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[Masaki Takeguchi](https://orcid.org/0000-0002-0282-6020), [Kazutaka Mitsuishi](https://orcid.org/0000-0002-9361-4057), [Ayako Hashimoto](https://orcid.org/0000-0002-1985-7667)

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[Facile preparation of graphene–graphene oxide liquid cells and their application in liquid-phase STEM imaging of Pt atoms](https://mdr.nims.go.jp/datasets/086ecec8-8845-4f51-bf94-f1171d00658a)

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Facile preparation of graphene–graphene oxide liquid cells and their application in liquid-phase STEM imaging of Pt atomsApplied Physics Express     LETTER • OPEN ACCESSFacile preparation of graphene–graphene oxideliquid cells and their application in liquid-phaseSTEM imaging of Pt atomsTo cite this article: Masaki Takeguchi et al 2024 Appl. Phys. Express 17 085001 View the article online for updates and enhancements.You may also likeEvaluation of crystallographic strain,rotation and defects in functional oxides bythe moiré effect in scanning transmissionelectron microscopyA B Naden, K J O’Shea and D AMacLaren-Sb-saturated high-temperature growth ofextended, self-catalyzed GaAsSbnanowires on silicon with high qualityP Schmiedeke, M Döblinger, M AMeinhold-Heerlein et al.-Pt Based Alloy Nanoparticles for OxygenReduction Prepared By a SolvothermalMethodCenk Gumeci, Archis Marathe, RachelLynn Behrens et al.-This content was downloaded from IP address 144.213.253.16 on 02/08/2024 at 02:02https://doi.org/10.35848/1882-0786/ad63f2/article/10.1088/1361-6528/aaae50/article/10.1088/1361-6528/aaae50/article/10.1088/1361-6528/aaae50/article/10.1088/1361-6528/aaae50/article/10.1088/1361-6528/ad06ce/article/10.1088/1361-6528/ad06ce/article/10.1088/1361-6528/ad06ce/article/10.1149/MA2014-01/20/883/article/10.1149/MA2014-01/20/883/article/10.1149/MA2014-01/20/883Facile preparation of graphene–graphene oxide liquid cells and their application inliquid-phase STEM imaging of Pt atomsMasaki Takeguchi1* , Kazutaka Mitsuishi2 , and Ayako Hashimoto1,31Research Center for Energy and Environmental Materials, National Institute for Materials Science, Japan2Center for Basic Research on Materials, National Institute for Materials Science, Japan3Degree Programs in Pure and Applied Sciences, University of Tsukuba, Japan*E-mail: TAKEGUCHI.Masaki@nims.go.jpReceived June 26, 2024; revised July 9, 2024; accepted July 16, 2024; published online August 1, 2024Graphene–graphene oxide (GO) hybrid liquid cells (LCs) for liquid-phase scanning transmission electron microscopy (STEM) were fabricatedusing a facile method with commercial graphene on a polymethyl methacrylate sheet and GO on a TEM grid. LCs containing Pt nanoparticles(NPs) and pure water were efficiently produced and observed via STEM. Their composition and thickness were characterized by STEM-electronenergy-loss spectroscopy. High-resolution (HR) STEM revealed slow-moving Pt NPs’ atomic structures and fast-moving single Pt atoms at the LC’sthin edges. Minimal damage during HR STEM indicated stable LCs because of their excellent electrical and thermal conductivities and radiolysisspecies scavenging ability. © 2024 The Author(s). Published on behalf of The Japan Society of Applied Physics by IOP Publishing LtdLiquid-phase transmission electron microscopy (LP-TEM) is a powerful tool for observing samples inliquid with high spatial and temporal resolutions.1–6)A liquid cell (LC) separates the liquid environment ofsamples from an electron microscope’s vacuum using topand bottom membrane windows. The most popular mem-brane material is a low-stress silicon nitride film deposited ona silicon wafer.7–9) Using Micro Electro Mechanical Systems(MEMS) fabrication technology, a self-standing siliconnitride membrane window is formed on a silicon chip viaback-side etching. Two of the chips are sandwiched andliquid samples are enclosed inside a narrow space betweenthem to complete the LC. Owing to