Environment-friendly 0D/2D nanocomposites for broadband UV-vis-NIR-sensitive photodetectors

• Applicant: Professor Dr. Dietrich R. T. Zahn
• Subject Area: Experimental Condensed Matter Physics
• Term: from 2019 to 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 424154386

• Final Report Year: 2023

Final Report Abstract

Size dependent optical and electronic properties of low dimensional semiconductors define a constant interest in their photochemical and photophysical applications as photocatalysts, light-emitting bio-labels, photovoltaic and other optoelectronic devices. This project intended to synthesize, study, and combine 0D (quantum dots - QDs) materials with exfoliated 2D materials and explore the potential of their composites as broadband photodetectors. In the project, we developed new reliable protocols for the synthesis of multicomponent ternary and mixed quaternary Ag(Cu)-In-Se, Ag(Cu)-In-S, Ag-Ga-S, and other QDs by environmentally friendly ("green") colloidal synthesis under mild conditions using biocompatible glutathione ligands, water as a solvent, and avoiding toxic metals. The QDs obtained exhibit absorption and strong photoluminescence (PL) mostly in visible range due to the quantum confinement effect. Changing the composition of QDs revealed the interesting phenomenon of band bowing for mixed Ag(Cu)-In-chalcogenides and internal stress for Ag-Ga-S both shifting the absorption tail to the near infrared (NIR) range. The multicomponent Ag(Cu)-In-selenides exhibit broadband PL similar to sulfides, indicating a similar origin of PL apparently due to self-trapped excitons. Liquid phase exfoliated 2D material graphitic carbon nitride (g-C3N4) exhibited bright blue photoluminescence distinct from that typical for multinary Ag(Cu)-In-chalcogenide QDs with green, yellow, or red emission. 2D g-C3N4 flakes self-assembled with parallel stacking to each other and preferable orientation to a substrate. In thin films the small photoresponse of g-C3N4-based structures observed is attributed to its extremely weak charge transport properties as measured in the direct current (dc) mode both in the dark and under illumination. However, the concept of 2D/0D devices remains reasonable when combining QDs with high absorption coefficients with 2D materials possessing good transport properties. Here, a planar structure of Ag-In-S QDs with crystalline flakes of bilayer MoS2 showed a responsivity on the order of tens of A/W in the visible range (e.g. ~15 A/W at ~1.95 eV in the excitonic maximum of Ag-In-S QDs) with an onset close to the NIR at ~1.7-1.8 eV. This example clearly demonstrates the potential of broadband 2D/0D photodetectors.

Publications

• Composition-Dependent Optical Band Bowing, Vibrational, and Photochemical Behavior of Aqueous Glutathione-Capped (Cu, Ag)–In–S Quantum Dots. The Journal of Physical Chemistry C, 124(35), 19375-19388.
  Raievska, Oleksandra; Stroyuk, Oleksandr; Azhniuk, Yuriy; Solonenko, Dmytro; Barabash, Anastasia; Brabec, Christoph J. & Zahn, Dietrich R. T.
  
• Graphitic carbon nitride nanotubes: a new material for emerging applications. RSC Advances, 10(56), 34059-34087.
  Stroyuk, Oleksandr; Raievska, Oleksandra & Zahn, Dietrich R. T.
  
• Phonon Spectra of Strongly Luminescent Nonstoichiometric Ag–In–S, Cu–In–S, and Hg–In–S Nanocrystals of Small Size. The Journal of Physical Chemistry C, 124(28), 15511-15522.
  Dzhagan, Volodymyr; Selyshchev, Oleksandr; Raievska, Oleksandra; Stroyuk, Oleksandr; Hertling, Lukas; Mazur, Nazar; Valakh, Mykhailo Ya. & Zahn, Dietrich R. T.
  
• Raman and X-ray Photoemission Identification of Colloidal Metal Sulfides as Potential Secondary Phases in Nanocrystalline Cu2ZnSnS4 Photovoltaic Absorbers. ACS Applied Nano Materials, 3(6), 5706-5717.
  Selyshchev, Oleksandr; Havryliuk, Yevhenii; Valakh, Mykhailo Ya.; Yukhymchuk, Volodymyr O.; Raievska, Oleksandra; Stroyuk, Oleksandr L.; Dzhagan, Volodymyr & Zahn, Dietrich R.T.
  
• Ultra-small aqueous glutathione-capped Ag–In–Se quantum dots: luminescence and vibrational properties. RSC Advances, 10(69), 42178-42193.
  Raievska, Oleksandra; Stroyuk, Oleksandr; Dzhagan, Volodymyr; Solonenko, Dmytro & Zahn, Dietrich R. T.
  
• Effect of pH and Polyelectrolytes on the Spectral-Kinetic Properties of AIS/ZnS Semiconductor Quantum Dots in Aqueous Solutions. Journal of Applied Spectroscopy, 87(6), 1057-1066.
  Motevich, I. G.; Zenkevich, E. I.; Stroyuk, A. L.; Raevskaya, A. E.; Kulikova, O. M.; Sheinin, V. B.; Koifman, О. I.; Zahn, D. R. T. & Strekal, N. D.
  
• High-Throughput Time-Resolved Photoluminescence Study of Composition-and Size-Selected Aqueous Ag–In–S Quantum Dots. The Journal of Physical Chemistry C, 125(22), 12185-12197.
  Stroyuk, Oleksandr; Raievska, Oleksandra; Kupfer, Christian; Solonenko, Dmytro; Osvet, Andres; Batentschuk, Miroslaw; Brabec, Christoph J. & Zahn, Dietrich R. T.
  
