A novel process for the fabrication of Long Range Surface Plasmon Polariton (LRSPP) waveguide based biosensors is presented herein. The structure of the biosensor is comprised of Au stripe waveguide devices embedded in thick CYTOP claddings with a SiO2 solvent diffusion barrier and etch-stop layer. The SiO2 layer is introduced to improve the end quality of Au waveguide structures, which previously deformed during the deposit of the upper cladding process and to limit the over-etching of CYTOP to create micro-fluidic channels. The E-beam evaporation method is adapted to deposit a thin SiO2 on the bottom cladding of CYTOP. A new micro-fluidic design pattern is introduced. Micro-fluidic channels were created on selective Au waveguides through O2 plasma etching. The presented data and figures are refractive index measurements of different materials, thickness measurements, microscope images, and AFM images. Optical power cutback measurements were performed on fully CYTOP-cladded symmetric LRSPP waveguides. The end-fire coupling method was used to excite LRSPP modes with cleaved polarization maintaining (PM) fibre. The measured mode power attenuation (MPA) was 6.7 dB/mm after using index-matched liquid at input and output fibre-waveguide interfaces. The results were compared with the theoretical calculations and simulations. Poor coupling efficiency and scattering due to the SiO2 are suspected for off-target measurements.

Over the years, the view on proteases as relatively non-specific protein degradation enzymes, mainly involved in food digestion and intracellular protein turnover, has shifted and they are now recognized as key regulators of many biological processes that determine the fate of a cell. Besides their biological role, proteases have emerged as important tools in various biotechnical, industrial and medical applications. At present, there are worldwide efforts made that aim at deciphering the biological role of proteases and understanding their mechanism of action in greater detail. In addition, with the growing demand of novel protease variants adapted to specific applications, protease engineering is attracting a lot of attention. With the vision of contributing to the field of protein science, we have developed a platform for the identification of site-specific proteolysis, consisting of two intracellular genetic assays; one fluorescence-based (Paper I) and one antibiotic resistance-based (Paper IV). More specifically, the assays take advantage of genetically encoded short-lived reporter substrates that upon cleavage by a coexpressed protease confer either increased whole-cell fluorescence or antibiotic resistance to the cells in proportion to the efficiency with which the substrates are processed. Thus, the fluorescence-based assay is highly suitable for high-throughput analysis of substrate processing efficiency by flow cytometry analysis and cell sorting, while the antibiotic resistance assay can be used to monitor and identify proteolysis through (competitive) growth in selective media. By using the highly sequence specific tobacco etch virus protease (TEVp) as a model in our systems, we could show that both allowed for (i) discrimination among closely related substrate peptides (Paper I & IV) and (ii) enrichment and identification of the best performing substrate-protease combination from a background of suboptimal variants (Paper I & IV). In addition, the fluorescence-based assay was used successfully to determine the substrate specificity of TEVp by flow cytometric screening of large combinatorial substrate libraries (Paper II), and in a separate study also used as one of several methods for the characterization of different TEVp mutants engineered for improved solubility (Paper III). We believe that our assays present a new and promising path forward for high-throughput substrate profiling of proteases, directed evolution of proteases and identification of protease inhibitors, which all are areas of great biological, biotechnical and medical interest. / QC 20110516

