Graphene has many excellent optical, electrical and mechanical properties due to its unique two-dimensional structure. High-efficiency preparation of large area graphene film is the key to achieve its industrial applications. In this paper, an ultrafast quenching method was firstly carried out to flow a single pulse current through the surface of a Si wafer with a size of 10 mm × 10 mm for growing fully covered graphene film. The wafer surface was firstly coated with a 5-nm-thick carbon layer and then a 25-nm-thick nickel layer by magnetron sputtering. The optimum quenching conditions are a pulse current of 10 A and a pulse width of 2 s. The thus-prepared few-layered graphene film was proved to cover the substrate fully, showing a high conductivity. Our method is simple and highly efficient and does not need any high-power equipment. It is not limited by the size of the heating facility due to its self-heating feature, providing the potential to scale up the size of the substrates easily. Furthermore, this method can be applied to a variety of dielectric substrates, such as glass and quartz. Graphene, a two-dimensional honeycomb network crystal with monolayer atomic thickness, is favored by scientists all over the world for its excellent and unique optical, electrical, thermal, mechanical and other physical properties. Graphene can be used as an ideal material in fields such as multifunctional composites, organic optoelectronic materials, hydrogen storage materials, supercapacitors and microelectronic devices, electromagnetic attenuation materials and so on ,2,3,4. I2 in 3–6 s on a glass substrate pre-coated with a 5–28-nm-thick Ni film covered with olive oil [Currently, people tend to obtain large area graphene in an economical synthesis method to realize its promising industrial applications. The CVD method usually uses a single crystal Cu, Ni or alloy substrate, as well as polycrystalline metal substrate with specific crystal plane, to act as catalysts to promote the growth of graphene, then the grown graphene generally needs to be transferred to a target material. It is easy to cause defects such as wrinkles, breakages and contaminants in the transfer process, which greatly reduce the properties of the obtained graphene ,15,16,17live oil . HoweverIn general, the current growth methods for large area graphene are mainly restricted by the film transfer process, the size of furnace chamber and the high-power heat source for industrial applications. In our previous work, an ultrafast quenching method was reported to make graphene functional Ni tips using a pulse current . In this2 on Si substrate) is shown in −1, the G peak near 1581 cm−1 and the 2D peak near 2708 cm−1. Compared with the G and 2D peaks of single-layered graphene, the G peak of as-grown graphene film shifts to a lower wavenumber, while the 2D peak shifts to a higher wavenumber, which prove that few-layered graphene has been grown [2D/IG is less than 1, also implicating that the graphene produced was few-layered. The above results prove that few-layered graphene is almost fully covered on the surface of the sample. The quality of as-grown graphene, as well as the morphology of the surface of quenched Si wafer, was similar to that of graphene synthesized by laser direct writing [The schematic diagram of the experimental set-up for ultrafast growth of large area graphene on Si wafer . The calculation formula is as follows:F is the correction coefficient. The Si wafer is square and the ratio of the sample lateral size to the probe spacing is 10; the correction coefficient is 0.927. The measured and corrected values of five sets of points were 50.3167 Ω·sq−1, 44.4257 Ω·sq−1, 50.0836 Ω·sq−1, 62.0398 Ω·sq−1, 62.751 Ω·sq−1, respectively. These resistance values are more than one order smaller than those of the graphene glasses synthesized by CVD (~1000 Ω·sq−1) [−1) [−1) showed a good electrical conductivity of the graphene-functionalized Si substrate, indicating the formation of large area and continuous graphene on Si. This agrees with the above Raman results. Ω·sq−1)  and four−1) [−1) . The aveOur method is simple and highly efficient. The Joule heat produced by a pulse current within 2 s does not need any high-power equipment used for growth graphene. More importantly, it is not limited by the size of the heating facility due to its self-heating feature, providing the potential to scale up the size of the substrates easily.2D/IG is around 1, which proves bilayer graphene has been grown in most areas of the holes. The value of ID/IG in the blue Raman spectrum is obviously bigger than that in the red and green Raman spectra, suggesting that few-layer graphene on the surface of dendritic islands has more defects than the graphene on the holes.Raman spectra were obtained by a spectroscope integrated with a SEM to further analyze in situ the corresponding relationship between the surface composition and the microstructure of the film on the surface of quenched Si wafer. The optical microscope image a, the SE3C and two peaks at 288.9 eV and 286.6 eV can be assigned to hydroxy and carbonyl functional groups attached to the graphene film. For the Ni 2p region  by magnetron sputtering method.In our experiment, 5-nm-thick carbon thin film  and 25-nm-thick nickel thin film  were formed successively on the Si wafers  with a current of 10 A and a pulse width of 2 s was provided by an external power supply for ultrafast heating. As shown in The coated Si wafers were quenched by the following ultrafast quenching methods developed by us. As shown in the schematic diagram of the experimental set-up in Scanning electron microscopy  studies were performed on as-grown graphene film on Si wafer surface to observe the surface morphologies and the corresponding element composition. Raman spectroscopy  was used to measure the characteristics of graphene. Surface topography images were obtained using an atomic force microscope  and white light interferometer . The graphene film was identified by using a RISE Raman system with a Sigma 300 SEM instrument . The laser wavelength was 532 nm. The Raman mapping of graphene film was carried out with a grid spacing of 200 nm and an accumulation time of 1 s at each spot. Ni 2p and C 1s XPS spectra were recorded using an X-ray photoelectron spectroscopy . Al Kα radiation was used as an excitation source. The XPS analysis area was set to a diameter of 500 μm and the step size to 0.05 eV with a base pressure of 10−9 Pa during all measurements.−1. Our method is simple and highly efficient and does not need any high-power equipment. The sample can be self-heated by the pulse current without the need for an additional heating facility to provide heat; this provides the potential to scale up the synthesized graphene film by adjusting the pulse current or pulse width applied to a larger size of different substrates. Furthermore, this transfer-free method can be applied to a variety of dielectric substrates, such as glass, quartz, sapphire and so on. The thus-produced graphene-functionalized various substrates can be used for sensors, electrical heating devices, biological scaffolds, and so on.In this paper, we successfully grew a large area of graphene film on Si wafer using an ultrafast single pulse current quenching method. A single pulse current flew through the Ni layer on the surface of the Si wafer successively coated with a 5-nm-thick C layer and a 25-nm-thick Ni layer. During the process of quenching, nickel carbide was firstly generated at a lower temperature, then it decomposed into nickel atoms and carbon atoms with the temperature increasing (above 400 °C); the carbon atoms were converted into graphene at a higher temperature (around 1100 °C). The optimal quenching condition is a pulse current of 10 A and a pulse width of 2 s. The thus-prepared few-layered graphene film on the Si wafers proved to cover the substrate fully with a size of 10 mm × 10 mm. Moreover, it showed a high conductivity with an average sheet resistance of about 53.9 Ω·sq


Fluorescence excitation spectroscopy at cryogenic temperatures carried out on hybrid assemblies composed of photosynthetic complexes deposited on a monolayer graphene revealed that the efficiency of energy transfer to graphene strongly depended on the excitation wavelength. The efficiency of this energy transfer was greatly enhanced in the blue-green spectral region. We observed clear resonance-like behavior for both a simple light-harvesting antenna containing only two chlorophyll molecules (PCP) and a large photochemically active reaction center associated with the light-harvesting antenna (PSI–LHCI), which pointed towards the general character of this effect. Graphene is a two-dimensional hexagonal lattice of carbon atoms in sp2 hybridization. This structure yields unique electrical or thermal properties, which are a direct consequence of the energy band structure, i.e., linear dispersion relation in the vicinity of Dirac points ,2, in adEnergy transfer in hybrid nanostructures that include graphene as the energy/charge acceptor has been studied for a variety of emitters, including molecules, polymers, and semiconductor nanocrystals, both in solution and in a layer geometry ,4. The pRecently, research has focused on the energy transfer in hybrid graphene assemblies has been extended towards systems that are more complex than molecules or nanocrystals, such as the natural pigment–protein complexes that take part in photosynthesis ,7. Such a-protein (PCP), is that fluorescence decay times measured for PCP deposited on graphene change with the excitation wavelength. Specifically, it was shown that upon excitation with 405 nm, the decay times were substantially