{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,6]],"date-time":"2025-11-06T12:32:56Z","timestamp":1762432376982,"version":"build-2065373602"},"reference-count":40,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2023,7,28]],"date-time":"2023-07-28T00:00:00Z","timestamp":1690502400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Conseil r\u00e9gional de Bourgogne through the CPER program","award":["2017EKCS35_002"],"award-info":[{"award-number":["2017EKCS35_002"]}]},{"name":"Conseil r\u00e9gional Bourgogne Franche-Comt\u00e9 through the Envergure Program MatElectroCap (2020\u20132024)","award":["2017EKCS35_002"],"award-info":[{"award-number":["2017EKCS35_002"]}]},{"name":"Italian Ministry of Education, University and Research (MIUR)","award":["2017EKCS35_002"],"award-info":[{"award-number":["2017EKCS35_002"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Sensors"],"abstract":"<jats:p>The versatility of metal complexes of corroles has raised interest in the use of these molecules as elements of chemical sensors. The tuning of the macrocycle properties via synthetic modification of the different components of the corrole ring, such as functional groups, the molecular skeleton, and coordinated metal, allows for the creation of a vast library of corrole-based sensors. However, the scarce conductivity of most of the aggregates of corroles limits the development of simple conductometric sensors and requires the use of optical or mass transducers that are rather more cumbersome and less prone to be integrated into microelectronics systems. To compensate for the scarce conductivity, corroles are often used to functionalize the surface of conductive materials such as graphene oxide, carbon nanotubes, or conductive polymers. Alternatively, they can be incorporated into heterojunction devices where they are interfaced with a conductive material such as a phthalocyanine. Herewith, we introduce two heterostructure sensors combining lutetium bisphthalocyanine (LuPc2) with either 5,10,15-tris(pentafluorophenyl) corrolato Cu (1) or 5,10,15-tris(4-methoxyphenyl)corrolato Cu (2). The optical spectra show that after deposition, corroles maintain their original structure. The conductivity of the devices reveals an energy barrier for interfacial charge transport for 1\/LuPc2, which is a heterojunction device. On the contrary, only ohmic contacts are observed in the 2\/LuPc2 device. These different electrical properties, which result from the different electron-withdrawing or -donating substituents on corrole rings, are also manifested by the opposite response with respect to ammonia (NH3), with 1\/LuPc2 behaving as an n-type conductor and 2\/LuPC2 behaving as a p-type conductor. Both devices are capable of detecting NH3 down to 10 ppm at room temperature. Furthermore, the sensors show high sensitivity with respect to relative humidity (RH) but with a reversible and fast response in the range of 30\u201360% RH.<\/jats:p>","DOI":"10.3390\/s23156773","type":"journal-article","created":{"date-parts":[[2023,7,31]],"date-time":"2023-07-31T02:13:32Z","timestamp":1690769612000},"page":"6773","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Ammonia and Humidity Sensing by Phthalocyanine\u2013Corrole Complex Heterostructure Devices"],"prefix":"10.3390","volume":"23","author":[{"given":"Lorena","family":"Di Zazzo","sequence":"first","affiliation":[{"name":"Institut de Chimie Mol\u00e9culaire de l\u2019Universit\u00e9 de Bourgogne, UMR CNRS 6302, Universit\u00e9 de Bourgogne, 9 Avenue Alain Savary, 21000 Dijon, France"},{"name":"Department of Electronic Engineering, University of Rome Tor Vergata, Via Politecnico 1, 00133 Roma, Italy"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3154-2246","authenticated-orcid":false,"given":"Sujithkumar","family":"Ganesh Moorthy","sequence":"additional","affiliation":[{"name":"Institut de Chimie Mol\u00e9culaire de l\u2019Universit\u00e9 de Bourgogne, UMR CNRS 6302, Universit\u00e9 de Bourgogne, 9 Avenue Alain Savary, 21000 Dijon, France"}]},{"given":"Rita","family":"Meunier-Prest","sequence":"additional","affiliation":[{"name":"Institut de Chimie Mol\u00e9culaire de l\u2019Universit\u00e9 de Bourgogne, UMR CNRS 6302, Universit\u00e9 de Bourgogne, 9 Avenue Alain Savary, 21000 