Ultrafast Spectroscopy Laboratory

Ultrafast Spectroscopy Laboratory (USL) was established in 2016 as a platform for multidisciplinary research at Dalian University of Technology (DUT). USL (the first in DUT and the second in Liaoning province) aimed at time-resolved measurements in the field of solar cells, photochemistry of functional dyes, nanoscience, photocatalysis,etc.

USL includes various spectroscopic instruments: home-made femtosecond pump-probe technique, time correlated single photon counting (TCSPC), fluorescence up-conversion, Z-scan technique, coherent anti-stokes Raman scattering microscopy (CARS), steady-state spectrophotometer and spectrofluorometer. All measurements can be performed at low temperatures down to 77K.

Ultrafast time-resolved laser spectroscopy has wide applications in studies of molecular excited states, photochemical reactions, photocatalytic, energy and charge transfer processes (including the primary processes in photosynthesis, artificial photovoltaics, light emitting devices, etc.), nanomaterials characterization, protein folding kinetics, superconductors, spintronics and biomedicine.

Projects

Enhancement of S₂ fluorescence in H₂TTP-SURMOF

The ultrafast transient dynamics of a free-base tetraphenylporphyrin (H₂TPP) surface-mounted metal organic framework (SURMOF) is spectroscopically characterized. Dramatic increase of the quantum yield of the Soret band fluorescence (S₂→S₀) is observed in the H₂TPP-SURMOF, which is accompanied by an increase of the S₂ fluorescence lifetime and a broadening of the fluorescence spectrum.

Ultrafast relaxation dynamics of ZnTTP-SURMOF

Dramatic quenching of both upper excited singlet state S₂ and the first excited state S₁ was observed in zinc tetraphenylporphyrin ZnTPP/SURMOF, which is explained in terms of highly efficient Förster Resonance Energy Transfer (FRET) between the neighboring porphyrin moieties.

Singlet fission in cofacial perylene dimer

Singlet fission is a spin-allowed process when one excited-state molecule shares its energy with  neighboring ground-state molecule to produce two triplet excited molecules. Direct singlet fission was detected from the upper excited vibrational and electronic states of cofacial perylene dimers, bypassing the relaxed state S₁, thus violating classical Kasha-Vavilov rule.

Ultrafast polaron and triplet exciton formation in six-thiophene thin film and single crystal

 In six-thiophene (6T) thin film and single crystal, the dominant photocarriers were identified as polarons which caused the transient absorption spectral diffusion. Singlet fission was observed from the upper vibrational levels of S₁ state within 30 fs. The remarkably different lifetimes of both polarons and triplet excitons in 6T thin film and single crystal is discussed in terms of the film morphology and molecular packing of conjugated oligomers.

Instrumentation

 Femtosecond Pump-Probe

 Femtosecond transient absorption spectra with time resolution of 20-30 fs can be obtained by use of home-made pump-probe setup. It consists of mode-locked Ti-sapphire amplified laser system (Spitfire Ace, Spectra-Physics). The pump beam (240-2400 nm) is   generated through an optical parametric amplifier (TOPAS, Light conversion). The probe   beam, white light continuum (350-850 nm), is generated in CaF₂ plate.

Time-Correlated Single Photon Counting (TCSPC)

Time-resolved photoluminescence measurements can be carried out by time-correlated single photon counting (TCSPC) technique (PicoHarp 300, PicoQuant). By use of deconvolution/fit program (FluoFit, PicoQuant) the time resolution can be reached down to 10 ps. The second and third harmonic of tunable titanium−sapphire laser (Mai Tai DeepSee, Spectra-Physics) at 230-540 nm (150 fs, 80 MHz) is used as the excitation source. 

Up-conversion  

Fluorescence lifetimes down to 100 fs are recorded by use of up-conversion method with a time resolved fluorescence spectrometer (TRFLS, Newport) in combination with a mode-locked Ti-sapphire laser (Mai Tai DeepSee, Spectra-Physics). Excitation wavelength is 400 nm, fluorescence detection range is 420-750 nm.

About Us

Gagik Gurzadyan

Leader of laboratory, Supervisor

Nonlinear optics, ultrafast laser spectroscopy, laser photochemistry, two-quantum  photoprocesses, singlet fission, relaxation processes, energy and charge transfer in  various components of solar cells, functional dyes, polymers, graphene, organic crystals,  MOF/SURMOFs.

