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Choon Meng Tan, Naoya Fukui, Kenji Takada, Hiroaki Maeda, Ekaterina Selezneva, [Cédric Bourgès](https://orcid.org/0000-0001-9056-0420), Hiroyasu Masunaga, Sono Sasaki, [Kazuhito Tsukagoshi](https://orcid.org/0000-0001-9710-2692), [Takao Mori](https://orcid.org/0000-0003-2682-1846), Henning Sirringhaus, Hiroshi Nishihara

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[Lateral Heterometal Junction Rectifier Fabricated by Sequential Transmetallation of Coordination Nanosheet](https://mdr.nims.go.jp/datasets/20a76e7c-c268-4427-b58d-eab466dae9e5)

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Lateral Heterometal Junction Rectifier Fabricated by Sequential Transmetallation of Coordination Nanosheet**Electronic Materials Very Important PaperLateral Heterometal Junction Rectifier Fabricated by SequentialTransmetallation of Coordination Nanosheet**Choon Meng Tan+, Naoya Fukui+, Kenji Takada, Hiroaki Maeda, Ekaterina Selezneva,Cédric Bourgès, Hiroyasu Masunaga, Sono Sasaki, Kazuhito Tsukagoshi, Takao Mori,Henning Sirringhaus, and Hiroshi Nishihara*Abstract: Heterostructures of two-dimensional materials realise novel and enhanced physical phenomena, making themattractive research targets. Compared to inorganic materials, coordination nanosheets have virtually infinitecombinations, leading to tunability of physical properties and are promising candidates for heterostructure fabrication.Although stacking of coordination materials into vertical heterostructures is widely reported, reports of lateralcoordination material heterostructures are few. Here we show the successful fabrication of a seamless lateralheterojunction showing diode behaviour, by sequential and spatially limited immersion of a new metalladithiolenecoordination nanosheet, Zn3BHT, into aqueous Cu(II) and Fe(II) solutions. Upon immersion, the Zn centres ininsulating Zn3BHT are replaced by Cu or Fe ions, resulting in conductivity. The transmetallation is spatially confined,occurring only within the immersed area. We anticipate that our results will be a starting point towards exploringtransmetallation of various two-dimensional materials to produce lateral heterojunctions, by providing a new and facilesynthetic route.Electronically conducting two-dimensional (2D) materialssuch as graphene[1] and transition metal dichalcogenides[2](TMDCs) are fascinating research targets in both physicsand chemistry as their unique topological properties andfunctionalities open new scientific and technological fields.The combination of different 2D materials expands thevariation of electro-, photo-, and magneto-functions, realis-ing a variety of device applications inaccessible by singlematerial systems.[3] Heterostructures of 2D materials can befabricated in two ways: as vertical heterojunctions or lateralheterojunctions.[4] Confinement of charge carriers within thetwo-dimensional plane enhances physical properties: henceunique in-plane devices such as p-n diode,[5] Schottkydiode,[6] photocurrent generation,[7] electroluminescence[8]and CMOS inverter[9] can be realised. However, construc-tion of the lateral heterojunction is challenging comparedwith the vertical heterojunction, which can be simplyachieved by stacking two flakes of different materials withthe naturally obtained atomically flat surfaces.[10]Nowadays, conductive 2D materials are explored notonly in inorganic materials but also in organic materials,which are in most cases light and flexible.[11,12] Coordinationnanosheets, composed of planar organic ligands coordinat-ing to metal ions with a square planar geometry, have beena representative conductive 2D organic material since ourreport of the synthesis of nickel benzenehexathiol (BHT)[*] Dr. C. M. Tan,+ Dr. N. Fukui,+ Dr. K. Takada, Dr. H. Maeda,Dr. E. Selezneva, Prof. H. NishiharaResearch Institute for Science and Technology, Tokyo University ofScience2641 Yamazaki, Noda, Chiba 278 8510 (Japan)E-mail: nisihara@rs.tus.ac.jpDr. E. Selezneva, Prof. K. Tsukagoshi, Prof. T. MoriWPI International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS)Namiki 1-1, Tsukuba 305-0044 (Japan)Dr. E. Selezneva, Prof. H. SirringhausCavendish Laboratory, University of CambridgeJJ Thomson Avenue, Cambridge CB3 0HE (UK)Dr. C. BourgèsInternational Center for Young Scientists (ICYS), National Institutefor Materials Science (NIMS)Namiki, Tsukuba, 305-0044 (Japan)Dr. H. MasunagaJapan Synchrotron Radiation Research Institute (JASRI)1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan)Prof. S. SasakiFaculty of Fiber Science and Engineering, Kyoto Institute ofTechnology1 Matsugasaki Hashikami-cho, Sakyo-ku, Kyoto 606-8585 (Japan)andRIKEN SPring-8 Center1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan)[+] These authors contributed equally to this work.