Semiconductor wafer bonding has been a subject of interestfor many years and a wide variety of wafer bonding techniqueshave been reported in literature. In adhesive wafer bondingorganic and inorganic adhesives are used as intermediatebonding material. The main advantages of adhesive wafer bondingare the relatively low bonding temperatures, the lack of needfor an electric voltage or current, the compatibility withstandard CMOS wafers and the ability to join practically anykind of wafer materials. Adhesive wafer bonding requires nospecial wafer surface treatmentssuch as planarisation.Structures and particles at the wafer surfaces can be toleratedand compensated for some extent by the adhesive material.Adhesive wafer bonding is a comparably simple, robust andlowcost bonding process. In this thesis, adhesive wafer bondingtechniques with different polymer adhesives have beendeveloped. The relevant bonding parameters needed to achievehigh quality and high yield wafer bonds have been investigated.A selective adhesive wafer bonding process has also beendeveloped that allows localised bonding on lithographicallydefined wafer areas. Adhesive wafer bonding has been utilised in variousapplication areas. A novel CMOS compatible film, device andmembrane transfer bonding technique has been developed. Thistechnique allows the integration of standard CMOS circuits withthin film transducers that can consist of practically any typeof crystalline or noncrystalline high performance material(e.g. monocrystalline silicon, gallium arsenide,indium-phosphide, etc.). The transferred transducers or filmscan be thinner than 0.3 µm. The feature sizes of thetransferred transducers can be below 1.5 µm and theelectrical via contacts between the transducers and the newsubstrate wafer can be as small as 3x3 µm2. Teststructures for temperature coefficient of resistancemeasurements of semiconductor materials have been fabricatedusing device transfer bonding. Arrays of polycrystallinesilicon bolometers for use in uncooled infrared focal planearrays have been fabricated using membrane transfer bonding.The bolometers consist of free-hanging membrane structures thatare thermally isolated from the substrate wafer. Thepolycrystalline silicon bolometers are fabricated on asacrificial substrate wafer. Subsequently, they are transferredand integrated on a new substrate wafer using membrane transferbonding. With the same membrane transfer bonding technique,arrays of torsional monocrystalline silicon micromirrors havebeen fabricated. The mirrors have a size of 16x16 µm2 anda thickness of 0.34 µm. The advantages of micromirrorsmade of monocrystalline silicon are their flatness, uniformityand mechanical stability. Selective adhesive wafer bonding hasbeen used to fabricate very shallow cavities that can beutilised in packaging and component protection applications. Anew concept is proposed that allows hermetic sealing ofcavities fabricated using adhesive wafer bonding. Furthermore,microfluidic devices, channels and passive valves for use inmicro total analysis systems are presented. Adhesive wafer bonding is a generic CMOS compatible bondingtechnique that can be used for fabrication and integration ofvarious microsystems such as infrared focal plane arrays,spatial light modulators, microoptical systems, laser systems,MEMS, RF-MEMS and stacking of active electronic films forthree-dimensional high-density integration of electroniccircuits. Adhesive wafer bonding can also be used forfabrication of microcavities in packaging applications, forwafer-level stacking of integrated circuit chips (e.g. memorychips) and for fabrication of microfluidic systems.

A presente pesquisa se propôs a avaliar a influência de cinco tratamentos dentinários na resistência de união à dentina de quatro cimentos de ionômero de vidro modificados por resina (CIVRMs). O ensaio experimental foi realizado in vitro, fazendo uso de 200 incisivos bovinos. Destes, foram obtidos 200 fragmentos de dentina, que foram distribuídos aleatoriamente em 20 grupos (n=10), segundo os fatores de variação que compreendem cinco tratamentos dentinários (Grupo controle, ou seja, sem tratamento; Ácido Poliacrílico a 20%, Clearfil SE Bond; Single Bond Universal e Primer do Vitremer) e quatro cimentos ionoméricos (GC Fuji II LC® CAPSULE; GC Fuji LINING® LC (Paste Pak); Vitrebond® e Vitremer). Após a confecção dos corpos de prova e 24h de armazenamento em estufa à 37oC, foi realizado o teste de microcisalhamento na máquina de ensaios universal (Instron 5942 - Canton, MA, EUA) com velocidade de 1mm/min, seguido da análise do padrão de fratura em microscópio digital. A análise estatística dos 400 resultados obtidos foi feita por meio do teste paramétrico ANOVA para dois fatores de variação (cimento e tratamento) (p<0,05%) e pelo teste auxiliar de Tukey (p<0,05%). Os testes estatísticos demonstraram haver diferença estatística tanto entre os tratamentos, como entre os cimentos e na interação de ambos (p<0,0001). Os sistemas adesivos Clearfil SE (X?=18,26 ± 2,78) e SingleBond (X?=17,28 ± 2,49) promoveram os valores de resistência adesiva mais elevados em comparação aos demais tratamentos, mas sem apresentarem diferença estatística entre si, o que representou um aumento na resistência de união de 121% para o Clearfil SE e 109,2% para o Single Bond Universal em relação ao Grupo Controle. O uso do Ácido Poliacrílico (X?