Email: gurzadyan@dlut.edu.cn

Xiaoxin Li

Graduated

ZnTPP and H2TPP SURMOF
Perovskite cell fluorescence characterization

 Wenjun Ni (Juno)

 Ph.D student

 Photophysical processes in perylene-TCNO co-crystals. Singlet fission in rubrene nanoparticles. Singlet fission based solar cells. Singlet fission from higher excited electronic states in perylene systems (solution, films).

 Email: wjni@mail.dlut.edu.cn

Yichen Zhou (Chloe)

Ph.D student

 Ultrafast relaxation dynamics of highly excited states of organic compounds

 Email: zyc124zyc@qq.com

 Tong Wu (Tonya)

 Master student

 Singlet fission in organic thin films

 Email: 14273043@bjtu.edu.cn

 

Tongyu Zhao (Tanya)

 Master student

 Ultrafast relaxation dynamics in organic thin films and single crystals

 Email: 914286467@qq.com

 

Zhiyong Zhang

 Master student

 Ultrafast relaxation dynamics of MOF organic systems

 Email: 799989893@qq.com

Tianjiao Li (Lilit)

 Master student

 Singlet fission in organic compounds and films. DFT calculations

 Email: 18864832250@163.com

Jing Feng (Elena)

 Master student

 Ultrafast relaxation dynamics of MOF organic systems

 Email: fengjinglinjj@163.com

Publications

Books

[1] G.G. Gurzadyan, G. Lanzani, C. Soci, T.C. Sum. Ultrafast dynamics in molecules, nanostructures and interfaces. World Scientific Publishing Company, Singapore, 304 p, ISBN-10: 9814556912, ISBN-13: 978-9814556910, 2014.

[2] G. Yu Kryuchkyan, G.G. Gurzadyan, A.V. Papoyan. Modern optics and photonics.  World Scientific Publishing Co Pte Ltd, Singapore, 400 p, ISBN-10: 9814313262, ISBN-13: 9789814313261, 2010. 

[3] 作者: (俄罗斯)德米特里耶夫(V.G. Dmitriev), (亚美尼亚)古尔扎姜(G.G. Gurzadyan), (俄罗斯)尼科戈相(D.N. Nikogosyan), 译者: 王继扬, 注释、解说词: 吴以成, 非线性光学晶体手册(第3版修订本)(Handbook of Nonlinear Optical Crystals). 高等教育出版社, 中国, ISBN: 9787040277807, 2009.

[4] H.J. Eichler, B. Eppich, J. Fischer, R. Güther, G.G. Gurzadyan, A. Hermerschmidt, A. Laubereau, V.A. Lopota, O. Mehl, C.R. Vidal, H. Weber, B. Wende. Laser Physics and Applications. Springer-Verlag, Berlin Heidelberg, New-York, 268 p, ISBN: 3-540-00105-0, 2005. 

[5] F. Charra, G.G. Gurzadyan. Nonlinear dielectric susceptibilities. Landolt-Börnstein, New series III, Germany, 486 p, ISBN: 3-540-65567-0, 2000. 

[6] G.G. Gurzadyan, A.V. Karmenyan. New trends in atomic and molecular spectroscopy. Proceedings of SPIE, 232 p, ISBN: 978-0819436894, 2000.

[7] V.G. Dmitriev, G.G. Gurzadyan, D.N. Nikogosyan. Handbook of nonlinear optical crystals (third, revised edition). Springer-Verlag, Berlin, Heidelberg, New-York, 414 p, ISBN: 3-540-65394-5, 1999.

[8] V.G. Dmitriev, G.G. Gurzadyan, D.N. Nikogosyan. Handbook of nonlinear optical crystals (Springer series in optical sciences). Springer-Verlag, Berlin, Heidelberg, New-York, 222 p, ISBN: 3-540-53547-0, 1991. 

[9] G.G. Gurzadyan, V.G. Dmitriev, D.N. Nikogosyan. Nonlinear optical crystals. Properties and applications in quantum electronics (in Russian). Radio and Communications, Moscow, Russia, 160 p, ISBN: 5-256-00859-5, 1991.

Articles

[1] Wenjun Ni, Licheng Sun, Gagik G. Gurzadyan. Ultrafast spectroscopy reveals singlet fission, ionization and excimer formation in perylene film. Sci. Rep. 11, 5220, 2021.