[**]A previous version of this manuscript has been deposited on apreprint server (https://doi.org/10.21203/rs.3.rs-3186809/v1).© 2024 The Authors. Angewandte Chemie International Editionpublished by Wiley-VCH GmbH. This is an open access article underthe terms of the Creative Commons Attribution License, whichpermits use, distribution and reproduction in any medium, providedthe original work is properly cited.AngewandteChemieCommunicationswww.angewandte.orgHow to cite: Angew. Chem. Int. Ed. 2024, 63, e202318181doi.org/10.1002/anie.202318181Angew. Chem. Int. Ed. 2024, 63, e202318181 (1 of 6) © 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbHhttp://orcid.org/0000-0002-9806-260Xhttp://orcid.org/0000-0003-4021-3193http://orcid.org/0000-0002-7531-6865http://orcid.org/0000-0001-9552-7478http://orcid.org/0000-0003-0479-7443http://orcid.org/0000-0001-9056-0420http://orcid.org/0000-0002-0939-2114http://orcid.org/0000-0001-7374-9854http://orcid.org/0000-0001-9710-2692http://orcid.org/0000-0003-2682-1846http://orcid.org/0000-0001-9827-6061http://orcid.org/0000-0002-6568-5640https://doi.org/10.21203/rs.3.rs-3186809/v1https://doi.org/10.1002/anie.202318181http://crossmark.crossref.org/dialog/?doi=10.1002%2Fanie.202318181&domain=pdf&date_stamp=2024-01-23nanosheet Ni1.5BHT in 2013.[13] The combination of BHTand various transition metals can afford M/BHT family ofnanosheets, porous M1.5BHT[14–16] and non-porousM3BHT[17–21] with wide-ranging physical and chemical prop-erties such as superconductivity,[20] topological spin glass[18]and redox control of conductivity.[22] They have also beenincorporated into devices as hole buffer layer,[23]photodetectors[24] or pseudocapacitors.[19]Facile postsynthetic modification is an advantage ofcoordination nanosheets. Metal centres in coordinationmaterials can be replaced with other metal ions, in apostsynthetic transmetallation reaction by only immersing inthe corresponding metal salt solution.[25] This method allowsthe synthesis of materials that cannot be synthesized bydirect reaction: such as when undesirable metal-ligand sidereactions occur, kinetic coordination competition withinmetal ion mixtures. The previous example is Schlüter andco-workers’ work which reported that bis(terpyridine)zincnanosheet was transmetallated with Co(II), Pb(II) andFe(II) to give the respective bis(terpyridine)metalnanosheets.[26] Since bis(terpyridine)metal nanosheet gener-ally possesses poor electrical conductivity, conductive nano-sheets obtained by transmetallation are required for futureapplication to electronics. For example, BHT-based coordi-nation nanosheets may affords various conducting nano-sheets after transmetallation and moreover lead to hetero-junction by spatially controlled immersion into differentmetal solutions. However, research of transmetallation as amethod to fabricate heterostructures is still in an early stage.In this study, we attempted to synthesize lateral hetero-junction of conducting metalladithiolene nanosheets utilisingsequential transmetallation. For this purpose, we firstsynthesized and characterized Zn-BHT coordination nano-sheet. We found that Zn forms nonporous Zn3BHT nano-sheet. Next, we investigated the transmetallation of Zn3BHTsheet with Cu(II) and Fe(II). Both metals replaced Zn togive transmetallated nanosheets tmCu and tmFe, respec-tively. Finally, we synthesized lateral tmFe/tmCu hetero-junction by sequential transmetallation of Zn3BHT. Aseamless boundary was realised with physical and electricalconnection maintained, taking advantage of transmetallationmethod. We found that this heterojunction shows a rectify-ing behaviour. Thermoelectric measurements and Kelvinforce microscopy reveal that a p-p junction caused therectification.Initial trials of the liquid-liquid interfacial synthesis ofZn/BHT nanosheet, by layering a solution of Zn(OAc)2 ontop of a dichloromethane solution of BHT at room temper-ature and stoichiometric amount of (Zn2+: BHT=3 :1) weredone. Allowing the reaction to proceed for 24 hours underinert atmosphere gave a thick opaque white film. Wemeasured the powder X-ray diffraction (PXRD) pattern ofthe film as shown in Figure 1b. Broad diffraction peaks wereobserved which show that periodicity occurs only in smalldomains. To obtain higher crystalline Zn/BHT suitable forstructure determination, Zn/BHT was synthesized at highertemperature (45 °C), replacing dichloromethane with chloro-form (Figure 1a). As shown in Figure 1b, the crystallinity ofthe resulting Zn/BHT was greatly improved. This improve-ment of the crystallinity at higher temperature is commonlyseen in the synthesis of M3BHT nanosheets such as Fe3BHTand Cu3BHT.