photosensitizers like protoporphyrin (PpIX). Irradiation of the cells with a simple 23 W white LED induced increased oxidative stress, leading to reduced cell viability. Simultaneously, the CD-pepsin NPs functioned as a drug delivery vehicle, enabling the sustained release of the model drug, doxorubicin, over 4-5 days. These combined functionalities-bioimaging, photosensitization, and drug delivery-highlight CD-pepsin NPs as a versatile and effective multipurpose platform, overcoming key limitations of pristine CDs for advanced theranostics.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"130 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122363","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NanoscalePub Date : 2025-05-23DOI: 10.1039/D5NR00253B
Daphika S. Dkhar, Supratim Mahapatra and Pranjal Chandra
{"title":"An electrochemically charged nanoengineered bioelectronic immunosensing device for osteopontin detection in serum samples†","authors":"Daphika S. Dkhar, Supratim Mahapatra and Pranjal Chandra","doi":"10.1039/D5NR00253B","DOIUrl":"10.1039/D5NR00253B","url":null,"abstract":"<p >Osteopontin (OPN) is a crucial biomarker for osteosarcoma, an aggressive bone cancer. Elevated levels of OPN are found in osteosarcoma tissues and blood samples, associated with tumor growth, metastasis, and poor prognosis. The present electrochemical voltammetric detection methods are mainly assisted by redox couple/chemical mediators in a measuring solution. However, in resource-confined settings, such a detection strategy undermines the potential for the development of precise and easy-to-use point-of-care bioelectronic devices. To simplify the detection method, herein, we present a reliable and straightforward clinically deployable immunosensor <em>via</em> engineering an electrochemically charged surface that does not require mediators in the solution phase. Such an electroactive surface offers a simplistic label-free detection of the protein OPN, requiring only the use of a buffer solution to obtain the signals. The electroactive immunosensor probe was engineered using electrodeposited gold, bimetallic FeGdHCF redox nanoparticles, and oxidized graphene nanoplatelets for immobilizing the OPN antibodies. Since the detection is precisely dependent on the redox-active electrode surface for obtaining analytical signals, this strategy was further designed into a miniaturized device cascade for the direct and on-site detection of OPN. The immunosensor probe showed a low LOD of 0.437 (±0.002) (RSD < 4.09%, <em>n</em> = 5) pg mL<small><sup>−1</sup></small> and a wide LDR of 5 × 10<small><sup>2</sup></small> to 2 × 10<small><sup>6</sup></small> pg mL<small><sup>−1</sup></small>. It was applied to detect OPN in serum samples and was also evaluated for its selectivity against various molecules coexisting in real clinical samples and was found to be stable for a period of six weeks.</p>","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":" 22","pages":" 13668-13684"},"PeriodicalIF":5.8,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}