• High‐Throughput Robotic Synthesis and Photoluminescence Characterization of Aqueous Multinary Copper–Silver Indium Chalcogenide Quantum Dots. Particle & Particle Systems Characterization, 38(10).
  Stroyuk, Oleksandr; Raievska, Oleksandra; Langner, Stefan; Kupfer, Christian; Barabash, Anastasia; Solonenko, Dmytro; Azhniuk, Yuriy; Hauch, Jens; Osvet, Andres; Batentschuk, Miroslaw; Zahn, Dietrich R. T. & Brabec, Christoph J.
  
• Raman and X-ray Photoelectron Spectroscopic Study of Aqueous Thiol-Capped Ag-Zn-Sn-S Nanocrystals. Materials, 14(13), 3593.
  Dzhagan, Volodymyr; Selyshchev, Oleksandr; Havryliuk, Yevhenii; Mazur, Nazar; Raievska, Oleksandra; Stroyuk, Oleksandr; Kondratenko, Serhiy; Litvinchuk, Alexander P.; Valakh, Mykhailo Ya. & Zahn, Dietrich R. T.
  
• Room-Temperature Electron Paramagnetic Resonance Study of a Copper-Related Defect in Cu2ZnSnS4 Colloidal Nanocrystals. The Journal of Physical Chemistry C, 125(18), 9923-9929.
  Vorona, Igor; Dzhagan, Volodymyr; Nosenko, Valentyna; Kondratenko, Serhiy; Selyshchev, Oleksandr; Valakh, Mykhailo; Okulov, Serhiy; Mazur, Nazar; Raievska, Oleksandra; Stroyuk, Oleksandr L. & Zahn, Dietrich R. T.
  
• Single-layer carbon nitride: synthesis, structure, photophysical/photochemical properties, and applications. Physical Chemistry Chemical Physics, 23(37), 20745-20764.
  Stroyuk, Oleksandr; Raievska, Oleksandra & Zahn, Dietrich R. T.
  
• Spontaneous alloying of ultrasmall non-stoichiometric Ag–In–S and Cu–In–S quantum dots in aqueous colloidal solutions. RSC Advances, 11(34), 21145-21152.
  Stroyuk, Oleksandr; Raievska, Oleksandra; Solonenko, Dmytro; Kupfer, Christian; Osvet, Andres; Batentschuk, Miroslaw; Brabec, Christoph J. & Zahn, Dietrich R. T.
  
• Copper-Content Dependent Structural and Electrical Properties of CZTS Films Formed by “Green” Colloidal Nanocrystals. Electronic Materials, 3(1), 136-153.
  Dzhagan, Volodymyr; Selyshchev, Oleksandr; Kondratenko, Serhiy; Mazur, Nazar; Havryliuk, Yevhenii; Raievska, Oleksandra; Stroyuk, Oleksandr & Zahn, Dietrich R. T.
  
• Optical and Structural Characteristics of Rare Earth-Doped ZnO Nanocrystals Prepared in Colloidal Solution. Photochem, 2(3), 515-527.
  Toma, Maria; Selyshchev, Oleksandr; Havryliuk, Yevhenii; Pop, Aurel & Zahn, Dietrich R. T.
  
• Raman Spectroscopy and Thermoelectric Characterization of Composite Thin Films of Cu2ZnSnS4 Nanocrystals Embedded in a Conductive Polymer PEDOT:PSS. Nanomaterials, 13(1), 41.
  Havryliuk, Yevhenii; Dzhagan, Volodymyr; Karnaukhov, Anatolii; Selyshchev, Oleksandr; Hann, Julia & Zahn, Dietrich R. T.
  
• Self-assembly of colloidal single-layer carbon nitride. Nanoscale, 14(34), 12347-12357.
  Stroyuk, Oleksandr; Raievska, Oleksandra; Brabec, Christoph J.; Dzhagan, Volodymyr; Havryliuk, Yevhenii & Zahn, Dietrich R. T.
  
• Synthesis and Optical Properties of Ag–Ga–S Quantum Dots. physica status solidi (b), 259(10).
  Azhniuk, Yuriy; Lopushanska, Bohdana; Selyshchev, Oleksandr; Havryliuk, Yevhenii; Pogodin, Artem; Kokhan, Oleksandr; Ehm, Alexander; Lopushansky, Vasyl; Studenyak, Ihor & Zahn, Dietrich R.T.
  
• Core and Shell Contributions to the Phonon Spectra of CdTe/CdS Quantum Dots. Nanomaterials, 13(5), 921.
  Dzhagan, Volodymyr; Mazur, Nazar; Kapush, Olga; Selyshchev, Oleksandr; Karnaukhov, Anatolii; Yeshchenko, Oleg A.; Danylenko, Mykola I.; Yukhymchuk, Volodymyr & Zahn, Dietrich R. T.
  
• Enhanced photoconductivity of hybrid 2D-QD MoS2–AgInS2 structures. The Journal of Chemical Physics, 159(4).
  Kondratenko, Serhiy; Datsenko, Oleksandr I.; Babich, Danylo; Dzhagan, Volodymyr; Pan, Yang; Rahaman, Mahfujur; Selyshchev, Oleksandr & Zahn, Dietrich R. T.
  
• Influence of Thermal and Flash-Lamp Annealing on the Thermoelectrical Properties of Cu2ZnSnS4 Nanocrystals Obtained by “Green” Colloidal Synthesis. Nanomaterials, 13(11), 1775.
  Havryliuk, Yevhenii; Dzhagan, Volodymyr; Karnaukhov, Anatolii; Selyshchev, Oleksandr; Hann, Julia & Zahn, Dietrich R. T.