[17,20] It can be explained by the thermallyenhanced reversibility of complexation, which promotes theformation of thermodynamically stable crystal structure.The diffraction peaks of Zn/BHT provided enough informa-tion to determine its structure as depicted in Figure 1c. Thepattern was reproduced by an AB slipped parallel stackingof nonporous structure, Zn3BHT, where one monolayer wassimulated as a flat layer, and the next layer translated in aslipped parallel fashion. This gave a Zn3BHT structure withunit cell parameters a=b=8.7 Å, c=7.1 Å, α=β=90°, γ=120° with a translation of the B-layer 0.8 units in the a-direction and 0.45 units in the b-direction (Figure 1c). TheFigure 1. Characterization of Zn3BHT. a, Schematic and photo ofZn3BHT synthesis. b, Experimental and simulated PXRD patterns ofZn3BHT (λ=0.8 Å), synthesized at room temperature and 45 °C. c,model structures of Zn3BHT viewed along c- (left), and a-axes (right).The unit cell is drawn with black solid lines. The red dot lines show thecorresponding unit cell of the slipped neighboring layer. d, SEM/EDSelemental maps of Zn3BHT nanosheet. e, Narrow X-ray photoelectronspectra of Zn3BHT.AngewandteChemieCommunicationsAngew. Chem. Int. Ed. 2024, 63, e202318181 (2 of 6) © 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH 15213773, 2024, 9, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202318181 by Cochrane Japan, Wiley Online Library on [29/02/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensein-plane structure of Zn3BHT is similar to that of otherM3BHT (M=Mn, Fe, Ni, Cu) but different in that the otherM3BHT materials adopt the AA stacking mode.[17–21] Thecrystallinity of Zn3BHT was affected by the type of anion inthe salt. Zn(OAc)2, Zn(BF4)2, and Zn(NO3)2 afforded highlycrystalline Zn3BHT while ZnCl2 afforded poorly crystallineZn3BHT (Figure S1). It is also noteworthy that a zinc ion inZn3BHT takes square-planar geometry while zinc ionsgenerally prefer tetrahedral geometry.SEM images (Figure 1d) show the monolithic structureof Zn3BHT and the EDS elemental maps confirm theuniform distribution of Zn, S and C in the sheet structure.These images confirm that the nanosheets are composed ofZn(II) ions and BHT ligands coordinated to form Zn3BHTat the confined liquid-liquid interfacial region resulting in aflat topography with 30 nm thickness as shown in AFMimages (Figure S2).X-ray photoelectron spectroscopy (XPS) of Zn3BHTindicates the presence of each element Zn and S (Figure 1e).The S2p narrow spectrum can be deconvoluted into a pair ofpeaks which are assigned to 2p3/2 at 161.6 eV and 2p1/2 at162.9 eV. The atomic ratio of Zn :S is 1 : 1.6, which is close tothe ratio 1 :2 implied by the nonporous structure, Zn3BHT.Metal exchange reactions of Zn3BHT were conductedusing Fe(II) and Cu(II) ions. Samples of Zn3BHT immobi-lised on SiO2/Si substrate were immersed in 50 mM saltsolution for 3 days (Figure 2a). The residual metal salts werethoroughly washed with a 1 :1 solution of water:ethanol. TheZn3BHT after transmetallation by each metal ion solution(tmM) was investigated with SEM/EDS, XRD, Ramanspectroscopy, and electrical measurements. The elementmaps of the tmM nanosheets (M=Cu, Fe) are shown inFigures 2b and 2c. For this EDS measurement, the Zn3BHTwas partially immersed for the clear comparison betweenpristine and immersed Zn3BHT samples (Figure 2a). Cu andFe were uniformly distributed in the immersed region oftmCu and tmFe, respectively, while they are absent in thepristine region. On the other hand, according to the EDSanalyses, Zn was not detected in the immersed region(Figures S3 and S4). Carbon and sulphur are uniformlydistributed over both pristine and immersed regions. Thisobservation suggests the successful transmetallation ofZn3BHT into