shorter than those obtained with 630 nm excitation [An important issue that needs to be addressed when photosynthetic proteins are deposited on various nanostructures relates to the modifications of the optical properties of such hybrid systems due to mutual interactions between the components. Among the most surprising effects encountered for relatively simple light-harvesting antennae, such as peridinin-chlorophyll citation . This recitation ,47, is ia pair, where charge separation occurred.In this work, we aimed at precise determination of the wavelength dependence of the energy transfer efficiency in a hybrid structure in which photosynthetic complexes of various size, composition, and function were deposited on a monolayer graphene. First, we designed and performed a systematic fluorescence excitation microscopy analysis, where the emission intensity was monitored for varying excitation wavelengths. Second, we carried out this analysis both for the PCP complex and for a photosystem I with its associated light-harvesting antenna (PSI–LHCI), that has been previously used in various types of biohybrid solar energy conversion devices ,23,28,48The results of fluorescence excitation microscopy measurements indicated that for both photosynthetic proteins (PCP and PSI–LHCI), a substantial reduction in fluorescence intensity occurred upon excitation into the blue-green spectral region. Importantly, the spectral dependence of the emission intensity exhibited a resonance-type character. These results point toward a more complex role of graphene in assemblies in which both energy transfer and tightly focused illumination take place.a, were visible in the absorption spectrum of PCP . This, along with close resemblance between absorption and excitation spectra, indicated highly efficient energy transfer between Pers and Chls, reaching 90% [In hing 90% ,50,51,52a in light-harvesting; however contributions from Cars were also clearly visible, mostly in the green spectral range. In the case of PSI–LHCI complex, the Chl a molecules were responsible for fluorescence emission (red curve), although there were different subpopulations of these fluorophores present in the spectra, as suggested by significant broadening of the emission spectrum. Energy pathways within the PSI–LHCI complex and associated kinetics have been studied previously [Compared to PCP, the PSI–LHCI complex was much larger, containing nearly 200 cofactors enclosed within the protein scaffold ,54,55. Teviously ,53,56.The optical properties of graphene are unique in the sense that it features flat absorption of light across the visible spectral range, and thus, it can be considered as an ideal energy absorber. Our recent investigation of energy coupling between PCP complexes and graphene indicated that the fluorescence decay time depended on the excitation wavelength . This obIn order to systematically study the excitation wavelength dependence on the emission properties of photosynthetic complexes deposited on a graphene monolayer, we conducted a photoluminescence excitation experiment using a microscope objective for both excitation and light collection. By tuning the excitation wavelength, we measured fluorescence spectra and extracted emission intensities. There are two important comments needed before the discussion of the results. First of all, it was necessary to perform such an experiment in a microscopic setup, as we wanted to probe only these complexes that were in the vicinity of graphene. This imposed another criterion that needs to be fulfilled, namely, the very small thickness of the PVA layer containing the photosynthetic complexes. On the other hand, pigment–protein complexes are highly suitable for studying energy transfer processes, as the protein scaffold itself provides a spacer between the pigments and graphene, which, while not very thick, is sufficient to partially inhibit the energy transfer. In other words, should the pigment molecules be placed directly onto graphene, the efficiency of the energy transfer would be extremely, high leading to essentially complete quenching of fluorescence emission, regardless of the experimental conditions ,5,57.The emission intensities extracted by integrating the spectra on a graphene monolayer and on glass for PCP and PSI–LHCI complexes are compared in In contrast, the excitation spectrum of PCP complexes on graphene was radically different, in that a substantial and systematic decrease in emission intensity was observed for the blue-green spectral range. The emission intensity seemed to recover for the wavelengths shorter than 400 nm. The experiment was repeated for more than 10 spots on each sample, and the result was always the same as shown in Similar experiments performed for PSI–LHCI on graphene yielded qualitatively identical results see b. This iBy dividing the excitation spectra measured for photosynthetic complexes deposited on graphene by the corresponding reference, we gained insight into the character of this wavelength-dependent interaction between both modules of the hybrid assembly. As shown in ® . For both types of photosynthetic pigment–protein complexes, we used single-layer graphene (SLG) deposited on 1 cm × 1 cm p-doped silicon (p-Si) substrates covered with a 285 nm thick silicon dioxide layer. In the case of SLG, 97% of the surface was a monolayer graphene. The presence of graphene on the p-Si substrate was confirmed by Raman spectroscopy (not shown).Graphene substrates were purchased from Graphene SupermarketDinoflagellates and a PSI–LHCI complex from a red microalga, Cyanidioschyzon merolae. Aqueous solution of PCP from Amphidinium carterae was purchased from BD Pharmingen . The PCP complexes contained only 10 pigments: 8 peridinins (Pers) and 2 chlorophyll (Chl) a molecules [a because of very efficient energy transfer from Pers to Chl a. The PSI–LHCI complexes from C. merolae contained 157–159 Chl a molecules [C. merolae culture growth, thylakoid isolation, solubilization, and PSI–LHCI complex purification, described in detail previously [w/v) glycerol, 0.03% (w/v) DDM). This was followed by an anion exchange chromatography step using a UNOTM Q12 column [a, snap-frozen in liquid N2, and stored at −80 °C prior to use. The absorption of the PSI–LHCI complex is very broad; thus, similar ranges of excitation wavelengths were applied for both samples.For the optical experiments, we used two photosynthetic complexes: a water-soluble PCP light-harvesting antenna present in olecules ,59,60,61olecules ,54 and 3olecules ,54,62 aneviously ,55. At tThe samples were prepared as follows: the stock solution of PCP complexes was further diluted to the concentration of 0.05 mg/mL with 0.2% polyvinyl alcohol (PVA). The solution was then spin-coated on the graphene substrate (30 µL at 17 rps). The PSI–LHCI complexes (0.02 mg/mL) were suspended in a buffer composed of 40 mM HEPES, 3 mM CaCl2, and 0.03% DDM, with pH 8.0; resuspended in 0.2% PVA; then spin-coated as above. The reference samples consisted of the same concentration for each pigment–protein complex that was spin-coated onto a glass coverslip.Absorption, excitation, and emission spectra in solution were measured using a Varian Cary 50 spectrophotometer and Horiba Jobin Yvon Fluorolog 3 spectrofluorometer , respectively. The optical properties of the hybrid nanostructures composed of pigment–protein complexes embedded in a PVA matrix on a monolayer graphene were studied using photoluminescence excitation (PLE) microscopy by measuring sequences of emission spectra for varied excitation wavelengths. The experiment was performed in a back-scattering geometry. For excitation, the frequency-doubled output of an optical parametric oscillator (OPO), synchronously pumped by a mode-locked Ti:sapphire laser or the second harmonic (SH) of the mode-locked Ti:sapphire laser, was used. The typical temporal pulse width was 140 fs, with a repetition rate of 80 MHz. The laser beam was focused on the sample surface by Mitutoyo M PlanApo 50 × objective (NA 0.55) . To avoid photobleaching, the samples were placed in a liquid helium cryostat at 5 K during the entire measurement. In order to filter out the emission of photo-synthetic complexes, we used a set of suitable optical filters . The emission was detected using a CCD camera coupled to an Acton SP2500 monochromator  equipped with a grating with 600 lines/mm and blaze at 700 nm.In this work, we systematically studied the wavelength dependence of the energy transfer between two types of photosynthetic complexes and graphene. The results of microscopic fluorescence excitation spectroscopy indicated that in the blue-green spectral region, the efficiency of the energy transfer was substantially increased compared with that in other wavelengths. This phenomenon, which was proven for both simple light-harvesting pigment–protein complexes and photochemically active reaction centers, opens the unexplored field of tuning the properties of hybrid graphene nanostructures for optimized optoelectronics and photovoltaics applications.