the development of stableand robust LC membranes and MEMS technologies, a set ofmass-produced LC chips and dedicated LC TEM holders arecommercially available10) to many researchers, enablingobservations of the morphology, structural changes, andchemical reactions of inorganic and biological materials inliquid.1–14) MEMS-fabricated LCs offer reproducibility, easeof handling, and expandability (e.g., incorporating electrodesand flow systems). However, the membrane thickness(∼50 nm) results in resolution deterioration.3,9,15–17)Another popular type of LC is a graphene LC (GLC), whichcomprises a pocket containing the liquid and samplesbetween two graphene sheets composed of a single or a fewlayers.18–21) GLCs are widely used in academia. Graphene isan ideal LC membrane material as it offers atomic-levelthicknesses, low electron scattering characteristics, mechan-ical flexibility, electrical and thermal conductivity, andchemical stability, enabling atomic-resolution imaging ofsamples in liquid. However, GLC use is limited becausecomplicated and delicate chemical treatment processes alongwith technical expertise are needed to prepare GLCs,22–25)i.e., graphene transfer from CVD-graphene to TEM grids.Furthermore, graphene’s hydrophobicity can limit the pro-duction yield of liquid pockets.The present work examines the fabrication of graphene–graphene oxide (GO) LCs using commercially availablesingle-layer graphene sheets and GO-supported TEM grids.Pure water and Pt nanoparticles (NPs) are enclosed in thegraphene–GO LC. Characterization was performed usingscanning TEM (STEM) and electron energy-loss spectro-scopy (EELS) with an aberration-corrected electron micro-scope (JEM-ARM200F, JEOL Ltd) at 200 kV. The resolutionof LP-STEM is better than that of LP-TEM, and aberration-corrected STEM enables imaging of the atomic structures ofsamples and even single atoms in liquid, whereas scanningspeed limits the temporal resolution.2,17,26) Generally, thebasal plane of GO produced by chemical oxidation methods,like the modified Hummers method, predominantly containsepoxy and hydroxyl functional groups,27–32) resulting instrong water adhesion (i.e., hydrophilicity). This is expectedto increase the production yield of liquid sample pockets onGO relative to graphene. Furthermore, GO, similar tographene, has a radical scavenging effect that migratesradiolysis-induced undesired chemical reactions.33–35)However, GO is an electrical and thermal insulator, affectingsample and LC stability during TEM. A graphene–GO hybridsheet exhibits good conductivity,36) thereby solving thisissue. The use of GO for LC (S)TEM has rarely beenreported, except for LCs using plasma- or UV-treatedgraphene,19) which is thought to be partially oxidized. Tothe authors' knowledge, LCs with GO for photoelectronspectroscopy37) and scanning electron microscopy,38) alongwith silicon nitride-adhered GO LCs for TEM,34) have beenreported so far. Hence, this study attempts to analyzegraphene–GO hybrid LCs with STEM for the first time.Double layers of GO on holey silicon nitride TEM grids(GNO-2, EMJapan Co. Ltd, Japan) and a single layer ofgraphene sheet (Trivial Transfer Graphene®, ACS MaterialsLLC, USA) were used as the GO bottom layer and thegraphene top layer of the LCs. The Pt colloidal solutionstabilized with tetramethylammonium (4 wt%, TanakaKikinzoku Kogyo K. K., Japan) was diluted five times withpure water. Figure 1 shows the graphene–GO LC preparationmethod. The “Trivial Transfer Graphene®” produced iscomposed of graphene adhered to a polymethyl methacrylate(PMMA) sheet, with a polymer protection sheet covering it,as shown in Fig. 1(a). The polymer protection sheet waseasily removed from the graphene/PMMA sheet by floatingContent from this work may be used under the terms of the Creative Commons Attribution 4.0 license. Any further distribution of thiswork must maintain attribution to the author(s) and the title of the work, journal citation and DOI.085001-1© 2024 The Author(s). Published