Dijon, France"}]},{"given":"Eric","family":"Lesniewska","sequence":"additional","affiliation":[{"name":"Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR CNRS 6303, Universit\u00e9 de Bourgogne, 9 Avenue Alain Savary, 21000 Dijon, France"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0543-4348","authenticated-orcid":false,"given":"Corrado","family":"Di Natale","sequence":"additional","affiliation":[{"name":"Department of Electronic Engineering, University of Rome Tor Vergata, Via Politecnico 1, 00133 Roma, Italy"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2380-1404","authenticated-orcid":false,"given":"Roberto","family":"Paolesse","sequence":"additional","affiliation":[{"name":"Department of Chemical Science and Technology, University of Rome Tor Vergata, Via della Ricerca Scientifica, 00133 Roma, Italy"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2272-6633","authenticated-orcid":false,"given":"Marcel","family":"Bouvet","sequence":"additional","affiliation":[{"name":"Institut de Chimie Mol\u00e9culaire de l\u2019Universit\u00e9 de Bourgogne, UMR CNRS 6302, Universit\u00e9 de Bourgogne, 9 Avenue Alain Savary, 21000 Dijon, France"}]}],"member":"1968","published-online":{"date-parts":[[2023,7,28]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"710","DOI":"10.1038\/35021028","article-title":"A colorimetric sensor array for odour visualization","volume":"406","author":"Rakow","year":"2000","journal-title":"Nature"},{"key":"ref_2","first-page":"227","article-title":"Molecular semiconductor-based gas sensors","volume":"Volume 6","author":"Grimes","year":"2006","journal-title":"The Encyclopedia of Sensors"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"121","DOI":"10.1142\/9789814322386_0006","article-title":"54 Porphyrin-Based Chemical Sensors","volume":"Volume 12","author":"Paolesse","year":"2011","journal-title":"Handbook of Porphyrin Science"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"2517","DOI":"10.1021\/acs.chemrev.6b00361","article-title":"Porphyrinoids for Chemical Sensor Applications","volume":"117","author":"Paolesse","year":"2017","journal-title":"Chem. Rev."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"3712","DOI":"10.1021\/la063114i","article-title":"New Hybrid Films Based on Cellulose and Hydroxygallium Phthalocyanine. Synergetic Effects in the Structure and Properties","volume":"23","author":"Parra","year":"2007","journal-title":"Langmuir"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"70","DOI":"10.1016\/j.snb.2005.11.067","article-title":"Sorting of apricots with computer screen photoassisted spectral reflectance analysis and electronic nose","volume":"119","author":"Filippini","year":"2006","journal-title":"Sens. Actuators B Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"180","DOI":"10.1016\/j.electacta.2013.12.079","article-title":"Evaluation of red wines antioxidant capacity by means of a voltammetric e-tongue with an optimized sensor array","volume":"120","author":"Apetrei","year":"2014","journal-title":"Electrochim. Acta"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1209","DOI":"10.1016\/S0956-5663(03)00086-1","article-title":"Lung cancer identification by the analysis of breath by means of an array of non-selective gas sensors","volume":"18","author":"Macagnano","year":"2003","journal-title":"Biosens. Bioelectron."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"3103","DOI":"10.1002\/anie.200463009","article-title":"Organic-inorganic hybrid sol-gel materials incorporating functionalized cobalt(III) corroles for the selective detection of CO","volume":"44","author":"Barbe","year":"2005","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1348","DOI":"10.1002\/elan.201200077","article-title":"meso-Tritolylcorrole-functionalized single-walled carbon nanotube donor-acceptor nanocomposites for NO2 detection","volume":"24","author":"Wang","year":"2012","journal-title":"Electroanalysis"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"13811","DOI":"10.1039\/c2jm31281f","article-title":"Corroles as anion chemosensors: Exploiting their fluorescence behaviour from solution to solid-supported devices","volume":"22","author":"Santos","year":"2012","journal-title":"J. Mater. Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"129507","DOI":"10.1016\/j.snb.2021.129507","article-title":"Influence of interfering gases on a carbon monoxide differential sensor based on SAW devices functionalized with cobalt and copper corroles","volume":"332","author":"Vanotti","year":"2021","journal-title":"Sens. Actuators B Chem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1277","DOI":"10.1039\/D1CS00662B","article-title":"Corroles at work: A small macrocycle for great applications","volume":"51","author":"Gros","year":"2022","journal-title":"Chem. Soc. Rev."},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Johnson, A.W., and Kay, I.T. (1965). 306. Corroles. Part I. Synthesis. J. Chem. Soc., 1620\u20131629.","DOI":"10.1039\/jr9650001620"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1307","DOI":"10.1039\/a903247i","article-title":"5,10,15-Triphenylcorrole: A product from a modified Rothemund reaction","volume":"14","author":"Paolesse","year":"1999","journal-title":"Chem. Commun."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1427","DOI":"10.1002\/(SICI)1521-3773(19990517)38:10<1427::AID-ANIE1427>3.0.CO;2-1","article-title":"The first direct synthesis of corroles from pyrrole","volume":"38","author":"Gross","year":"1999","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1940001","DOI":"10.1142\/S1793604719400010","article-title":"Synthesis and gas sensitivity properties of novel metallocorroles and functionalized graphene oxide","volume":"12","author":"Tang","year":"2019","journal-title":"Funct. Mater. Let."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1776","DOI":"10.1039\/b906786h","article-title":"Molecular semiconductor-doped insulator (MSDI) heterojunctions: An alternative transducer for gas chemosensing","volume":"134","author":"Parra","year":"2009","journal-title":"Analyst"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"19974","DOI":"10.1021\/acsami.8b03601","article-title":"Comprehensive Study of poly(2,3,5,6-tetrafluoroaniline): From electrosynthesis to heterojunctions and ammonia sensing","volume":"10","author":"Mateos","year":"2018","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"132453","DOI":"10.1016\/j.cej.2021.132453","article-title":"Tuning of interfacial charge transport in polyporphine\/phthalocyanine heterojunctions by molecular geometry control for an efficient gas sensor","volume":"429","author":"Kumar","year":"2022","journal-title":"Chem. Eng. J."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"141465","DOI":"10.1016\/j.cej.2023.141465","article-title":"Electrosynthesized copper polycorroles as versatile materials in double lateral heterojunctions","volume":"458","author":"Kumar","year":"2023","journal-title":"Chem. Eng. J."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"1849","DOI":"10.1021\/acssensors.0c00877","article-title":"Modulating the electrical properties of organic heterojunction devices based on phthalocyanines for ambipolar sensors","volume":"5","author":"Ouedraogo","year":"2020","journal-title":"ACS Sens."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1694","DOI":"10.1016\/j.snb.2017.08.184","article-title":"New n-type molecular semiconductor\u2013doped insulator (MSDI) heterojunctions combining a triphenodioxazine (TPDO) and the lutetium bisphthalocyanine (LuPc2) for ammonia sensing","volume":"255","author":"Wannebroucq","year":"2018","journal-title":"Sens. Actuators B Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"129505","DOI":"10.1016\/j.snb.2021.129505","article-title":"Tuning of organic heterojunction conductivity by the substituents\u2019 electronic effects in phthalocyanines for ambipolar gas sensors","volume":"332","author":"Sahin","year":"2021","journal-title":"Sens. Actuators B Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"864","DOI":"10.1016\/j.snb.2015.09.021","article-title":"Reduced graphene oxide (rGO) encapsulated Co3O4 composite nanofibers for highly selective ammonia sensors","volume":"222","author":"Feng","year":"2016","journal-title":"Sens. Actuators B Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"79","DOI":"10.4028\/www.scientific.net\/AMR.669.79","article-title":"Ammonia gas sensor based on aniline reduced graphene oxide","volume":"669","author":"Huang","year":"2013","journal-title":"Adv. Mater. Res."