MoP nanorod-array catalysts were directly synthesized on graphene passivated silicon photocathodes without secondary phase.Mo-O-C covalent bondings and energy band bending at heterointerfaces facilitate the electron transfer to the reaction sites.Numerous catalytic sites and drastically enhanced anti-reflectance of MoP nanorods contribute to the high solar energy conversion efficiency.−2 at 0 V versus RHE and high stability. Besides, low dependence on pH and temperature is observed with MoP nanorods incorporated photocathodes, which is desirable for practical use as a part of PEC cells. These results indicate that the direct synthesis of TMPs and TMDs enabled by graphene interlayer is a new promising way to fabricate Si-based photocathodes with high-quality interfaces and superior HER performance.Transition metal phosphides (TMPs) and transition metal dichalcogenides (TMDs) have been widely investigated as photoelectrochemical (PEC) catalysts for hydrogen evolution reaction (HER). Using high-temperature processes to get crystallized compounds with large-area uniformity, it is still challenging to directly synthesize these catalysts on silicon photocathodes due to chemical incompatibility at the heterointerface. Here, a graphene interlayer is applied between p-Si and MoP nanorods to enable fully engineered interfaces without forming a metallic secondary compound that absorbs a parasitic light and provides an inefficient electron path for hydrogen evolution. Furthermore, the graphene facilitates the photogenerated electrons to rapidly transfer by creating Mo-O-C covalent bondings and energetically favorable band bending. With a bridging role of graphene, numerous active sites and anti-reflectance of MoP nanorods lead to significantly improved PEC-HER performance with a high photocurrent density of 21.8 mA cmThe online version contains supplementary material available at (10.1007/s40820-021-00605-7). GH). The other problem is that it suffers from photo-corrosion in aqueous solution because of the thermodynamical reduction potential of silicon adjacent to water reduction potential (H+/H2) [Hydrogen is expected to become sustainable future energy owing to zero-emission, non-toxicity, and large energy density . However (H+/H2) .2 [2 [2 [2/WS2/WSe2 [xCly  [xSi induced the parasitic light absorption resulting in the low photocurrent density. Also, Hasani et al. [3 film on p-Si, spin-coating (NH4)2MoS2 on it, and converting them into MoS2 film. Even though the uniformly distributed and thickness-controlled thin films are synthesized, the photocathodes exhibited leakage current density arising from interfacial secondary phase between silicon and MoS2 [By employing photoelectrochemical catalysts, both the interfacial reactions can be expedited via lowering the activation energy, and the silicon can be protected from photoactive dissolution . Recentl2 , WS2 [192 [2  synthesi2 [2 [2 , MoS2/WSWS2/WSe2 , MoQxCly= S, Se) , and CoP= S, Se)  have bee= S, Se)  directlyi et al.  developeand MoS2 , 28. As xSi layer does not exist. As a result, most of the incident light can be delivered to silicon photocathodes as graphene only absorbs 2.8–4.3% of visible light [−2 at 0 V versus a reversible hydrogen electrode (RHE) and enhanced long-term stability. While MoS2 NRs/graphene/p-Si shows a dramatic degradation with increasing pH, MoP NRs/graphene/p-Si was considerably stable to changes in pH. Besides, it maintained high PEC performance with increasing electrolyte temperature up to 70 ℃. Using graphene interlayer, not only MoP but also various catalysts such as nickel phosphide and cobalt phosphide can be directly synthesized on silicon photoelectrode. This study demonstrates the huge potential of the graphene to solve the interfacial incompatibility and will contribute to a large-scale direct synthesis of nanostructured transition metal-based materials exhibiting an efficient hydrogen production performance.Here, we demonstrate the direct growth of highly uniform MoP catalysts on p-Si photocathodes by applying the graphene interlayer at the heterointerface. As graphene completely suppresses the chemical reaction between the silicon and Mo atoms, the Mole light . Also, nle light , 31. In 2 at 70 sccm with a total pressure of 5 Torr; then, monolayer graphene film was grown at 1040 °C for 2 h by additionally introducing 1% CH4 diluted in H2 at 2 sccm. During the cooling process after growth, the 1% CH4 diluted in H2 gas injection was kept until the film had cooled to 600 °C, then only H2 was introduced until the temperature reached under 150 °C to allow unloading of the sample.Monolayer graphene film was grown by chemical vapor deposition on Cu foil . First, the Cu foil was annealed at 1030 °C for 4 h under flow of H++-Si were cut into pieces with a size of 1.5 × 1.5 cm2. The silicon pieces were cleaned using acetone, isopropyl alcohol, and DI water by ultrasonication for 15 min at each step. To remove the native oxide layer, cleaned Si wafers were soaked into HF for 30 s. The PMMA/graphene layer was transferred onto the silicon surface and PMMA was removed by acetone at 60 ℃ for 15 min. MoP NRs/Gr/p-Si photocathodes were fabricated by MoO3 precursor (Taewon Co.) deposition and high-temperature phosphorization process. Vertically aligned molybdenum trioxide nanorods with 100 nm thickness were deposited on graphene/p-Si photocathodes by glancing angle deposition (GLAD) electron beam evaporator. The substrates were tilted at an angle of 80° and rotated with a speed of 80 rpm. The base pressure and growth rates were 1.0 × 10–6 mTorr and 1.5 Å s−1, respectively. By simple phosphorization process, MoO3 nanorods turned into MoP nanorods. High-purity H2 gases mixed with N2 gases were utilized for this process in a thermal chemical vapor deposition (CVD) system. At first, the temperature of the CVD chamber was increased to 500 ℃ and maintained for 15 min under the flow of H2 and N2 at 0.85 Torr. The flow rate of H2 and N2 was 100 and 500 cm3 min−1, respectively, measured by mass flow controllers. The temperature was increased to 900 ℃ maintaining for 15 min. The sublimation of phosphorus powder  proceeded in the other heating zone. The temperature of the sublimation region was set at 400 ℃ and 0.7 g of powder was used.The boron-doped (100) p-type silicon wafers (1–10 Ω cm) for MoP nanorods(NRs)/graphene(Gr)/p-Si photocathodes and the conductive arsenic-doped (100) n-type silicon wafers (0.001–0.005 Ω cm) for MoP NRs/Gr/n3 film with intended thickness of 5 nm was deposited on graphene/p-Si and HF-treated bare p-Si for the fabrication of MoP film/Gr/p-Si and MoP NPs/p-Si, respectively. During deposition, the substrates were kept horizontal without rotation. The base pressure and growth rates were 1.0 × 10–6 mTorr and 0.1 Å s−1, respectively. After film deposition, the phosphorization process with the temperature of 700 ℃ in H2 and N2 (100 and 500 cm3 min−1) atmosphere proceeded for 15 min. The other heating zone where 0.7 g of phosphorus powder sublimates was maintained at 400 ℃.The MoO3, Fe2O3, CoO3, and NiO with intended thickness of 5 nm were deposited on graphene/p-Si for the synthesis of CuPx, WPx, FePx, CoPx, and NiPx catalysts. Also, MoO3 and WO3 film with 5 nm thickness were deposited to synthesize MoS2 and WS2 on graphene/p-Si. During the phosphorization and sulfurization process, the temperature of the CVD furnace was maintained at 700 ℃ for CuPx, CoPx, WS2, and 900 ℃ for WPx, FePx, NiPx, MoS2 catalysts. The temperature of the sublimation region was set at 400 ℃ with 0.7 g of phosphorus powder and 300 ℃ with 0.7 g of sulfur powder.The metal oxide films of CuO, WOThe Raman spectra were obtained using Lab RAM HR  with 532 nm excitation wavelength. The FT-IR spectra measurements were conducted with Nicolet iS50 (Thermo Fisher Scientific). The surface morphology and cross-sectional images were acquired by FE-SEM . Low magnification, high-resolution images, and EDS data were obtained with TEM . The chemical bonding states and work function of MoP nanorods/graphene/p-Si were characterized by XPS . The crystal structures of MoP film and MoP nanorods were analyzed by XRD . The reflectance and absorption spectra were obtained with UV–visible spectroscopy . The electrical properties of the deposited catalysts were measured by an Agilent 4156C semiconductor analyzer.2SO4 standard solution was used as an electrolyte. A quartz vessel showing high transmittance for UV wavelengths of 200 nm or less was utilized. A Xe arc lamp calibrated to 100 mW cm−2 (AM 1.5 G condition) was used as a light source. In the process of the linear sweep voltammogram (LSV) measurements, the photocathodes were polarized at a scan rate of 10 mV s−1 under AM 1.5 G. The IPCE data were obtained with a monochromator (MonoRa150) and the potential of 0 V vs. RHE was applied. Electrochemical impedance spectroscopy (EIS) was carried out with the frequency from 250 kHz to 1 Hz using 10 mV alternating current.The photoelectrochemical properties of as-synthesized photocathodes were measured with a potentiostat  using a three-electrode system consisting of a saturated calomel electrode (SCE) as the reference electrode and a graphite rod as the counter electrode. 