[2] Tong Wu, Wenjun Ni, Gagik G. Gurzadyan, Licheng Sun. Singlet fission from upper excited singlet states and polaron formation in rubrene film. RSC Adv. 11, 4639, 2021.
[3] Noreen Rehmat, Ivan V. Kurganskii, Zafar Mahmood, QingLin Guan, Jianzhang Zhao, Yong Heng Xing, Gagik G. Gurzadyan, Matvey V. Fedin. Spin-orbit Charge Transfer Intersystem Crossing (SOCT-ISC) in Anthracene-Perylenebisimide Compact Electron Donor/Acceptor Dyads and Triads and Photochemical Dianion Formation. Chem. Europ. J. 27, 5521 –5535, 2021.

[4] Tongyu Zhao, Christian Kloc, Wenjun Ni, Licheng Sun, Gagik G. Gurzadyan. Revealing ultrafast relaxation dynamics in six-thiophene thin film and single crystal. J. Photochem. Photobiol. A 404, 112920, 2021.

[5] Dabin Lin, Lin Ma, Wenjun Ni, Cheng Wang, Fangteng Zhang, Huafeng Dong, Gagik G. Gurzadyan and Zhaogang Nie. Unveiling hot carrier relaxation and carrier transport mechanisms in quasi-two-dimensional layered perovskites. J. Mater. Chem. A DOI: 10.1039/D0TA09530C, 2020.

[6] Wenbo Yang, Andrei A. Sukhanov, Jong Hyeon Lim, Xiaoxin Li, Yinshan Meng, Jianzhang Zhao, Haoling Sun, Jin Yong Lee, Gagik G. Gurzadyan, Violeta K. Voronkova. N^N Pt(II) bisacetylide complexes with oxoverdazyl radical ligands: Preparation, photophysical properties, and magnetic exchange interaction between the two radical ligands. Inorg. Chem. 59, 12471-12485, 2020.

[7] Qingxuan Fan, Wenjun Ni, Lingcheng Chen, Gagik G. Gurzadyan, Yi Xiao. Singlet relaxation dynamics and long triplet lifetimes of thiophene-coupled perylene diimides dyads: New insights for high efficiency organic solar cells. Chin. Chem. Lett. 31, 2965-2969, 2020.

[8] Yichen Zhou, Gagik G. Gurzadyan, Wenjun Ni, Maxim F. Gelin, Licheng Sun. Upper excited state photophysics of malachite green in solution and films. J. Phys. Chem. B 124, 4293-4302, 2020.

[9] Wenjun Ni, Gagik G. Gurzadyan, Lin Ma, Peng Hu, Kloc, Christian, Licheng Sun. Ultrafast tuning of various photochemical pathways in perylene-TCNQ charge-transfer crystals. J. Phys. Chem. C 124, 13894-13901, 2020.

[10] Yanming Lei, Kepeng Chen, Geliang Tang, Jianzhang Zhao, Gagik G. Gurzadyan. Bodipy-phenylethynyl anthracene dyad: spin-orbit charge transfer intersystem crossing and triplet excited-state equilibrium. J. Photochem. Photobiol. A 398, 112573, 2020.

[11] Yuang Zhang, Gagik G. Gurzadyan, Rongwen Lu, Shufen Zhang, Xin Jin, Bingtao Tang. Efficient photothermal conversion of Fe₂O₃-RGO guided from ultrafast quenching effect of photoexcited state. ALChE J. e16975, 2020. 

[12] Hainan Shi, Jun Du, Jungang Hou, Wenjun Ni, Chunshan Song, Keyan Li, Gagik G. Gurzadyan, Xinwen Guo. Solar-driven CO₂ conversion over Co²⁺ doped 0D/2D TiO₂/g-C₃N₄ heterostructure: Insights into the role of Co²⁺ and cocatalyst. J. CO₂ Util. 38, 16-23, 2020.

[13] Wenbo Yang, Jianzhang Zhao, Geliang Tang, Xiaoxin Li, Gagik G. Gurzadyan. Direct observation of long-lived upper excited triplet states and intersystem crossing in anthracene-containing PtII complexes. J. Phys. Chem. Lett. 10, 7767-7773, 2019.