=9,94 ± 3,55) alcançou valores intermediários, correspondendo a um aumento de 20% na resistência adesiva em relação ao Grupo Controle. Esse tratamento se diferenciou estatisticamente dos maiores valores, porém não apresentou diferença frente ao Primer do Vitremer (X?=8,91 ± 2,97). O grupo controle (X?=8,26 ± 4,17) evidenciou os menores valores, se diferenciando estatisticamente dos sistemas adesivos e do Ácido Poliacrílico, mas com resultados que o equiparou ao tratamento com o Primer do Vitremer. Ao se analisar a interação entre cimento e tratamento, todos os cimentos de ionômero de vidro resinomodificados (CIVRMs) testados neste estudo apresentaram seus maiores resultados quando um dos sistemas adesivos foi utilizado como tratamento dentinário, independente de qual sistema adesivo. Com base nesses resultados, pôde-se concluir que os dois sistemas adesivos autocondicionantes foram capazes de melhorar significativamente a resistência adesiva dos CIVRMs. / This research aims to evaluate the influence of five dentin pretreatments on microshear bond strength of four resin-modified glass ionomer (RMGI). The experiment was performed in vitro, using 200 bovine incisors. From these, there were obtained 200 dentine fragments that were randomly distributed into 20 groups (n = 10) according to the variation factors comprising five dentin treatment (control group, i.e., no treatment; Polyacrylic Acid 20%; Clearfil SE Bond; Single Bond Universal and Vitremer Primer) and four glass ionomer cements (GC Fuji II LC® CAPSULE; GC Fuji LC LINING® (Paste Pak); Vitrebond® and Vitremer). After preparation of the samples and 24h storage at 37 °C, was performed microshear test in a universal testing machine (Instron 5942 - Canton, MA, USA) with speed of 1mm/min, followed by analysis of the pattern fractures in digital microscope. Statistical analysis of the 400 results was performed by ANOVA nonparametric test for two variation factors (cement and treatment) (p <0.05%) and the post-hoc Tukey (p <0.05%). The tests demonstrated there are statistical difference between treatments, cements and between the interaction of both (p <0.0001). The Clearfil SE (X?=18,26 ± 2,78) and SingleBond (X?=17,28 ± 2,49) promoted the highest bond strength values compared to the other treatments, but showing no statistical difference between them, which represented an increase in bond strength of 121% for Clearfil SE and 109.2% for Single Bond Universal compared to control group. The Polyacrylic Acid (X?=9,94 ± 3,55) has reached intermediate values, corresponding to a 20% increase in adhesive strength compared to control group. This treatment differed significantly from the higher values, but showed no difference compared to Primer Vitremer (X?=8,91 ± 2,97). The control group (X?=8,26 ± 4,17) showed the lowest values, statistically differing from the adhesives and polyacrylic acid, but with results that matched to the treatment with Vitremer Primer. When analyzing the interaction between cement and treatment, all cements tested in this study had higher results when one of the adhesive systems was used as dentin treatment, regardless of which adhesive system. Based on these results, it could be concluded that the two adhesive systems were able to significantly improve the adhesive strength of RMGIs.

Os estudos sobre contaminação apresentam difícil comparação devido a variedade dos delineamentos experimentais como o tipo de substrato testado, o momento na sequência do procedimento adesivo em que a contaminação acontece e a forma como essa contaminação é tratada de maneira a limpar este campo operatório. Assim, novos estudos fazem-se necessários para investigar com maior profundidade as condições já descritas na literatura e assim, obter um protocolo de conduta mais seguro para lidar com a contaminação. Esse estudo objetivou analisar,através de Microscopia Eletronica de Varredura (MEV), a interface adesiva de restaurações realizadas com sistema adesivo autocondicionante de dois passos (Clearfill SE Bond Kuraray), contaminadas por sangue em dois momentos diferentes, recebendo essa contaminaçao dois tratamento distintos. Para tanto foram selecionados 15 molares humanos que foram divididos em 5 grupos experimentais (n=3): G1 controle (sem contaminaçao); G2 contaminação antes do primer, com tratamento de lavagem e secagem; G3 contaminação antes do primer com tratamento de secagem; G4 contaminação após bond fotopolimerizado com tratamento de lavagem e secagem; G5 contaminação após