on behalf ofThe Japan Society of Applied Physics by IOP Publishing LtdApplied Physics Express 17, 085001 (2024) LETTERhttps://doi.org/10.35848/1882-0786/ad63f2https://crossmark.crossref.org/dialog/?doi=10.35848/1882-0786/ad63f2&domain=pdf&date_stamp=2024-08-01https://orcid.org/0000-0002-0282-6020https://orcid.org/0000-0002-0282-6020https://orcid.org/0000-0002-9361-4057https://orcid.org/0000-0002-9361-4057https://orcid.org/0000-0002-1985-7667https://orcid.org/0000-0002-1985-7667mailto:TAKEGUCHI.Masaki@nims.go.jphttps://creativecommons.org/licenses/by/4.0/https://doi.org/10.35848/1882-0786/ad63f2the sample in pure water for several minutes. Two methodswere used to scoop the graphene/PMMA sheet. One involveda loop, as shown in Fig. 1(b). A water droplet with thegraphene/PMMA sample was scooped with a loop and placedon a GO-supported TEM grid, as shown in Fig. 1(c).Immediately before this process, a GO-supported TEM gridwas illuminated with UV light from an ozone lamp at apower of 4W for 30–60 s, and a droplet of a sample solution(Pt colloidal solution) was drop-cast onto it. After completelydrying the TEM grid, it was immersed in acetone for 30 minto dissolve the PMMA, as shown in Fig. 1(f). It was thenrinsed with a mixture of fresh acetone and ethanol. Adisadvantage of this method was the difficulty of suspendinggraphene/PMMA on a water droplet inside the loop, espe-cially when the size of the graphene/PMMA sample wassmaller than the loop diameter. Conversely, if the graphene/PMMA size was too large, it covered both the top and bottomsides of the TEM grid. An alternative method involvedscooping the graphene/PMMA sample directly with a UV-treated GO-supported TEM grid, as shown in Fig. 1(d),followed by slowly drying it in air. When water on the TEMgrid was almost evaporated (not completely dried), a smallamount of the Pt colloidal solution was drop-cast onto it tosoak into the gap between the GO and graphene, as shown inFig. 1(e). A drawback of this method was the dilution of thesample solution with the remaining water on the TEM grid.Figure 2(a) shows an annular dark-field (ADF) STEMimage at low magnification, presenting a wide-area view of agraphene–GO membrane suspended across a silicon nitridehole. Enhanced contrast reveals the morphology of thegraphene–GO membrane, while the brightness at the siliconnitride region was saturated. Figure 2(b) is a medium-magnification ADF-STEM image, in which large gray areas,as indicated with white arrowheads, and many bright small(a)(b) (c)(d) (e)(f)Fig. 1. The graphene–GO LC preparation method: (a) structure of “Trivial Transfer Graphene®”; (b) removal of a polymer protection sheet from graphene/polymethyl methacrylate (PMMA) in pure water, followed by scooping it with a loop; (c) sample drop-casting and placing graphene/PMMA on a GO-supported TEM grid; (d) removal of the polymer protection sheet from graphene/PMMA in pure water, followed by scooping with a GO-supported TEM grid;(e) sample-soaking in a gap between graphene/PMMA and GO on a TEM grid; and (f) PMMA dissolution via acetone treatment.Fig. 2. (a) Annular dark-field (ADF)-STEM wide-area image of a graphene–GO membrane supported on a silicon nitride TEM grid hole; (b) a medium-magnification ADF-STEM image showing large and small graphene–GO LCs; and (c) a schematic of the cross-section of a graphene–GO LC containing waterand Pt NPs.085001-2© 2024 The Author(s). Published on behalf ofThe Japan Society of Applied Physics by IOP Publishing LtdAppl. Phys. Express 17, 085001 (2024) M. Takeguchi et al.dots are seen. These correspond to liquid pockets (i.e., LCs)and Pt NPs, respectively. Pt NPs appear to decorate the LC’sedges and wrinkles of graphene, suggesting the presence ofthe Pt solution. This is consistent with previous reports ofliquids enclosed in dome-shaped pockets and wrinkles ofgraphene.19,22) Figure 2(c) illustrates the cross-section of theLC seen at the center of Fig. 2(b), showing that Pt NPs weretrapped at the edges of the LC. This trapping occurs becausePt NPs move freely in thicker water but slow down andbecome immobile in the high-viscosity thin water regions,causing them to accumulate at the edge of the LCs. InFig. 