0.5 M HxSi layer, a secondary compound of silicon and Mo atoms, is laterally formed between p-Si and MoP catalyst. It induces parasitic light absorption resulting in a reduction of photogenerated charges. In addition, due to its low shunt resistance, some of the light-generated electrons are trapped in the metallic layer and can not reach the MoP catalyst. As unintended hydrogen evolution reaction occurs at the secondary phase with no suitable reaction sites, the photocathode shows low catalytic activity and PEC performance. One possibility for hydrogen production to be active in silicide layer may be a spillover effect in which hydrogen species adsorbed to reaction sites with negative ΔGH diffuse to the sites with positive ΔGH [GH of P sites, the most catalytic sites of MoP, changes from negative to positive when H coverage increases, which means that as soon as the hydrogen is adsorbed, it is desorbed immediately before the spillover effect occurs [In Fig. tive ΔGH . Howevert occurs . As a re2-hybridized lattice is grown on copper foil with large grain size  [3 nanorods are deposited on graphene with a thickness of 100 nm. MoP nanorod-array catalysts are finally synthesized on graphene passivated silicon wafer by vapor phase phosphorization of MoO3 precursor. As for the comparative group, MoP nanoparticles and MoP film are synthesized on p-Si and graphene/p-Si, respectively . The photographic images of centimeter-scale Graphene/p-Si and MoP NRs/Gr/p-Si is represented in Fig. S3a, b. It indicates that the graphene monolayer is uniformly transferred to p-Si substrates, and MoP nanorod-arrays are successfully grown on graphene.Figure ig. S2a) . It is tH and acting as “H delivery” [3 precursors are successfully transformed into MoP catalysts without remaining MoO3 layers. Moreover, the formation of MoxSi layers is prevented by using graphene passivation.The vertically aligned nanorod structure is identified by SEM images. In Fig. elivery” , 38, incelivery” . The hig3+ 3d3/2/Mo3+ 3d5/2) and 130.5 eV/129.6 eV (P 2p1/2/P 2p3/2) are ascribed to MoP [3, MoO2, and PO43− caused by surface oxidation [The surface constituents and chemical nature of MoP nanorods and film are further investigated by X-ray photoelectron spectroscopy (XPS). The full XPS spectra show the existence of Mo, P, O, and C . The XPS profiles of Mo 3d and P 2p of both MoP film and MoP nanorods are presented in Fig. S6b and c. Two pairs of doublets at 231.5 eV/228.4 eV  are provided in Fig. S9.Secondly, the electrical interaction between graphene and silicon photocathode is analyzed using ultraviolet photoelectron spectroscopy (UPS) to demonstrate the band alignment of heterostructure in hydrogen production. In Fig. 2 NRs/Gr/p-Si, MoP NPs/p-Si, and MoP film/Gr/p-Si is carried out under a simulated air mass 1.5 G condition with a standard three-electrode set-up using 0.5 M H2SO4 electrolyte. The graphite rod is used as a counter electrode. As shown in current density versus potential (J-V) curves in Fig. −2, respectively. However, from potential above − 0.4 V versus RHE, a discernible leakage current is shown due to a low shunt resistance caused by MoxSi layer between the crystalline silicon and MoP nanoparticles [2/Mo/MoxSi/n+p-Si photocathode fabricated by Benck et al. [The PEC characterization of MoP NRs/Gr/p-Si photocathode compared to bare p-Si, graphene/p-Si, MoSarticles . Though k et al. , it is c−2 and a photocurrent density of 21.8 mA cm−2 at 0 V versus RHE. The 100 nm thickness of MoP nanorod-arrays is an optimized value to get maximum photocurrent density at 0 V versus RHE. Figure S12 indicates that the photocathode with 100 nm MoP NRs shows the highest photocurrent density at 0 V versus RHE compared to the photocathodes with 70 and 130 nm MoP NRs catalysts.In this respect, by applying the graphene interlayer, we can completely suppress the formation of the metallic secondary phase as seen that no leakage current is visible with MoP film/Gr/p-Si and MoP NRs/Gr/p-Si photocathodes. In Fig. S11, resistance analysis clearly shows that the leakage current flowing laterally through the silicide layers can be effectively suppressed by applying graphene interlayer. Though the graphene shows no remarkable PEC performance as catalysts, MoP film/Gr/p-Si and MoP NRs/Gr/p-Si photocathodes show the dramatic improvement in PEC performance. Mainly, MoP NRs/Gr/p-Si photocathode exhibits a remarkable catalytic activity for the HER with an onset potential of 0.24 V vs. RHE to reach -1 mA cmRct) and constant phase elements (CPEs). The smaller arcs in Nyquist plots indicate the lower charge transfer resistance at each interface. Compared to each semicircle of MoP NPs/p-Si photocathode, the photocathodes to which the graphene interlayer is applied show smaller arcs. Notably, the resistances of MoP NRs/Gr/p-Si photocathode at each interface are remarkably decreased.Electrochemical impedance spectroscopy (EIS) measurements were conducted to understand the PEC performance concerning charge transfer resistance, as shown in Fig. Rct,1 of bare p-Si shows two orders of magnitude higher than the total resistance of other MoP deposited photocathodes. It reflects that molybdenum phosphide enables the electrons to move faster at the interfaces and provides a large number of active sites for energetic kinetics. For the resistances at MoP/electrolyte interface, Rct,3 of MoP NRs/Gr/p-Si photocathode exhibits the lowest value compared to Rct,3 of MoP film/Gr/p-Si and Rct,2 of MoP NPs/p-Si photocathodes. It confirms that for the nanorod-structured MoP, electron transfer to the redox couples is enhanced, which is ascribed to the highly-exposed 1D structure showing the shortest distance towards MoP/electrolyte interface and the largest amount of active sites. Moreover, to identify the synergistic effects of graphene, we compared the resistances at heterointerfaces with and without graphene. The sum of Rct,1 and Rct,2 of both the graphene-passivated photocathodes is lower than Rct,1 of MoP NPs/p-Si photocathode, which provides compelling evidence that the graphene can act as a highway to help the electrons move from p-Si to MoP catalysts. This result is in good agreement with the formation of Mo-O-C covalent bondings and energetically favorable band bending identified by Raman, FT-IR spectroscopy, and UPS.The exact values of fitted charge transfer resistance corresponding to each interface are tabulated in Table The summarized charge transport resistance values of bare p-Si, MoP NPs/p-Si, MoP film/Gr/p-Si, and MoP NRs/Gr/p-Si photocathodes.The capability of photocathodes to convert the incident photons to electrical current is investigated by the incident photon-to-current conversion efficiency (IPCE) at an applied bias of 0 V versus RHE, as shown in Fig. −2 at 0 V versus RHE is not endured 80% of photocurrent density until 1 h. As the catalysts do not fully cover the silicon surface, the formation of an insulating layer is accelerated, hindering charge transfer and finally shutting down the overall activity. On the other hand, it is found that the long-term stability of over 10 h is maintained with the MoP film and MoP nanorod-arrays directly synthesized on graphene. For the MoP NRs/Gr/p-Si photocathode, significantly, the photocurrent degradation is considerably suppressed with retaining over 88% of the performance for 10 h. As shown in Fig. S13, the SEM image reveals that MoP nanorod-arrays show no structural change after a 10-h stability test. Interestingly, it is estimated that the total amount of hydrogen generated at the wafer scale for 10 h is apparently larger than that required for the synthesis of MoP nanorod catalysts, but much lower than that required for the synthesis of graphene in Fig. S13.The stability of bare p-Si, MoP NPs/p-Si, MoP film/Gr/p-Si, and MoP NRs/Gr/p-Si photocathodes are evaluated by chronoamperometric measurements in Fig. The Faradaic efficiency is obtained by conducting a gas chromatography (GC) measurement that collects the evolved hydrogen gas. In Fig. 2/p-Si NWs [xCly/n+pp+-Si MPs [To compare the PEC performance of MoP NRs/Gr/p-Si photocathode with that of state-of-the-art photocathodes synthesized by the in-vacuum high-temperature process, photocurrent density at 0 V versus RHE and long-term stability are plotted in Fig. p-Si NWs  and MoSx+-Si MPs  photocat2 NRs/Gr/p-Si photocathodes changes at each voltage as the pH changes from 0.26 to 2. The pH of the electrolyte is controlled by mixing 0.5 M H2SO4 with neutral DI water. In the case of MoS2 nanorod-array catalysts (inset), considering the contours with the current density of 1, 10, and 20 mA cm−2, the potential required to obtain each current density value dramatically increases as the acidity of electrolyte becomes weaker. On the other hand, the MoP nanorod-arrays catalysts show no definite change up to pH 1.2, and after that, the PEC performance gradually weakened. Similarly, the current density variation depending on electrolyte temperature is plotted in Fig. For further practical use of MoP NRs/Gr/p-Si photocathode as part of PEC cell, it needs to be operated with high reliability against variations in the pH and temperature of electrolyte. In Fig. 2 having a 2D atomic structure. MoS2 nanorod-arrays and film are synthesized in the same process with MoP nanorod-arrays and MoP film, respectively, except for using sulfur powder. The Raman and XRD spectrums of MoS2 nanorods are provided in Fig. S14a, b. As shown in Fig. S14c, there is a noticeable degradation in PEC performance when the nanorod structure is applied to MoS2. Besides, it does not maintain its activity for a long time . Considering that MoS2 has a layered crystal structure held by weak van der Waals force [We also investigated how the nanorod structure, which caused a significant increase in PEC performance of MoP having a 3D atomic structure, affects that of MoSls force , the pho++-Si wafers are used as metallic cathodes. In Fig. S15a, MoP nanorod-array catalysts exhibit a smaller onset potential and overpotential at a current density of 10 mA cm−2 compared to MoP film. Also, the Tafel slope for MoP NRs/Gr/n++-Si is 97.19 mV per decade, which is lower than the values of 108.99 mV per decade for MoP film/Gr/n++-Si, as shown in Fig. S15b. From these result, a larger amount of surface active sites is exposed and faster catalytic activity occurs for MoP nanorods than film electrocatalyst. Since the thickness of our MoP nanorods catalysts is optimized for the PEC system, an enhanced electrocatalytic performance can be obtained by increasing the thickness in the EC system.The electrochemical (EC) HER performances of MoP-based catalysts on graphene/p-Si are also investigated in Fig. S15 and Table S2. To achieve graphene-based direct growth on silicon, highly doped nx, WPx, FePx, CoPx, NiPx, MoS2, and WS2 on graphene/p-Si substrates. They were