bond fotopolimerizado com tratamento de secagem. Os dentes foram submetidos ao corte do terço oclusal da coroa para obtenção de superfície dentinária plana. Essa superfície foi regularizada com lixas SiC e a camada de esfregaço padronizada foi obtida com lixa SiC #600 por 1 min. Os espécimes foram contaminados, de acordo com os grupos experimentais, com sangue obtido de um único doador o próprio autor armazenado em tubos Vacuette® com heparina sódica e utilizado em até 7 dias. Então foram restaurados com uma camada de resina flow (Filtek Z-350 Flow 3M-ESPE) e duas camadas de resina microhibrida (Filtek Z-350 3MESPE). Após a construção dos espécimes, estes foram seccionados ao meio e passaram por preparo para análise em MEV. Os resultados obtidos foram descritos de duas formas: Análise Morfológica: onde foram observadas alterações na formação da camada híbrida (CH) em grupos com a presença do contaminante, e Análise Morfométrica, que foi analisada estatisticamente, e pode-se constatar uma relação entre a presença do contaminante e a diminuição do tamanho de tags em m, quando comparados ao grupo controle (p 0,05). Adicionalmente, foi observado que o tratamento de lavagem com água não foi suficiente para reestabelecer a formação de camada híbrida semelhante a observada no grupo controle. / Studies on contamination are difficult to compare due to the variety of experimental designs as the type of substrate, the time when contamination takes place during the adhesive procedure and how this contamination is treated in order to clean the operatory field. Thus, further studies are needed to investigate more thoroughly the conditions described in the literature and obtain a protocol to deal with contamination. This study aimed to observe, by scanning electron microscopy (SEM), the interface of adhesive restorations performed with a two-stepself-etching adhesive system (Clearfill SE Bond - Kuraray), contaminated with blood at two different times, receiving two different treatment to the contamination . Therefore, 15 selected human molars were divided into five experimental groups (n = 3): G1 - control (no contamination), G2 - contamination before primer, and rinsing and drying treatment, G3 - contamination before priming treatment, thendrying; G4 - contamination after light curing bond, rinsing and drying treatment; G5 - after light curing bond and drying. The teeth were then seccioned in order to obtain a flat dentin surface. This surface was regularized with SiC sandpaper and a standardized smear layer was obtained with SiC sandpaper # 600 for 1 min. The specimens were subsequently contaminated, according to the experimental groups, with blood obtained from a single donor - the author stored inVacuette ® tubes with sodicheparin and used within 7 days. They were restored with a layer of flowable composite (Filtek Z-350 Flow - 3M-ESPE) and two layers of microhybridresin (Filtek Z-350 - 3M-ESPE). After construction, the specimenswere divided in two, exposing the center of restorationand passed through preparation for SEM analysis. The results were described in two ways: Morphological Analysis where changes were observed in hybrid layer (HL) formation of groups in the presence of the contaminant, and Morphometric Analysis, which was analyzed statistically andaassociation between presence of the contaminant and a decreasing size of tags was found when compared to the control group (p 0.05). Additionally, it was observed that treatment of washing with water was not sufficient to restore the formation of hybrid layer similar to that observed in the control group.

Made available in DSpace on 2014-08-20T14:30:07Z (GMT). No. of bitstreams: 1 Dissertacao_giana_da_silveira_lima.pdf: 1493174 bytes, checksum: 68e4c67538ad95eba022c0a0e790d4b8 (MD5) Previous issue date: 2007-12-21 / To investigate the influence of different water concentrations in self-etching primers solvents on microtensile bond strength (μTBS) of an experimental adhesive system. Five experimental self-etching primers with 0, 5, 10, 20 and 40 water concentration (wt %) in solvent, were synthesized. Clearfil SE Bond (CSEB) was used as commercial adhesive. Sixty bovine incisive were randomize separated in six groups (n=20). Vestibular enamel was removed to expose the superficial coronal dentin, this surface was polished wet to create a standardized smear layer. After rinsing, water was removed, leaving the surface visibly dried. The dentin surfaces were etched with primer and air-dried, after coating adhesive resin was applied and photo-activated, following the composite resin restoration was accomplished. After storage for 24 