corresponding tmM by exchanging zinc ionsand iron or copper ions with the BHT framework main-tained.The atomic structures of tmCu and tmFe after thetransmetallation were obtained by studying their PXRDpatterns (Figure 2d). The position of diffraction peaks oftmFe is the same as that of Zn3BHT, implying that theyshare the same unit cell. On the other hand, the intensity ofthe peaks differs between tmFe and Zn3BHT, with broaderpeaks in tmFe than in Zn3BHT. These results suggest thattmFe maintains the framework originating from Zn3BHT(with Fe ions replacing Zn ions) and that during thetransmetallation slight disorder was introduced in the sheet.Notably, the structure of tmFe (AB stacking) is hencedifferent from that of previously reported Fe3BHT (AAstacking).[17] The situation is different in tmCu, as theresulting structure of the material resembles that ofCu3BHT, with the (001) peak shifting from a 2θ value of12.9° in Zn3BHT to 13.2° in tmCu, which is different from13.5° in Cu3BHT directly synthesized from Cu(II) andBHT.[20,21,27] This implies that while the in-plane structure oftmCu is similar to that of Cu3BHT, the interlayer distance ofFigure 2. Characterization of tmM. a, Schematic illustration of thesynthesis of tmM/Zn3BHT heterojunction. b, c, SEM/EDS elementalmaps of (b) tmCu, and (c) tmFe nanosheets, d, PXRD patterns of tmMtogether with Zn3BHT before transmetallation (λ=0.8 Å). e, I–V curvesof tmM nanosheets measured by four-point probe method.AngewandteChemieCommunicationsAngew. Chem. Int. Ed. 2024, 63, e202318181 (3 of 6) © 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH 15213773, 2024, 9, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202318181 by Cochrane Japan, Wiley Online Library on [29/02/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons LicensetmCu (3.49 Å) is in-between that of Zn3BHT (3.58 Å) andCu3BHT (3.43 Å). A possible explanation is that thestructure of tmCu is Cu-substituted Zn3BHT with ABslipped stacking and an expanded interlayer distance, a newphase of Cu/BHT group.Four-point-probe electrical conductivity measurementwas performed on Zn3BHT and tmM nanosheets. Althoughthe M3BHT series reported so far are well-known to beconductive coordination nanosheets,[17–20] Zn3BHT is aninsulator as shown in Figure S5. This can be attributed tothe closed-shell electronic structure of the Zn(II) ion, fromwhich it is difficult to generate free electrons or holes. Onthe contrary, once Zn ions are exchanged with othertransition metal ions, the tmM nanosheets become electricalconductors. Their electrical conductivity ranges from 3.06×10� 3 Scm� 1 for tmFe to 26.6 Scm� 1 for tmCu (Figure 2e).We also investigated the thermoelectric behaviour of tmM.tmCu is p-type with a Seebeck coefficient of about+15 μVK� 1 at room temperature. This value is 2–3 times aslarge as that of Cu3BHT previously reported.[27,28] Thereduced conductivity and enhanced Seebeck coefficientcould potentially reflect differences in the electronic struc-ture between tmCu and Cu3BHT due to the slipped AB vsAA stacking, but they may also be manifestations of ahigher concentration of defects in the films prepared bytransmetallation, such as defects induced by residual Zn.tmFe is also p-type with Seebeck coefficient of about +100μV K� 1 at room temperature, which is a typical magnitudefor a semiconductor (Figure S6). The larger Seebeck coef-ficient implies its lower carrier concentration compared totmCu.tmM nanosheets possess a variety of electrical character-istics as mentioned above. This inspired us to combine thetwo types of tmM to fabricate electronic devices byimmersing Zn3BHT sequentially in two different metal ionsolutions. Thin Zn3BHT nanosheet immobilised on SiO2/Sisubstrate was partially immersed in 50 mM Cu(II) or 50 mMFe(II) solution for 3 days. A boundary between Zn3BHTand tmCu or tmFe could be observed optically (Figure S7),suggesting that transmetallation proceeds exclusively at theimmersed region which enables its facile spatial control. Thenon-immersed area containing pristine Zn3BHT was sub-sequently immersed in 50 mM Fe(II) solution for 3 days(Figure 3a). Scanning electron microscopy was performed toimage the boundary area of a tmFe/tmCu lateral hetero-junction formed using the sequential-transmetallation meth-od (Figure 3b). The tmFe/tmCu boundary showed clearcontrast in the secondary electron image, where tmCu wasdark and tmFe was bright, and