prepared by phosphorization of CuO, WO3, Fe2O3, CoO3, NiO, and sulfurization of MoO3, WO3. The synthesis temperature of CuPx, CoPx, and WS2 is 700 ℃, while that of WPx, FePx, NiPx, and MoS2 is 900 ℃. In Fig. J-V) curves of TMPs/Gr/p-Si photocathodes under a simulated air mass 1.5 G condition are shown. For all the TMPs, the onset potentials are shifted toward the anodic direction compared to bare p-Si, indicating that the various TMPs work as efficient PEC catalysts on graphene/p-Si photocathodes. Among them, NiPx and CoPx exhibit a remarkable current density of 12.9 and 6.1 mA cm−2 at 0 V vs. RHE, respectively. Also, Fig. J-V) curves of TMDs/Gr/p-Si photocathodes. Similarly, the onset potentials of MoS2/Gr/p-Si and WS2/Gr/p-Si photocathodes are shifted toward the anodic direction. If the thickness control or nanostructuring is achieved with these catalysts, the enhanced photoelectrochemical activity will be obtained.To further demonstrate that the synergistic direct growth on graphene interlayer can be applied to various TMPs and TMDs, we have synthesized CuP−2 at 0 V versus RHE and long-term stability of over 10 h. Through the graphene passivation process, not only the secondary compound which absorbs a parasitic light and provides an inefficient electron path are prevented, but also the synergistic effects of Mo-O-C bondings and strong band bending enhanced the photogenerated electron transport. Benefiting from a large surface area exposing numerous active sites and anti-reflectance of MoP nanorods, the obtained photocathodes exhibited a high quantum efficiency. Furthermore, its high performance was maintained with the increase of pH and temperature. This study provides the framework to rationally design nanostructured PEC catalysts directly on graphene/p-Si photocathodes with high-quality interfaces and superior HER performance.We successfully demonstrated that MoP nanorod-array catalysts grown on graphene-passivated silicon photocathodes remarkably improve PEC-HER performance in balance with the high photocurrent density of 21.8 mA cmSupplementary file1 (PDF 1344 kb)


Xenografted athymic nude mice bearing 624-MEL PD-L1POS or PD-L1NEG tumors were injected with the tracer and ex vivo biodistribution was performed 1 h 20 min post-injection. Ideal 68Ga-labeling conditions were found at 50 °C for 15 min. [68Ga]Ga-NOTA-mal-hPD-L1 Nb was obtained in 80 ± 5% DC-RCY with a RCP > 99%, and was stable in injection buffer and human serum up to 3 h (>99% RCP). The in vitro characterization showed that the NOTA-functionalized Nb retained its affinity and specificity. Ex vivo biodistribution revealed a tracer uptake of 1.86 ± 0.67% IA/g in the positive tumors compared with 0.42 ± 0.04% IA/g in the negative tumors. Low background uptake was measured in the other organs and tissues, except for the kidneys and bladder, due to the expected excretion route of Nbs. The data obtained show that the site-specific 68Ga-labeled NOTA-mal-hPD-L1 Nb is a promising PET radio-immunotracer due to its ease of production, stability and specificity for PD-L1.Immune checkpoint inhibitors targeting the programmed cell death-1 (PD-1) and its ligand PD-L1 have proven to be efficient cancer therapies in a subset of patients. From all the patients with various cancer types, only 20% have a positive response. Being able to distinguish patients that do express PD-1/PD-L1 from patients that do not allows patients to benefit from a more personalized and efficient treatment of tumor lesion(s). Expression of PD-1 and PD-L1 is typically assessed via immunohistochemical detection in a tumor biopsy. However, this method does not take in account the expression heterogeneity within the lesion, nor the possible metastasis. To visualize whole-body PD-L1 expression by PET imaging, we developed a nanobody-based radio-immunotracer targeting PD-L1 site-specifically labeled with gallium-68. The cysteine-tagged nanobody was site-specifically conjugated with a maleimide -NOTA chelator and radiolabeling was tested at different nanobody concentrations and temperatures. Affinity and specificity of the tracer, referred to as [ Immune responses are managed through activatory and inhibitory signals at different checkpoints. Programmed cell death-protein-1 (PD-1) and its ligands, programmed death receptor ligands 1 and 2 , are a part of the inhibitory checkpoints modulating the activity of T lymphocytes ,4, and s68Ga, T1/2 = 68 min) that allowed non-invasive detection of PD-L1 positive tumor in xenografted mice Ga-NOTA-mal-hPD-L1 Nb tracer was able to target hPD-L1 positive tumors in vivo. Organ and tissue biodistribution results at 80 min post-injection (p.i.) are represented in 68Ga-labeled Nb showed higher uptake of 1.86 ± 0.67% IA/g (n = 12) in the positive tumors compared with 0.42 ± 0.03% IA/g (n = 6) in the negative tumors, which is significantly different (p = 0.0002). Kidney uptake was 27.9 ± 5.1% IA/g (n = 12) in the group bearing hPD-L1POS tumors. All other organs were at background level, as depicted in n = 12) and an average tumor-to-muscle ratio of 27.70 ± 12.59% (n = 12) were measured for the group bearing hPD-L1POS tumors. Flow cytometry (FC) analysis confirmed the hPD-L1 expression of the positive cells in tumors compared with the negative tumors  vs. 4.5 ± 0.9 mg/L (n = 2) vs. 11.2 ± 9.9 mg/L (n = 2), respectively). Maleimide-NOTA was site-specifically coupled to the hPD-L1 Nb bearing the Cys-tag, in similar recovery yields as for a random coupling on the lysines. Although, a cysteine–maleimide coupling requires an extra mild reduction step to ensure the thiol function of cysteine is free and no dimer and monomer capped with a glutathione are present. The reaction time remains similar as for the random coupling and is lower for the sortase-A mediated coupling .In particular, this technique can be applied to functionalize Nbs bearing a free cysteine in a Histerminus ,16. One ning Nbs . In the 68Ga-labeling of NOTA-mal-(hPD-L1) Nb required heating at 50 °C to reach similar DC-RCY as for the NCS-NOTA-coupled Nb , due to the difference in structure between the mal-NOTA and the NCS-NOTA used for the random coupling Ga-NOTA-mal-(hPD-L1) Nbs proved to be stable in injection buffer and in human serum up to 3 h of incubation. In vitro cell binding studies confirmed the functionality and specificity of [68Ga]Ga-NOTA-mal-(hPD-L1) Nbs. Stability during storage of the NOTA-mal-(hPD-L1) Nb at −20 °C in 0.1 M NH4OAc pH 7 was tested over two months. 68Ga-labeling remained equally efficient over time. Stability of the labeled compound in injection buffer, produced with the two months old NOTA-mal-(hPD-L1) Nb, showed that this radiolabeled Nb could also remain stable. These results are promising for clinical practice since the NOTA-conjugated Nb may be stored for long periods before being radiolabeled and used, although later time points remain to be tested.Ga-NOTA-mal-(hPD-L1) Nbs was significantly higher in the mice with hPD-L1POS tumors than with hPD-L1NEG tumors . The hPD-L1 expression in the dissected tumors was confirmed by FC. In the same tumor model, the tumor uptake was as similar to the currently reported [68Ga]Ga-NOTA-mal-(hPD-L1) as it was for the previously reported randomly and sortase-A mediated NOTA-coupled 68Ga-labeled Nb analogues ) Ga-NOTA-mal-(hPD-L1) Nb demonstrated a similar behavior to the two other analogues. One known main disadvantage is the loss in production efficiency compared with productions of His6-tag-containing only Nbs used in random labeling, although efficiency is comparable with the sortag-His6-tag-bearing Nb. Before clinical translation, the full His6-linker-Cys-tag should be optimized. This should be performed to, on one hand, reduce kidney retention (by removing the His6-tag or modifying the AAs in the linker) and, on the other hand, to improve the production yield by optimizing the linker (length and AAs). Finally, the process may be optimized for GMP production in yeast or E. coli.The tumor uptake of Ga-NOTA-mal-Nb; 15.2 ± 1.5 MBq, 39.6 GBq/μmol or 15.4 ± 0.6 MBq, 39.9 GBq/μmol, respectively. Apparent molar specific activities are reported for the time of injection. The biodistribution was evaluated at 80 min p.i. After euthanasia, main organs and tissues were isolated, weighed and counted against a standard of known activity using a γ-counter. The amount of radioactivity in organs and tissues was expressed as a percentage of the injected activity per gram (% IA/g), corrected for decay. A single cell suspension from the tumors was prepared and FC analysis was performed to characterize hPD-L1 expression .Results are expressed as mean ± SD. A non-parametric Mann–Whitney U test was carried out to compare data sets. Sample sizes and number of repetitions of experiments are indicated in the figure legends or in the materials and methods section. The number of asterisks in the figures indicates the statistical significance as follows: *, 68Ga-radionuclide. The 68Ga-labeling of NOTA-mal-conjugated Nb was efficient at 50 °C. The 68Ga-labeled Nb was stable and specific in vitro, and could specifically target hPD-L1 preclinically in vivo. Taken together, the 68Ga-labeled Nb via the mal–Cys chemistry is a promising PET imaging agent for future clinical assessment of PD-L1 expression.In this study, we have confirmed that our lead Nb targeting human PD-L1 could be efficiently coupled to mal-NOTA via the cysteine–maleimide strategy, yielding a homogenous product for site-specific incorporation of the Bridoux, J.; Broos, K.; Breckpot, K.; Xavier, C.; Lecocq, Q.; Keyaerts, M.; Devoogdt, N.; Raes, G.; Van Ginderachter, J. Human PD-L1-BINDING Immunoglobulins. No. PCT/EP2019/055133; WO/2019/166622; 6 September 2019.