hours, the specimens were sectioned with a refrigerated diamond saw at low-speed. Microtensile bond strength were measured and data were analyzed by one-way ANOVA/Tukey s test (α=0.05). Analysis of variance showed that primer composition was a significant factor for bond strength. There was not difference on bond strength of the primers with water concentration: 40% (53.9 ± 12.7 MPa), 20% (51.1 ± 11.5 MPa) and 10% (47.5 ± 11.4 MPa) and CSEB (52.44 ± 13.27 MPa). The group with 5% (38.6 ± 12.9 MPa) and 0% (31.5 ± 7.5 MPa), present similar bond strength amongst themselves but statistically smaller that the other groups. The water concentration, present in the primer solvent, exercise significant influence on the bond strength of this experimental self-etching adhesive system / Este estudo avaliou a influência de diferentes concentrações de água no solvente de um primer autocondicionante de um sistema adesivo dentinário experimental. Foram formulados cinco primers experimentais com diferentes concentrações, 0; 5; 10; 20; 40%, de água em massa e Clearfil SE Bond (CSEB) foi utilizado como referência comercial. Foram utilizados 60 incisivos bovinos, distribuídos aleatoriamente entre 6 grupos (n= 20). Na face vestibular dos dentes foi realizado desgaste com lixas até a exposição de dentina com lixa d água 600. O primer foi aplicado sobre a dentina previamente seca com papel absorvente, sendo aplicado jato de ar e em seguida o adesivo foi aplicado e foto-ativado com aparelho fotopolimerizador LED SDI Radii®. A restauração foi confeccionada utilizando 2 incrementos, fotoativados de acordo com as recomendações do fabricante. Após armazenagem por 24 horas em água destilada à 37°C, os dentes foram seccionados em cortadeira de precisão e a resistência de união mensurada, através de ensaio de microtração em uma máquina de ensaios mecânicos. Análise de Variância segundo um critério e teste complementar de Tukey foram utilizados na análise estatística (α=5%). Não houve diferença na resistência de união de P40 (53,9 ±12,7 MPa) P20 (51,1 ±11,5 MPa) e P10 (47,5 ±11,4 MPa) e CB (52,44 ±13,27 MPa). Os grupos P5 (38,6 ±12,9 MPa) e P0 (31.5 ±7.5 MPa) não apresentaram diferença estatística entre si, mas seus valores de adesão dentinária foram menores que os demais grupos (p<0,05). A resistência de união dentinária do sistema adesivo experimental testado sofre influência da concentração de água presente no solvente do primer autocondicionante

A novel process for the fabrication of Long Range Surface Plasmon Polariton (LRSPP) waveguide based biosensors is presented herein. The structure of the biosensor is comprised of Au stripe waveguide devices embedded in thick CYTOP claddings with a SiO2 solvent diffusion barrier and etch-stop layer. The SiO2 layer is introduced to improve the end quality of Au waveguide structures, which previously deformed during the deposit of the upper cladding process and to limit the over-etching of CYTOP to create micro-fluidic channels. The E-beam evaporation method is adapted to deposit a thin SiO2 on the bottom cladding of CYTOP. A new micro-fluidic design pattern is introduced. Micro-fluidic channels were created on selective Au waveguides through O2 plasma etching. The presented data and figures are refractive index measurements of different materials, thickness measurements, microscope images, and AFM images. Optical power cutback measurements were performed on fully CYTOP-cladded symmetric LRSPP waveguides. The end-fire coupling method was used to excite LRSPP modes with cleaved polarization maintaining (PM) fibre. The measured mode power attenuation (MPA) was 6.7 dB/mm after using index-matched liquid at input and output fibre-waveguide interfaces. The results were compared with the theoretical calculations and simulations. Poor coupling efficiency and scattering due to the SiO2 are suspected for off-target measurements.

Lower k and low-leakage silicon carbonitride (SiCxNy ) films were fabricated using single precursor by using radio-frequency (RF) plasma-enhanced chemical vapor deposition (PECVD). We explored precursors with (1) cyclic-carbon-containing structures, (2) higher C/Si ratio, (3) multiple vinyl groups, as well as (4) the incorporation of porogen for developing low-k SiCxNy films as etch-stop/diffusion barrier (ES/DB) layer for copper interconnects in this study. SiCxNy films with k values between 3.0 and 3.5 were fabricated at T≦ 200 o C, and k~4.0-4.5 at 300-400 °C. Precursors with vinyl groups yielded SiCxNy films with low leakage, excellent optical transmittance and high mechanical strength due to the formation of cross-linked Si-(CH2)n-Si linkages.