2(b), small aggregates of Pt NPs also exist, likelycorresponding to small LCs. In these thin LCs, Pt NPs aretrapped throughout the entire LC.STEM-EELS elemental mapping was performed to verifythe existence of water inside the graphene–GO LCs.Figure 3(a) shows an ADF-STEM image of an LC, whileFig. 3(b) shows EELS elemental maps of carbon (red),oxygen (green), and their mixture, acquired from the greenrectangle in Fig. 3(a). The gray center part in the LC containsoxygen and is surrounded by carbon, aligning with the modelin Fig. 2(c). It is noted that graphene wrinkles decorated withPt NPs are composed of oxygen and carbon, albeit withcarbon covering a wider region than oxygen, suggesting thatwater exists inside the graphene wrinkles. The thickness ofthe LC was estimated to be approximately 30 nm using thelog-ratio method, assuming that the inelastic scattering meanfree path length for water is 175 nm.39)Figure 4(a) is an enlarged ADF-STEM image of the LC inFig. 3(a). An area inside a green rectangle in Fig. 4(a) wasobserved by high-resolution (HR) STEM with 1024× 1024pixels at a rate of 19 s/frame. HR STEM movies were recordedusing an HD video function of the Gatan Microscopy Suite®(Gatan, USA), with each frame subsequently captured offline.Figure 4(b) is an HR STEM image captured from the movies,in which Pt NPs exist densely along the edge of the LC. Thebackground ADF intensity of the left side of the image isbrighter than the right side, indicating a greater amount ofwater on the left side. As NPs move slowly, which might becaused by the high viscosity of thin water, their atomicstructures can be clearly observed, highlighted with pseudo-color for better visibility. Furthermore, small bright dotscorresponding to single atoms can be detected, as indicatedby white arrows. However, it was difficult to trace the motionof single atoms because they moved faster than the STEMbeam scanning speed. Additionally, atoms moving to differentheights were defocused and blurred. Notably, there wasminimal LC damage during 6 min of HR STEM observations,attributed to their good electrical and thermal conductivities, asFig. 3. (a) ADF-STEM image of a graphene–GO LC containing water andPt NPs. (b) Results of STEM-EELS elemental mapping for a green rectanglearea in (a)—R (red) and G (green) correspond to carbon and oxygenelemental maps, respectively. The RGB map is a mixture of carbon andoxygen.Fig. 4. (a) An enlarged ADF-STEM image of the LC in Fig. 3(a). (b) HRADF-STEM image of Pt NPs and single atoms (indicated by white arrows)moving in pure water at the edge of the LC. This was a snapshot capturedfrom HR STEM movies.085001-3© 2024 The Author(s). Published on behalf ofThe Japan Society of Applied Physics by IOP Publishing LtdAppl. Phys. Express 17, 085001 (2024) M. Takeguchi et al.well as their ability to scavenge radiolysis species ofgraphene–GO hybrid LCs.In summary, graphene–GO hybrid LCs for LP (S)TEMwere fabricated through a facile method that uses commer-cially available graphene/PMMA sheets and GO-supportedTEM grids. These LCs, applied to STEM imaging of Pt NPsin pure water, exhibited a good production yield, displayeddome pockets, and formed wrinkles decorated with Pt NPs.Their composition and thickness were characterized bySTEM-EELS. Atomic structures of Pt NPs moving slowlyand Pt single atoms moving fast in water at the thin edgeregions of the LCs were observed by HR STEM. Minimaldamage during HR STEM observations demonstrated thatgraphene–GO LCs were stable and robust because of theirsuperior electrical and thermal conductivities, as well as theirradiolysis species scavenging ability.Acknowledgments The authors thank Ms. Y. Kobayashi forhelping fabricate graphene–GO LCs, Dr. J. 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