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"6448","DOI":"10.1039\/C8TC06309E","article-title":"Tungsten oxide\u2014Lutetium bisphthalocyanine n-p-n heterojunction: From nanomaterials to a new transducer for chemo-sensing","volume":"7","author":"Bouvet","year":"2019","journal-title":"J. Mater. Chem. C"},{"key":"ref_28","first-page":"37","article-title":"Radical phthalocyanines and intrinsic semiconduction","volume":"Volume 19","author":"Kadish","year":"2003","journal-title":"The Porphyrin Handbook"},{"key":"ref_29","doi-asserted-by":"crossref","unstructured":"Zhou, Y., and Han, S.T. (2020). Ambipolar Materials and Devices, Royal Society of Chemistry.","DOI":"10.1039\/9781788019279"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"139","DOI":"10.1016\/S0020-1693(00)85943-5","article-title":"Synthesis and characterization of some lanthanide phthalocyanines","volume":"130","author":"Clarisse","year":"1987","journal-title":"Inorg. Chim. Acta"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"550","DOI":"10.1021\/jo005661t","article-title":"Synthesis and Functionalization of meso-Aryl-Substituted Corroles","volume":"66","author":"Paolesse","year":"2001","journal-title":"J. Org. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"10791","DOI":"10.1021\/ic7014572","article-title":"Functionalization of corroles: The nitration reaction","volume":"46","author":"Stefanelli","year":"2007","journal-title":"Inorg. Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"501","DOI":"10.1016\/j.snb.2009.12.064","article-title":"Molecular semiconductor-doped insulator (MSDI) heterojunctions: Oligothiophene\/bisphtalocyanine (LuPc2) and perylene\/bisphthalocyanine as new structures for gas sensing","volume":"145","author":"Bouvet","year":"2010","journal-title":"Sens. Actuators B Chem."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"26","DOI":"10.1149\/1.3314449","article-title":"Measurements and prediction of electronic properties of discotic liquid crystalline triphenylenes and phthalocyanines","volume":"25","author":"Ahmida","year":"2010","journal-title":"ECS Trans."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"12851","DOI":"10.1039\/c0cp00381f","article-title":"Facile approaches to build ordered amphiphilic tris(phthalocyaninato) europium triple-decker complex thin films and their comparative performances in ozone sensing","volume":"12","author":"Chen","year":"2010","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"34103","DOI":"10.1051\/epjap\/2011110220","article-title":"Molecular semiconductor-doped insulator (MSDI) heterojunctions as new transducers for chemical sensors","volume":"56","author":"Bouvet","year":"2011","journal-title":"Eur. Phys. J. Appl. Phys."},{"key":"ref_37","first-page":"317","article-title":"Detection of carbon-fluorine bonds in organofluorine compounds by Raman spectroscopy using a copper-vapor laser","volume":"3537","author":"Sharts","year":"1999","journal-title":"Proc. SPIE-Int. Soc. Opt. Eng."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"269","DOI":"10.1039\/C005252C","article-title":"Development of carbon-fluorine spectroscopy for pharmaceutical and biomedical applications","volume":"149","author":"Menaa","year":"2011","journal-title":"Faraday Discuss."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"8104","DOI":"10.1021\/ja0113697","article-title":"Electronic Absorption, Resonance Raman, and electrochemical studies of planar and saddled copper(iii) meso-triarylcorroles. Highly substituent-sensitive Soret bands as a distinctive feature of high-valent transition metal corroles","volume":"124","author":"Wasbotten","year":"2002","journal-title":"J. Am. Chem. Soc."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"657","DOI":"10.1016\/j.snb.2017.11.146","article-title":"On the interest of ambipolar materials for gas sensing","volume":"258","author":"Wannebroucq","year":"2018","journal-title":"Sens. Actuators B Chem."}],"container-title":["Sensors"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1424-8220\/23\/15\/6773\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T20:21:49Z","timestamp":1760127709000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1424-8220\/23\/15\/6773"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,7,28]]},"references-count":40,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2023,8]]}},"alternative-id":["s23156773"],"URL":"https:\/\/doi.org\/10.3390\/s23156773","relation":{},"ISSN":["1424-8220"],"issn-type":[{"type":"electronic","value":"1424-8220"}],"subject":[],"published":{"date-parts":[[2023,7,28]]}}}