[14] Yingjie Zhao, Andrey A. Sukhanov, Ruomeng Duan, Ayhan Elmali, Yuqi Hou, Jianzhang Zhao, Gagik G. Gurzadyan, Ahmet Karatay, Violeta K. Voronkova, Chen Li. Study of the spin-orbit charge transfer intersystem crossing of perylenemonoimide-phenothiazine compact electron donor/acceptor dyads with steady-state and time-resolved optical and magnetic spectroscopies. J. Phys. Chem. C 123, 18270-18282, 2019.

[15] Wenjun Ni, Gagik G. Gurzadyan, Jianzhang Zhao, Yuanyuan Chen, Xiaoxin Li, Licheng Sun. Singlet fission from upper excited electronic states of cofacial perylene dimer. J. Phys. Chem. Lett. 10, 2428-2433, 2019.

[16] Zhiwei Liu, Fengling Song, Wenbo Shi, Gagik G. Gurzadyan, Huiyi Yin, Bo Song, Ri Liang, Xiaojun Peng. Nitroreductase-activatable theranostic molecules with high PDT efficiency under mild hypoxia based on a TADF fluorescein derivative. ACS Appl. Mater. Interfaces 11, 15426-15435, 2019.

[17] Kepeng Chen, Jianzhang Zhao, Xiaoxin Li, Gagik G. Gurzadyan. Anthracene-naphthalenediimide compact electron donor/acceptor dyads: electronic coupling, electron transfer, and intersystem crossing. J. Phys. Chem. A 123, 2503-2516, 2019.

[18] Li Zhang, Xichuan Yang, Weihan Wang, Gagik G. Gurzadyan, Jiajia Li, Xiaoxin Li, Jincheng An, Ze Yu, Haoxin Wang, Bin Cai, Anders Hagfeldt, Licheng Sun. 13.6% Efficient organic dye-sensitized solar cells by minimizing energy losses of the excited state. ACS Energy Lett. 4, 943-951, 2019.

[19] Hainan Shi, Saran Long, Jungang Hou, Lu Ye, Yanwei Sun, Wenjun Ni, Chunshan Song, Keyan Li, Gagik G. Gurzadyan, Xinwen Guo. Defects promoting ultrafast charge separation in graphitic carbon nitride enhanced visible-light-driven CO₂ reduction activity. Chem. Europ J. 5028-5035, 2019.

[20] Hainan Shi, Saran Long, Shen Hu, Jungang Hou, Wenjun Ni, Chunshan Song, Keyan Li, Gagik G. Gurzadyan, Xinwen Guo. Interfacial charge transfer in 0D/2D defect-rich heterostructures for efficient solar-driven CO₂ reduction. Appl. Catal. B: Environ. 245, 760-769, 2019.

[21] Xiaoxin Li, Gagik G. Gurzadyan, Maxim F. Gelin, Wolfgang Domcke, Chenghuan Gong, Jinxuan Liu, Licheng Sun. Enhanced S₂ fluorescence from a free-base tetraphenylporphyrin surface-mounted metal organic framework. J. Phys. Chem. C 122, 23321-23328, 2018.

[22] Maowei Hu, Junyu Shen, Ze Yu, RongZhen Liao, Gagik G. Gurzadyan, Xichuan Yang, Anders Hagfeldt, Mei Wang, Licheng Sun. Efficient and stable dye-sensitized solar cells based on a tetradentate copper(II/I) redox mediator. ACS Appl. Mater. Interfaces 10, 30409-30416, 2018.

[23] Mang Wang, Jinxuan Liu, Chunmei Guo, Xiaosu Gao, Chenghuan Gong, Yan Wang, Bo Liu, Xiaoxin Li, Gagik G. Gurzadyan, Licheng Sun. Metal-organic frameworks (ZIF-67) as efficient cocatalysts for photocatalytic reduction of CO₂: the role of the morphology effect. J. Mater. Chem. A 6, 4768-4775, 2018.

[24] Yingjie Zhao, Xiaoxin Li, Zhijia Wang, Wenbo Yang, Kepeng Chen, Jianzhang Zhao, Gagik G. Gurzadyan. Precise control of the electronic coupling magnitude between the electron donor and acceptor in perylenebisimide derivatives via conformation restriction and its effect on photophysical properties. J. Phys. Chem. C 122, 7, 3756-3772, 2018.