Indiana University-Purdue University Indianapolis (IUPUI) / While most sealants available are resin-based, glass ionomer-based cements can be used as sealants, with the advantage of being more tolerant to moisture during placement and of releasing fluoride. The objective of this study was to evaluate the influence of different fissure conditioning techniques on penetration and microleakage of glass ionomer (GI) and resin-modified glass ionomer cements (RMGI) used as sealants. Clinically sound extracted human molars were distributed into nine experimental groups (n = 15 each). Group 1 (control) was sealed with resin-based sealant (Delton) following clinically accepted techniques. Groups 2 through 6 were sealed with RMGI (Vitremer) after having the fissure conditioned with either polyacrylic acid (RMGI-control), 35-percent H3PO4, low viscosity 35-percent H3PO4 with a surfactant, self-etch conditioner, or 35-percent H3PO4 followed by self-etch conditioner. Groups 7 through 9 were sealed with GI sealant (Fuji Triage) after having the fissures conditioned with either polyacrylic acid (GI-control), 35- percent H3PO4 or low viscosity 35-percent H3PO4 with a surfactant. After aging through thermocycling (2500 cycles), specimens were incubated in methylene blue for four hours and sectioned at multiple locations. Digital images were obtained using a digital stereomicroscope, and microleakage was determined by scoring the dye penetration along the enamel-sealant interface. The penetration of the material was determined by calculating the percentage of the total length of the fissure penetrated by the material. Results: The use of self etch-conditioner significantly increased RMGI penetration, while surface conditioning with 35-percent phosphoric acid with surfactant significantly decreased microleakage of GI. The resin-based sealant placed after 35-percent phosphoric acid surface conditioning showed the best penetration and the least level of microleakage. In conclusion, results from this study suggest that the placement of glass ionomer-based sealants can be enhanced by modifying current conditioning methods.

Printed circuit board manufacturing involves subtractive copper (Cu) etching where fine features are developed with a specific spatial resolution and etch profile of the Cu interconnects. A UV-Vis ATR metrology, to characterize the chemical transitions, has been developed to monitor the state of the bath by an in-situ measurement. This method provides a direct correlation of the Cu etch bath and was able to predict a 35% lower etch rate that was not predicted by the three current monitoring methods (ORP, specific gravity, and conductivity). Application of this UV-Vis ATR probe confirmed that two industrial etch baths, in identical working conditions, confirmed a difference in Cu2+ concentration by the difference of the near IR 860nm peak. The scope of this probe allowed chemically specific monitoring of the Cu etch bath to achieve a successful regeneration for repeated use. Interlayer dielectrics (ILDs) provide mechanical and electrical stability to the 3D electrical interconnects found in IC devices. It is particularly important that the structural support is created properly in the multilayered architecture to prevent the electrical cross signaling in short range distances. A combined multiple internal reflection and transmission FTIR has been employed for the characterization of silicon oxycarbonitride (SiOCN) films. These dielectric low-k films incorporate various functional groups bonded to silicon and require chemical bonding insight in the transformation and curing process. Distinct SiOx bonding patterns were differentiated, and the structure of the films can be predicted based on the amount of Si network and caged species. Further optimization of the FTIR analysis must minimize interference from moisture that can impact the judgement of peak heights. To accommodate this, a high-quality glove box was designed for dry air feedthrough to achieve a 95% moisture reduction during analysis, where less than 0.1 mAbs of moisture is detected in the spectra (without additional correction). The glove box allows for the rapid analysis of multiple sample throughput to outpace alternative characterization methods while retaining low spectral noise and a dry environment for 24/7 analysis. There is a great need to identify new catalysts that are suitable for tackling current economic demands, one of which is the nitrogen reduction reaction (NRR). The development of the surface enhanced infrared absorption spectroscopy (SEIRAS) has been applied to characterize the NRR mechanisms on the vanadium oxynitride electrocatalyst. Electrochemical measurements demonstrate NRR activity that is up to three times greater in the presence of N2 than the control Ar. FTIR operando suggests that a considerable number of intermediates were formed and continued to increase in absorbing value under an applied potential of -0.8 V vs Ag/AgCl. XPS results of the post-NRR film suggest a restricting of the film where vanadium oxynitride films are prone to instabilities under the possible MvK mechanism. After 90 minutes of NRR, the NH3 generated was approximately 0.01 ppm was calculated for through the salicylate colorimetric method. On-going efforts are focusing on optimizing the vanadium oxynitride film by the tuning of the oxynitride ratios and crystalline properties to promote the formation of V≡N: during the nitrogen reduction reaction.