matches the elementaldistribution of the respective elements. The SEM-EDSmapping images and energy spectrum near the boundaryshow that Zn is absent all around the junction (Figure S8).Cu was distributed over the bottom half of the field of viewwhile Fe was found over the upper half of the EDS imagewhere Cu is absent. Therefore, we conclude that a lateralheterojunction of tmCu and tmFe was successfully formedwithout destroying the sheetlike morphology of the originalZn3BHT.Raman spectra across the tmFe/tmCu heterojunction(Figure 3c) revealed the formation of a seamless junction. Abroad peak at 320 cm� 1 was found in tmCu region whilesharp peaks at 356 cm� 1 and 409 cm� 1 was found in tmFeregion. These peaks are likely to originate from correspond-ing M� S vibration compared with previous studies.[27] Fig-ure 3d shows the Raman intensity taken at intervals of 1 μmacross the tmFe/tmCu junction visualised as 2D colour plot.The boundary around the position of 15 μm is estimated tobe �1 μm.The I–V curves of the lateral heterojunctions weremeasured at room temperature under Ar atmosphere by the2-probe method, using Au tips (Figure 4a). The boundaryarea in the middle can be roughly visualised with the slightcontrast in the images after transmetallation. Here wedescribe as Vij the voltage of tip i with respect to tip j. Iij isthe current flowing from tip i to tip j, likewise. FromFigure 4a, the I–V curve of I21 against V21, measurementacross the junction, reveals non-linear rectifying behaviouracross the junction. Current abruptly increased beyond+0.4 V while linear I–V characteristic was found in theFigure 3. Fabrication of tmM lateral heterojunction. a, Schematic of thefabrication of heterometal junction tmFe/tmCu. b, SEM image, EDSmaps of tmFe/tmCu heterojunction, and EDS spectrum of the mappedarea. The full spectrum is shown in Figure S8. c, Spatially resolvedRaman spectra taken every 1 μm across tmFe/tmCu heterojunctionfrom tmCu region (green lines, bottom) to tmFe region (blue lines,top). The triangles show remarkable peaks and the stars shows thepeak from the silicon substrate. d, 2D plot of Raman intensity againstRaman shift. The intensity was normalized to the peak top of eachregion. The silicon peak at 305 cm� 1 was analytically removed for theclarity by interpolation.AngewandteChemieCommunicationsAngew. Chem. Int. Ed. 2024, 63, e202318181 (4 of 6) © 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH 15213773, 2024, 9, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202318181 by Cochrane Japan, Wiley Online Library on [29/02/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensebackward direction. Confirmation that this behaviour is notdue to Schottky barriers between the Au tips and therespective tmM nanosheets is given by almost ohmic I–Vcurves measured between the 2 probes within each respec-tive tmFe or tmCu region (Figure S9). Therefore, we canconclude that it is the tmFe/tmCu junction that induces therectifying behaviour.To further investigate the electrical properties of bothtmFe and tmCu, Kelvin force microscopy (KFM) wasperformed on the nanosheets, obtaining the surface poten-tial. Figure 4b shows the topographic image of the tmFe/tmCu junction measured by AFM. There was no significantheight difference across the boundary between tmCu andtmFe even though clear colour contrast was observed in theoptical microscope image of the scanned region (Fig-ure S10). Hence, the transmetallation process in differentsolutions did not change the morphology of the film.Figure 4c shows the surface potential (SP) map of the samearea as Figure 4b, measured simultaneously by KFM. Anobvious clear boundary was observed on the SP map, incontrast to the topographical image. Given that the workfunction of Au surface is 5.30 eV,[29] the work function oftmFe and tmCu was calculated to be 5.33 eV and 5.46 eVrespectively, judging from SP profile across tmM/Au boun-dary (Figure S11). The SP profile shows that the SP changeswithin 2 μm of the boundary.These results of electrical conduction and KFM measure-ments are well explained by considering the formation of p-p junction at the tmFe/tmCu lateral junction. The banddiagrams before and after junction are depicted in Figure 4d.Since both tmCu and tmFe are p-type semiconductors, theirFermi levels are located above their valence bands. The holeconcentration of tmCu is expected to be much larger thantmFe judging from