[25] Yuang Zhang, Gagik G. Gurzadyan, Malik Muhammad, Umair Wentao, Rongwen Wang, Shufen Zhang, Bingtao Tang. Ultrafast and efficient photothermal conversion for sunlight-driven thermal-electric system. Chem. Engin. J 344, 402-409, 2018.

[26] Cheng Qi, Wenjing Jiao, Yinshan Jiang, Wenwen Meng, Liang Zhao, Junli Wang, Jixiang Hu, Gagik G. Gurzadyan, Chunying Duan, Tao Liu. Manipulation of successive crystalline transformations to control electron transfer and switchable functions. National Science Review 5, 507-515, 2018.

[27] Xiaoxin Li, Chenghuan Gong, Gagik G. Gurzadyan, Maxim F. Gelin, Jinxuan Liu, Licheng Sun. Ultrafast relaxation dynamics in zinc tetraphenylporphyrin surface-mounted metal organic framework. J. Phys. Chem. C 122, 50-61, 2018. 

[28] Ze Yu, Yuchen Zhang, Xiaoqing Jiang, Xiaoxin Li, Jianbo Lai, Maowei Hu, Mohammed Elawad, Gagik G. Gurzadyan, Xichuan Yang, Licheng Sun. High-efficiency perovskite solar cells employing a conjugated donor-acceptor co-polymer as a hole-transporting material. RSC Adv. 7, 27189-27197, 2017.

[29] Xiaoqing Jiang, Ze Yu, Yuchen Zhang, Jianbo Lai, Jiajia Li, Gagik G. Gurzadyan, Xichuan Yang, Licheng Sun. High-performance regular perovskite solar cells employing low-cost poly(ethylenedioxythiophene) as a hole-transporting material. Scientific Reports 7, 42564, 2017.

[30] Daniele Cortecchia, Jun Yin, Annalisa Bruno, Shu-Zee Alencious Lo, Gagik G. Gurzadyan, Subodh Mhaisalkar, Jean-Luc Brédas, Cesare Soci. Polaron self-localization in white-light emitting hybrid perovskites. J. Mater. Chem. C 5, 2771-2780, 2017.

[31] Jiajia Li, Xichuan Yang, Ze Yu, Gagik G. Gurzadyan, Ming Cheng, Fuguo Zhang, Jiayan Cong, Weihan Wang, Haoxin Wang, Xiaoxin Li, Lars Kloo, Mei Wang, Licheng Sun. Efficient dye-sensitized solar cells with [copper(6,6′-dimethyl-2,2′-bipyridine)2]2+/1+ redox shuttle. RSC Adv. 7, 4611-4615, 2017.

[32] Lin Ma, Peng Hu, Hui Jiang, Christian Kloc, Handong Sun, Cesare Soci, Alexander A. Voityuk, Maria E. Michel-Beyerle, Gagik G. Gurzadyan. Single photon triggered dianion formation in TCNQ and F₄TCNQ crystals. Sci. Rep. 6, 28510, 2016. 

[33] Gagik G. Gurzadyan. Femtosecond laser spectroscopy and singlet fission. J. Laser Opt. Photonics 3, 2016. 

[34] Manoj Kumar, Stfano Vezzoli, Zilong Wang, Varum Chaudhary, Raju V. Ramanujan, Gagik G. Gurzadyan,  Annalisa F. Bruno, Cesare Soci. Hot exciton cooling and multiple exciton generation in PbSe quantum dots. Phys. Chem. Chem. Phys. 18, 31107-31114, 2016. 

[35] Jun Yin, Manoj Kumar, Qiong Lei, Lin Ma, Sai Santosh Kumar Raavi, Gagik G. Gurzadyan, Cesare Soci. Small-size effects on electron transfer in P₃HT/InP quantum dots. J. Phys. Chem. C 119,  26783-26792, 2015.

[36] Anurag Krishna, Dharani Sabba, Jun Yin, Annalisa Bruno, Pablo P. Boix, Yang Gao, Herlina A. Dewi, Gagik G. Gurzadyan, Cesare Soci, Subodh G. Mhaisalkar, Andrew C. Grimsdale. Facile synthesis of a furan-arylamine hole-transporting material for high-efficiency mesoscopic perovskite solar cells. Chem. Eur. J. 21, 1-6, 2015.