A high-selectivity band pass filter with controllable attenuation based on graphene nanoplates is proposed in this paper. Graphene with controllable resistance has a good uniform attenuation effect to electric field intensity. The filter utilizes quarter wavelength stepped impedance resonators and mixed electromagnetic coupling to have compact circuits and high performance. The graphene nanoplates are loaded on the microstrip resonator to reduce the electric field intensity, which results in a flat attenuation in the passband. In addition, the filter has two transmission zeros, which lead to a strong selectivity. Finally, a high-selectivity bandpass filter with controllable attenuation is formed. By changing the bias voltage of graphene, a controllable attenuation of 1.64–11.13 dB can be achieved in the working passband centered at 1.36 GHz. In order to validate the concept, the prototype is fabricated and measured. The measurement results are in good agreement with the simulation results. The proposed high-selectivity bandpass filter with controllable attenuation based on graphene nanoplates has widely potential in reconfigurable wireless communication systems and radar systems due to its high integration and versatility. Graphene has attracted much attention due to its light weight, large surface area, excellent optical properties, and electrical properties. In recent years, significant advances have been made in the preparation methods of large-scale graphene ,2,3, proIn this paper, a high-selectivity bandpass filter with controllable attenuation based on graphene nanoplates is proposed, which can realize the function of tunable passband attenuation. First, an electromagnetic coupling high-selectivity filter composed of λ/4 step impedance resonators is designed . Then, tThe characteristics of graphene nanoplates, such as tunable resistivity, corrosion resistance, high temperature resistance, and ease of fabrication, make them a very important application prospect in microwave devices. In the fabrication process, graphene nanoplate dispersion is prepared at first. The specific fabrication procedure can be described as follows. Graphene nanoplates XF022-1 from a commercial company  are mixed with isopropyl alcohol at a concentration of 2.5 mg/mL. The mixture is sonicated for 40 min at 160 W. Graphene nanoplate dispersion is deposited at the specific locations of filter gaps by using a dropper and customized molds. When the isopropyl alcohol solution is completely vaporized, three pairs of graphene pads are formed. The resistance value of graphene nanoplates can be tunable by adjusting the bias voltage. Therefore, when the graphene nanoplates are loaded on the filter, the attenuation of the electric field can be tunable by controlling the bias voltage. m as shown in m as depicted in m and Lm. When the mixed electromagnetic coupling structure resonates at a certain frequency, the impedance will be infinity so as to produce a transmission zero (TZ). Because the coupling resonant frequency can be flexibly controlled, the TZs can be located on either side of the filter freely, which can effectively improve the filter’s passband selection characteristics. The simulation results shown in In order to study the effect of graphene nanoplates on the resonator, a second-order filter using λ/4 stepped impedance resonator (SIR) is designed as depicted in R. The relationship between the simulated value of the sheet resistance L and W are the length and width of graphene, respectively.First, a 400 Ω graphene nanoplate is loaded at a position with a small electric field strength, and the electric field distribution simulation diagram is shown in Before designing the model, a DC voltage source is used to power up the microstrip line with the graphene. The multimeter measures the DC resistance under bias current, and records the change in resistance as the voltage changes. The relationship between the resistance and the bias voltage is shown in The above mixed electromagnetic coupling filter only introduces transmission zeros in the high frequency stopband or low frequency stopband. The number of filter stages is also small and the out-of-band drop is slow, which is not suitable for high selectivity scenario. Higher-order filters can provide steeper transition bands to obtain a better square coefficient. In addition, constructing multiple sets of hybrids coupling structure can introduce multiple transmission zeros at the same time, thereby further improving the passband selection characteristics of the filter.In order to achieve practical application, a third-order SIR high-selectivity filter with tunable attenuation is constructed. Because the transmission zeros of the mixed electromagnetic coupling filter are individually controllable (discussed in The schematic diagram of a tunable resistance graphene-based bandpass filter with mixed electric and magnetic coupling is shown in The graphene nanoplates are regard as lumped resistors. When the value of R is high, graphene nanoplates are close to open circuit, resulting in small attenuation. By increasing the bias voltage, the value of R decreases and the absorptive of graphene nanoplates become more obvious, which lead to higher attenuation. In this paper, a high-selectivity bandpass filter with controllable attenuation based on graphene nanoplates is proposed. Applying different bias voltages to the graphene to maintain low reflection loss, the attenuation amplitude can be adjusted to more than 10 dB. Experiments have proved that controlling the bias voltage on graphene can change the resistance value of graphene, and achieve adjustable attenuation in the resonant structure. The measured results and the simulation results are basically consistent. The proposed tunable resistance graphene-based bandpass filter combines the functions of the filter and the attenuator well. It simplifies the building steps of the radio frequency system and reduces the production cost. The tunable resistance graphene-based bandpass filter design structure is simple and can be well transplanted to the design of other filters. It has very good application prospect in the development of the communication systems.


The following aspects have thus far remained unexplored: The interactional environment in which the construction occurs, how it is connected to the speaker’s embodied conduct, the way in which it contributes to mobilizing a response from the recipient, as well as the nature of this response. Our paper addresses these issues and shows that turn-final tu vois ‘you see’ is systematically produced with a final rising intonation and coupled with the speaker’s gaze directed to the recipient. This multimodal practice is recurrently deployed in turns conveying the speaker’s emotional stance, in turns performing a dispreferred action, like disagreeing, and in turns claiming insufficient knowledge. The response that is invited using this multimodal practice is distinctly tailored to each of these actions: an affiliative response, an aligning response, and a response addressing the prior speaker’s claim of insufficient knowledge from the recipient’s own point of view. By presenting an in-depth study of the action sequences in which tu vois ‘you see’ is employed, as well as of its multimodal packaging, this contribution highlights the prospective, i.e., response-mobilizing potential of this interactional resource and shows that its use entails sequential implications even when it accompanies actions that project only weakly a response from the recipient.One of the most frequent verbal expressions that people use when interacting with each other in French is you see’ . Drawing It also appeared to be most recurrently used in turn-final position . Previous studies on tu vois ‘you see’ in this position document only its use for marking the end of an utterance or for turn yielding by signaling the exit from the turn (see section “Background” infra). Complementing this research, our paper aims to provide a detailed account of the use of this construction in turn-final position, by exploring the conversational actions and also the participants’ systematic embodied conduct deployed in this sequential environment – something that has largely remained uninvestigated in the existing literature.The topic of this study has emerged naturally from the conversational data that we examined. Following tu vois ‘you see’ forms a multimodal practice featuring a consistent prosodic and embodied pattern that is deployed in turns conveying the speaker’s emotional stance, performing a dispreferred action, or claiming insufficient knowledge. Even when these turns project only weakly some action on the coparticipants’ part (Tu Vois ‘You See”’ infra). The analyses will show that it is the use of tu vois ‘you see’ with final rising intonation, in correlation with the speaker’s gaze addressed to the coparticipant, that contributes to mobilizing a response from the latter. Moreover, it will be shown that this multimodal practice is dynamically deployed, triggering a distinct response from the recipient in the three action sequences mentioned above.This contribution intends hence to show that ts’ part , 2021, aTu Vois ‘You See”’ describes the multimodal features of tu vois ‘you see’ and the activities performed in the sequential environment of its use, impacting on its production and interpretation. Section “Interactional Workings of Turn-Final Tu Vois ‘You See”’ presents multimodal analyses showing the speakers’ use of turn-final tu vois ‘you see’ in different action sequences. Section “Discussion and Conclusion” summarizes our main findings and discusses their implications for the understanding of the conversational use of tu vois ‘you see’ as a multimodal practice involved in the organization of turns and actions.The remainder of the paper is organized as follows: Section “Background” outlines the background of our study, reviewing some of the works that have dealt with the specific construction that we are interested in. Section “Data and Multimodal Features of Turn-Final tu vois ‘you see’ belongs to a type of verbal expression that has been discussed in the literature under various names. According to marqueurs discursifs propositionnels (énoncés parenthétiques (constructions parenthétiques (constructions à verbe recteur faible ((reduced) parenthetical clauses . These verbs have been documented to lose, in some of their conversational uses, their syntactic and semantic status as main clauses and become markers of epistemic stance, while still keeping traces of their original semantics  essentially in turn-initial and mid-turn positions, with only one example in turn-final position, as a resource for pursuing agreement, by appealing to shared knowledge, in an environment of potential disagreement. Recently, invokes a convergent orientation between recipient and speaker” . They identify two different subgroups for this function: Alignment that allows the recipient to show correct understanding of what the speaker said  and alignment that affiliates with the speaker’s stance . One important feature of both groups is the environment in which ‘you know’ is used: when affiliation or/and understanding emerge as ‘non-given’ or even problematic in the ongoing -sequence. Interestingly, some of our findings, namely those concerned with the use of tu vois ‘you see’ in turns conveying the speaker’s emotional stance, converge with Research on verbal expressions that are similar to tu vois ‘you see’ in French data. 2 , passing through cognition-related usages . The author has also shown that this semantic movement of tu vois ‘you see’ is coupled with a syntactic one, this construction evolving from complex syntax to syntactically autonomous usages. Bolly has also stated that the pragmaticalization of tu vois ‘you see’ is still in-progress nowadays, the pragmatic uses co-existing with the more ancient uses of this verbal expression, based on visual perception.Particularly germane to our analytic focus are works that have specifically examined the use of  data. 2  of tu votu vois ‘you see’ in spoken French according to the position in which it occurs in the utterance. In anteposition, tu vois ‘you see’ has been found to mark the introduction of a new piece of information, while in postposition, it has been documented to indicate the end of an utterance (functioning similarly to what ponctuants). In a parallel line of research, tu vois ‘you see’ in French conversations and have documented that, in turn-initial position, it serves to reactivate the coparticipant’s attention, and in turn-final position, it signals the speaker’s exit from the turn.tu vois ‘you see’ in different positions in the turn. While this approach provides a nice picture of the general functioning of this expression, it