the smaller Seebeck coefficient and thelarger conductivity of tmCu. Therefore, the Fermi level oftmCu will be almost on the top of the valence band, whereasthat of tmFe will be located away from the top of thevalence band (Figure 4d). The difference in their workfunction leads to the mismatch of the Fermi level by0.13 eV. The different Fermi level is compensated by theelectron transfer from tmFe to tmCu which causes adepletion layer in the tmFe side of the junction. Conse-quently, a built-in potential of 0.13 eV is generated and theheterojunction works as a rectifier. The experimental resultssuggested that a positive forward bias of 0.4 V applied totmCu with respect to tmFe is required for the current tostart flowing, which can be attributed to the consumedvoltage drop between the junction and the probes.In conclusion, we have successfully fabricated a seamlessheterojunction (within 1 μm) showing diode behaviour, bysequential and spatially limited immersion of a new coordi-nation nanosheet Zn3BHT into aqueous Cu(II) and Fe(II)ion solutions. Insulating Zn3BHT undergoes transmetalla-tion while maintaining its BHT framework, with thesequential transmetallation process resulting in conductingtmFe/tmCu heterojunctions. tmFe exhibits p-type conduc-tion with Seebeck coefficient of +100 μVK� 1 and workfunction of 5.33 eV, while tmCu exhibits p-type conductionwith Seebeck coefficient of +15 μVK� 1 and work functionof 5.46 eV respectively.These results highlight the potential of Zn3BHT, whoseversatility is showcased by how its characteristics can bechanged easily without special equipment. Zn3BHT enables,for example, an integrated circuit all made from a singlecoordination nanosheet and drawn by inkjet printingmethod without patchworking different kinds of coordina-tion nanosheets and other materials. Therefore, our findingsshow that transmetallation of two-dimensional materials canbe a powerful new avenue towards fabricating lateralheterostructures while avoiding labour-intensive processes.Supporting InformationIncluding experimental details, materials, X-ray diffractiondata, Raman spectra, TEM and SEM images, calculationdetails.Figure 4. Electrical characterization of tmFe/tmCu heterojunction. a,Rectifying I–V curves of tmFe/tmCu heterojunction. b, AFM topographyimage and c, KFM surface potential mapping image of tmFe/tmCu onAu/mica substrate. d, Band diagram of tmFe and tmCu before (left)and after (right) the formation of the junction. The conduction bandsare omitted for clarity.AngewandteChemieCommunicationsAngew. Chem. Int. Ed. 2024, 63, e202318181 (5 of 6) © 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH 15213773, 2024, 9, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202318181 by Cochrane Japan, Wiley Online Library on [29/02/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons LicenseAcknowledgementsThe authors acknowledge financial support from JST-CREST JPMJCR15F2, JSPS KAKENHI Grant Number19H05460, JSPS KAKENHI Grant Number 22K05055, JSPSKAKENHI Grant Number 22K14569, EPSRC-JSPS core-to-core program (EP/S030662/1, JPJSCCA20190005), andWhite Rock Foundation. C.B. and T.M. acknowledgesupport from JST-Mirai JPMJMI19A1. H.S. thanks theRoyal Society for a Royal Society Research Professorship(RP\R1\201082). PXRD measurements were performed atBL44B2 at SPring-8 with approval of RIKEN (20190021,20210072). The authors acknowledge the Advanced Re-search Infrastructure for Materials and Nanotechnology inJapan (ARIM) of the Ministry of Education, Culture,Sports, Science and Technology (MEXT)(JPMXP1223UT0025) for the XPS measurements.Conflict of InterestThe authors declare no conflict of interest.Data Availability StatementThe data that support the findings of this study are availablefrom the corresponding author upon reasonable request.Keywords: Coordination Nanosheet · Lateral Heterojunction ·Nanostructures · Rectifier · Transmetallation[1] K. S. Novoselov, V. I. Fal’Ko, L. Colombo, P. R. Gellert, M. G.Schwab, K. Kim, Nature 2012, 490, 192–200.[2] S. Manzeli, D. Ovchinnikov, D. Pasquier, O. V. Yazyev, A.Kis, Nat. Rev. Mater. 2017, 2, 17033.[3] P. V. Pham, S. C. Bodepudi, K. Shehzad, Y. Liu, Y. Xu, B. Yu,X. Duan, Chem. Rev. 2022, 122, 6514–6613.[4] A. Pant, Z. Mutlu, D. Wickramaratne, H. Cai, R. K. Lake, C.Ozkan, S. Tongay, Nanoscale 2016, 8, 3870–3887.[5] M. Y. Li, Y. Shi, C. C. Cheng, L. 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