remains essentially grounded on the macro-level of the conversation. This means that the identified functions of tu vois ‘you see’ are not minutely related to the specific conversational actions performed in the respective sequential positions. Moreover, the functions that have been documented for tu vois ‘you see’ in turn-final position are of fundamentally retrospective nature. The way in which this construction contributes to mobilizing a response from the recipient, as well as the nature of this response have thus far remained unexplored.These previous studies have been concerned with the use of tu vois ‘you see’ is attached. By presenting a more in-depth study of the action sequences in which tu vois ‘you see’ is employed, this contribution aims to highlight the prospective potential of this interactional resource and to show that its use is consequential even when it accompanies actions that project only weakly some response from the recipient. Our findings reveal that a recurrent embodied conduct of the speaker, namely his/her gazing at the coparticipant while producing tu vois ‘you see,’ combined with a consistent prosodic pattern , enhance the interactional and prospective potential of this construction. This research examines the way in which this verbal expression is connected to the co-occurring embodied conduct of the participants – a multimodal concern that has remained practically unexplored in the previous studies on tu vois ‘you see’ or on other linguistic items figuring in turn-final position .Our paper addresses these issues, by offering a detailed account of the conversational actions performed in the turns to which Through its concern for multimodality, this paper draws also on inquiries into the role of gaze, facial expressions, and gestures in the interactional management of turns and of conversational actions . This woThe database for this study consists of 28 video-recorded informal interactions between students in a Swiss university cafeteria, comprising a total of 9 h and 25 min. The recorded participants, of whom 34 are males and 33 females, agreed to sign an informed consent form for data collection and publication. The data were transcribed according to conversation analytic conventions . The tratu vois ‘you see’ were identified. It is in this position that the construction was found to be the most recurrently used . Since previous research on turn-final tu vois ‘you see’ has documented its use merely for indexing turn completion , we aimed to better understand its interactional functioning, by investigating both the actions performed in the turns it is attached to and the participants’ co-occurring bodily conduct.In these data, 123 occurrences of turn-final tu vois ‘you see’ was recurrently attached to turns conveying the speaker’s emotional stance , to turns performing dispreferred actions , and to turns claiming insufficient knowledge . In addition to this, it was also found that 95.02% of the turns belonging to these collections received a response from the recipient, making thus relevant an examination of the interactional features – in terms of praxeological and multimodal cues – that made such a sequential organization possible. The present study is based on the three collections that we have thus far sequentially and multimodally investigated. While 10 (8.1%) examples have been discarded for various technical reasons, about 15 (12.2%) of the remaining instances, which have not been systematically examined, seem to occur in informing sequences, 12 (9.8%) occurrences in storytellings and 3 (2.4%) cases in evidential vindication contexts  + the verb voir ‘to see’ conjugated in the present indicative (tu vois ‘you see’), the final ‘s’ marking the verbal ending of the second person singular.The French construction that we are interested in bears the same lexico-syntactic form as its English translated equivalent. More precisely, it is composed of the second person singular pronoun . After repeated listening to our data, we found that all occurrences of turn-final tu vois ‘you see,’ mobilized in the action sequences specified above (see section ‘‘Data’’), are prosodically attached to what precedes them in the turn, and are produced, with just four exceptions, with final rising intonation3.In what concerns the morpho-prosodic pattern of the construction, ibid.: 36). In most cases, the last or penultimate syllable carries the focal accent, which usually co-occurs with the lexico-syntactic and also the actional completion of the TCU  but there is a rise or slight rise again on vois ‘see’. Taken together, these features indicate that the focal accent on the last or penultimate syllable before tu vois ‘you see’ and its melodic movement (a rise in pitch) already project a transition relevance place, which is actually reached after the production of the construction, reinforcing thus the relevance of a response from the recipient.The prosodic pattern that tu vois ‘you see’.As for the third feature, the lengthening of the syllable carrying the focal accent, we observe – in some examples – a difference between Persson’s findings and ours. When a lengthening of the stressed syllable occurs, it is rather prominent. This is due to the Swiss variety of French, where the lengthening of the penultimate syllable is more frequent than in ‘standard French’ . Accorditu vois ‘you see’, we observe an equal distribution of final rising intonation when the construction is attached to turns performing a dispreferred action or to turns claiming insufficient knowledge, and a higher frequency of final rising intonation when the expression occurs at the end of turns conveying the speaker’s emotional stance.Concerning the intonation contour of tu vois ‘you see’ is interestingly coupled with a prevalent embodied conduct: the speaker’s gaze directed toward the recipient. All turn-final instances of tu vois ‘you see’ in our data are combined with this gaze conduct. tu vois ‘you see’, forming a multimodal practice that acquires response-mobilizing relevance in the three praxeological environments that we have thus far identified.The prosodic pattern of Tu Vois ‘You See”’), their implications for the understanding of the use of tu vois ‘you see’ being then discussed in the last section of this paper (“Discussion and Conclusion”).These findings emerging from the data are illustrated by the excerpts in the next section , are not produced by coparticipants. In this section, we show that the multimodal practice of producing tu vois ‘you see’ with a final rising intonation and with the speaker’s gaze directed to the recipient occurs in this environment. The practice is exploited in order to pursue affiliation from the interlocutor. Due to space constraints, we illustrate this by one excerpt, prototypical for our collection.In our data, the issues on which speakers take a stance are often delicate and related, among other things, to their relationship with other friends, the sexual orientation of young adults, unemployment, etc. They are hence emotionally charged and their production builds on the mutual manifestation of affiliation – which refers to “the affective level of cooperation” : 21 betwPrior to the beginning of this extract, Eliza announced to Ekta, who is seated with her back to the entrance of the cafeteria, that a mutual female friend had just arrived but gone to another room. Eliza then said that maybe this friend had not noticed them at the table, but Ekta replied the contrary, being sure that the friend only pretended to not have seen them. After stating that this friend might meet up with her boyfriend, following Eliza’s comment that she came in as if looking for someone, Ekta continues with what opens the extract:Given the exchange that precedes this extract as well as the way it begins (line 01), it is clear that Ekta’s relationship with this female friend has deteriorated. Ekta’s affirmation that she has no problem with anyone suggests thus that it’s not her fault if their relationship has become worse. While partially repeating her affirmation (line 02), Ekta directs her gaze to Eliza, inviting thus an affiliation from her part. Eliza responds only with a minimal acknowledgment token (line 03), without adding anything more during the pause that ensues despite Ekta still gazing at her.Ekta then, hesitantly, continues her talk by stating that she cannot interfere with her friend’s life (line 05). This is inferable from her turn, which remains syntactically unfinished at the end of line 05, suggesting, together with the hesitation markers that delimit the turn, and the pause, that this is an emotional subject, which is difficult to talk about . This isDespite Eliza’s multimodal reactions conveying her disengagement from the subject discussed, Ekta still continues to talk about it (lines 13–15). Her turn is again marked with several hesitations (lines 13 and 14) and pauses (lines 14 and 15) and with Ekta’s gazing down most of the time, indicating that the subject is highly sensitive and that the words cannot be easily chosen to refer to it. Toward the end of her turn, she redirects her gaze to Eliza and states that she did what she had to do (line 15), suggesting thus that she could not be held accountable for the degradation of her relationship. Her turn reaches a transition relevance place making relevant a response from Eliza, showing some sort of appreciation of Ekta’s struggle to save her friendship. The fact that a response is expected at this point of the interaction is indicated by Ekta’s gaze at Eliza and also by the pause that follows (line 16) in the course of which Ekta keeps gazing at her interlocutor, who starts nodding approval several times.tu vois ‘you see’ construction delivered with a rising intonation and combined with Ekta’s gaze directed to Eliza. Additionally, Ekta displays a grimace of dislike (see #2 at line 17), through which she facially suggests that she did more than her friend deserved , through which she insists on the efforts that she has put into saving their relationship, which was too much, suggesting hence that her friend did not deserve such an implication from Ekta’s part. In pursuit of an affiliative response from Eliza, Ekta recompletes her turn by using, this time, the rved see . The deptu vois ‘you see’, produced with final rising intonation and with the speaker’s gazing at the recipient, for successfully mobilizing an affiliative response from the coparticipant in an extended sequence that offers several opportunities for the interlocutor to display affiliation, but these have not been taken.This extract has thus illustrated the use of turn-final Preference organization refers to “practices through which certain interactional outcomes are promoted or favored vis-à-vis other outcomes” : 230. AnFor a majority of social actions, such alignment is achieved with answer types that can be glossed as “agreement”  . This idea points to the existence of a general preference for agreement in conversation . She then provides an account meant to support her disagreement: When dealing with an even number, one must work out the average (line 03). After a pause (line 04), during which Nathan does not react verbally to Joanne’s turn but instead gazes up into space (see #1), ‘doing thinking’ , Amanda,Amanda’s turn engenders a change in Joanne’s embodied conduct (see #2) as she shifts her gaze from Nathan to Amanda, who becomes thus Joanne’s focus of attention  until thgiven that (lines 09 and 12) and by its elliptical form ‘que’ that (line 10). Their production is bodily emphasized by Amanda’s “narrowed eyes” . She then launches an explanation based on several premises designed to substantiate her prior disagreement (line 05) and thus to make Joanne agree with her. The first two premises are formally introduced by the conjunctive phrase ‘vu que’ yes” cf. : 32 , emphasizing that a response from the latter is relevant at that point of the interaction. This multimodal conduct in this sequential position allows thus Amanda to mobilize a response from her coparticipant, which has been thus far unsuccessfully pursued.As no reaction is forthcoming from Joanne, Amanda continues her turn (l. 12) and provides a third premise, further substantiating her initial disagreement. While still gazing at Joanne, Amanda pauses again, offering hence the latter, in a stepwise fashion, a second  opportunity to react, which is again not seized (l. 13). Amanda then formulates the conclusion that ensues from the three prior premises and exposes the main argument meant to prove that Joanne’s reasoning was wrong (l. 14). In pursuit of an agreement from Joanne, Amanda marks the end of her turn by using the oh (yeah (l. 15), as well as her indication of how to correctly do the exercise (l. 18) show Joanne’s agreeing with Amanda, suggesting thus indirectly that her initial reasoning was wrong.This multimodal conduct appears to trigger the expected response as Joanne finally reacts , by agreeing with Amanda: The use of the change-of-state token ‘a:h’ oh   or ‘fin des trucs plus ou moins euh intimes’ anyway some things more or less uh intimate (lines 23–24). These characteristics emphasize that Cédric’s response to Camille’s self-invitation is produced ‘on the fly.’Although he carefully gazes at Camille while the latter produces her proposal, Cédric does not immediately react to her turn but continues instead his excuse (lines 20–24), meant to account for his unavailability that very weekend. Cédric’s turn comprises several features that are particularly indicative of its unplanned, emergent occurrence: It is produced with several self-initiated self-repairs (lines 21 and 23) and is delivered in terms that remain quite vague, such as ‘quelque chose’ you see, produced with a final rising intonation, at the end of his turn (line 24) as a resource to mobilize a response from Camille. Moreover, after having gazed in several different directions , toward the end of his excuse and while producing this construction, Cédric gazes at Camille, making thus relevant that a response from her is expected at that point of the interaction. Camille responds to this by nodding approval (line 25) and gazing at Cédric, while chewing her apple, which she started eating before the beginning of the extract.At the same time, Cédric’s repetition, at line 20, of the beginning of his turn (line 17) that has been overlapped by Camille suggests that he orients to the implicative nature of his action, to which his interlocutor is hence expected to respond . This caCamille’s response, though minimal, is monitored by Cédric’s gazing at her and appears to be treated by the latter as sufficient indication of her accepting his excuse, especially since she continues chewing her mouthful of apple that she finally swallows only after the end of the quoted excerpt. It is hence only now, after having received the acceptance of his excuse, that Cédric orients to Camille’s proposal of visiting his parents’ place the following weekend, which he assesses positively (lines 28–29).tu vois ‘you see’ delivered with final rising intonation and combined with the speaker’s gaze at the recipient – that speakers recurrently exploit in our data in order to invite an aligning response . These findings are additionally borne out by the following excerpt in which the coparticipant’s response is missing (lines 10–13), despite its being targeted by the speaker using the tu vois ‘you see’ construction at the end of his turn. The noticeable absence of the recipient’s response leads the speaker to engage in further interactional work that is designed to repair this problem of uptake.Excerpts (3) and (4) have illustrated a multimodal practice – consisting of turn-final In this next excerpt, Ekti and Joanna are planning to organize a trip to Europa-Park, in Germany, with a group of friends. Prior to the beginning of this extract, they weighed whether to go by car, with one of their friends named Carla as a driver, or to take the bus. Eventually, they decided that the train would be the best option, allowing them to travel with the rest of their friends, as a group. Ekti then continues with what opens the excerpt, namely with her stating that Carla does not have anyway the necessary experience to drive to Germany.university) and deploys a palm-up open hand gesture emphasizing the obviousness of her argument . This dispreferred way of taking the turn is additionally coupled with Joanna’s disaffiliative stance: She downgrades the likeliness of Carla actually joining the group, dismissing thus the grounds for Ekti’s concerns. She then provides an account, in the form of a syntactically incomplete if-clause, for why Carla may be unwilling to join them (line 07). Moreover, when producing this account, Joanna stresses the word ‘l’uni’ .As no reaction is forthcoming from Ekti, Joanna continues her turn (line 09) by affirming that Carla’s place is not in this group. This membership categorization , emphasiDespite these verbal and embodied resources deployed by Joanna, her pursuit of a response from Ekti is not successful. Ekti first gazes to the left , probably distracted by loud laughter that is heard at that moment in the cafeteria, and then she gazes down into space (see #4 at line 12). Note that all this time, Ekti’s embodied conduct is carefully monitored by Joanna who keeps gazing at her, while still maintaining her palm-up open hand gesture directed to the latter, indexing thus bodily that a response from Ekti is relevant at that point of the interaction.Orienting to Ekti’s noticeable absence of response, Joanna produces a question (line 14), designed to check whether Ekti has properly attended to her talk thus far. The fact that Joanna launches this enquiry in this sequential position suggests that she treats Ekti’s lack of response as a result of her not having paid enough attention to Joanna’s prior talk. The question is thus meant to solve the interactional problem that Joanna orients to as having caused the absence of a response from Ekti at a moment where it has been made especially relevant , that the latter provides the response that has been previously expected by Joanna (lines 18–19). Still, this response appears to be disaligning with Joanna’s prior talk. Ekti’s response, in this sequential position, indicates that her lack of reaction has not been due to her not attending to Joanna’s talk but rather to her reluctance to agree with the latter’s arguments concerning Carla’s potential absence from their excursion. This is additionally seen in the design of her response as she proposes to nevertheless invite Carla to their trip. The sequence is then closed with Joanna’s agreeing with this and announcing that she has already written to Carla.tu vois ‘you see’ construction is noticeably absent, the speaker may engage in further interactional work so as to remedy this problem of uptake.This excerpt has illustrated that when the response that is called for by the multimodal use of the tu vois ‘you see’ is at the end of turns containing the expression ‘je (ne) sais pas’ I don’t know or in combination with other linguistic items . These turns occur as part of responsive or initiating actions. When occurring as responsive actions, these turns are used to display responsiveness without giving an explicit answer  – a response from the coparticipant, acknowledging thus the prior response.A third environment in which speakers of our data deploy the multimodal practice involving t answer . In thisximation  or projefunction . The twoI don’t know expression is followed by a complement clause (see ex. 6 infra) to which the tu vois ‘you see’ construction is attached. These turns convey the speaker’s relatively unknowing stance  sais pas’ g stance  or uncerg stance  about thBefore the beginning of the extract, Alexeï and Eddy talked about the first name of a mutual acquaintance whose pronunciation would suppose a nasalization of the last syllable but which professors, according to Alexeï, often do not produce when calling his name. The sequence is closed and a pause occurs in the course of which both participants gaze down to the sheets of paper in front of them. Alexeï then reopens the sequence with what follows:it’s like my first name (line 01) from the very beginning of his turn signals that a similar pronunciation error to the one previously talked about may concern his own forename. Then, after a cut-off (line 01), two self-initiated self-repairs (line 02 and 03), and a pause (line 03), Alexeï states that he does not know if his name should be pronounced with a stress on the second (Alexeï) or on the last syllables (Alexeï) (line 03).At lines 01 to 03, Alexeï expands the previously closed sequence on the mispronunciation of their acquaintance’s first name, by referring to his own given name. In this sense, his use of ‘c’est comme mon prénom’ I don’t ever know if it’s (line 02), which indicates that this matter has always been a dilemma for him. Alexeï marks the end of his turn by employing tu vois ‘you see’, produced with final rising intonation, while carefully gazing at Eddy (see #1 at line 03). This verbal construction seems to be multimodally exploited at this point of the interaction in order to mobilize a response from Eddy that possibly addresses Alexeï’s dilemma. Attached to Alexeï’s claim of insufficient knowledge, this construction appears to be doing more than just inviting, for instance, an acknowledging reaction: It sets the relevance for a response that would target the preceding claim, but from the recipient’s own perspective.In this sequential position, Alexeï’s claim of insufficient knowledge, also bodily enacted through a quick head shake (see line 03) conveys his uncertainty  regardinThe fact that Alexeï is expecting a response from his interlocutor is also confirmed by his gaze at Eddy, maintained throughout the extended pause that follows (line 04). Alexeï’s prolonged gaze at Eddy contributes to reinforcing the sequential implicativeness of his prior turn, emphasizing thus the relevance of a response from his interlocutor , to turns performing a dispreferred action, like disagreeing (see section “Tu Vois ‘You See’ Attached to Turns Performing a Dispreferred Action” supra), and to turns claiming insufficient knowledge (see section “Tu Vois ‘You See’ Attached to Turns Claiming Insufficient Knowledge” supra). In each of these distinct praxeological environments, it has been found that speakers exploit tu vois ‘you see’ in order to mobilize a response from their interlocutors. The analyses have shown that the response that is invited through the use of this construction differs from one action sequence to another: an affiliative response (see ex. 2), an aligning response , and a response addressing the prior speaker’s claim of insufficient knowledge from the recipient’s own perspective (see ex. 6).This paper has documented the use of turn-final tu vois ‘you see’ expression represents, through the second person pronoun, a form of addressing the interlocutor. Together with the verb, ‘voir’ to see, it projects, structurally speaking, a yes/no type of response and thus at least a minimal response. The form of this response depends on the conversational action performed by the turn to which tu vois ‘you see’ is attached (see in this sense section “Tu Vois ‘You See’ Attached to Turns Claiming Insufficient Knowledge”). Prosodically, the production of the construction with a final rising intonation, similar to the final intonations of questions in French . Bodily, the expression is systematically coupled with the speaker’s gaze directed to the recipient, a gaze pattern that signals turn completion and allocation in dyadic interaction . It is also this multimodal practice that enables speakers to eventually obtain a relevant response after several unsuccessful pursuits of such a response from their interlocutors (see ex. 2 and 3). The use of this multimodal practice provides recipients with a sequential opportunity for displaying co-participation  , it seems to appeal to the interlocutor’s intellectual comprehension of the talk that it is attached to, confirming thus Andersen (1997: 196–197). When the construction is used for inviting an affiliative response  or a response that would target the speaker’s claim of insufficient knowledge (see section “Tu Vois ‘You See’ Attached to Turns Claiming Insufficient Knowledge” supra), it appears to convey “an invitation not to seeing but to the experiential sharing […] in an empathic way” , as well as in other types of interactional settings. In the same vein, further research could look more thoroughly into the way in which the deployment of certain gestures, like the palm-up open hand gesture (see ex. 5), may contribute to enhancing the response-mobilizing potential of the tu vois ‘you see’ construction. Finally, the present study could be complemented by a future research on the multimodal use of this verbal expression across several languages so as to verify if the identified multimodal practice represents a phenomenon that participants orient to cross-linguistically and cross-culturally.These findings suggest that the multimodal practice involving turn-final The original contributions presented in the study are included in the article/supplementary material, further inquiries can be directed to the corresponding author/s.Ethical review and approval was not required for the study on human participants in accordance with the local legislation and institutional requirements. The patients/participants provided their written informed consent to participate in this study. 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