Abstract
1. Introduction
Since the discovery of the semiconducting nature of polythiophene, organic electronics have experienced tremendous development[
To solve these issues, it is important to utilize more advanced characterization techniques. Note that in-situ/operando techniques for studying organic semiconductors have been developed as powerful tools to achieve unprecedented insights into complex film growth, electronic states, and structure-property relationships under conditions relevant to device operation or device manipulation[
In this review, recent advances in the application of in-situ/operando techniques for the characterizations of organic semiconductors and devices are thoroughly summarized (Fig. 1). First, we focus on a variety of in-situ/operando optical and scanning probe microscopy for real-time observation of organic film crystallization, as well as characterization of local morphologies, electron/ion coupling, and semiconductor/electrolyte interface of organic devices with unprecedented resolution in complex solid/liquid environments. Then, we provide an introduction to in-situ spectroscopy techniques, including X-ray characterization techniques and ultraviolet photoelectron spectroscopy (UPS), to probe the crystal structures and electronic states of organic devices in-operando. These complementary in-situ techniques are beneficial to the study of the dynamic structure-property relationships, from centimeter to nanometer scales. Finally, challenges and outlooks for developing in-situ/operando techniques in organic semiconductors are discussed. Therefore, this review provides not only an overview of growth mechanisms and electronic properties of organic semiconductors but it also highlights the elegant in-situ/operando analytical methods that have helped to elucidate these mechanisms for more in-depth physics of organic electronics.
Figure 1.(Color online) Overview of various in-situ characterization techniques with different resolutions, from centimeter to nanometer, to study the dynamic structure-property relationship under manipulation.
2. In-situ/operando microscopy techniques
Organic semiconductors are assembled via weak noncovalent bonding among conjugated molecules, such as π–π interactions and van der Waals forces, leading to the important nature of self-assembly and multiple charge-transport mechanisms between molecules[
2.1. In-situ optical microscopy
Achieving high-quality organic crystalline films in large sizes is important to improve the electrical performance of organic devices. Considering the adjustments in molecular structures and deposition parameters, solution-based coating methods (e.g., drop-casting, spin-coating, bar-coating, solution-shearing, and floating-coffee-ring-driven-assembly) offer great potential to obtain organic crystals with large-area scalability, high morphological uniformity, and perfect crystalline order[
Recently, Leeet al. used in-situ optical microscopy to observe the crystallization process of TIPS-pentacene thin films using a continuous-flow microfluidic-channel-based meniscus-guided coating (CoMiC)[
Figure 2.(Color online) In-situ optical microscopy for characterizations of organic crystalline films. (a) Schematic diagram of CoMiC-based analytical system along the entire flow path connecting flow pattern, crystallization, and thin-film properties (upper panel of (a)). Side-view in-situ image analysis of meniscus shape variation during the coating (lower panel of (a)). (b) In-situ microscopy images showing the variation of solution/thin-film boundary and crystallization process of doped TIPS-pentacene using the FM-CoMiC and the SHM-CoMiC[
2.2. In-situ scanning probe microscopy
2.2.1. In-situ atomic force microscopy (AFM)
Non-contact in-situ optical microscopy can quickly characterize the kinetic process of solution-based crystallization of organic semiconducting films at the micrometer scale in real time of a few milliseconds; however, the large-scale property limits the observation of molecule assembling dynamics with nanometer resolution. In particular, it is still difficult to capture the moments of the assembling process of organic crystals on a local scale in real time. Although conventional X-ray diffraction (XRD) analyses have been used to study the molecular structure revolution, which only provide spatially and time-averaged structure transformation from the reciprocal diffraction data[
Recently, using real-time in-situ AFM, Chenet al. successfully imaged the entire self-assembly processes and the kinetics of crystalline films from amorphous solid states at the minute timescale[
Figure 3.(Color online) In-situ AFM characterizations. (a) Evolutionary selection growth approach and time-lapse sequence of representative AFM images showing the morphological evolution of the precursors on the SiO2 surface. Scale bar: 2
Note that the molecule assembly of solution-based techniques for organic crystals occurs at the liquid/solid interface, which is difficult to access by conventional optical and electron microscopies[
2.2.2. In-situ probe microscopy with advanced functions
The ability to probe electrical and electrochemical properties of organic semiconducting films in contact with a liquid solution during device operation is important because it can reveal real-time film crystallization, defects, and charge carrier transport properties for further performance optimization[
With the development of organic electronics, the coupling of organic semiconductors with biology is an emerging and continuously growing field for many advanced applications, such as molecular sensing, cell culture analysis, medical diagnostics, and synapses for neuromorphic computing[
Figure 4.(Color online) (a) Device cross-section schematic showing the working principle of (left) OFETs, (middle) EGOFETs, and (right) OECTs[
Recently, Surgailis et al. demonstrated that the ladder-type polymer BBL outperformed the NDI-T2 based glycolated P-90 random copolymer as the OECT channel material, and BBL exhibited a more efficient ion-to-electron coupling and higher OECT mobility (Fig. 4(b))[
Probing electrochemical processes and local structure-function relationships that affect ion transport in mixed ionic–electronic conductors is more significant for the application of OECTs. Among the different scanning probe microscopies, electrochemical strain microscopy is a novel technique that is capable of probing local ionic flows and electrochemical reactivity in semiconductors with unprecedented resolution in-situ and operando[
Furthermore, Kyndiah et al. demonstrated that the local conductivity and interfacial capacitance of the active channel in an EGOFET can be mapped in-operando using in-liquid scanning dielectric microscopy with high spatial resolution[
3. In-situ/operando spectroscopy techniques
Compared to inorganic materials, organic materials show significant advantages in terms of low processing cost, mechanical flexibility, and light transmittance[
3.1. In-situ X-ray characterization techniques
The development of organic devices has shown tremendous progress in terms of sensory and flexible applications[
For example, Giri et al. used the in-situ microbeam grazing-incidence wide-angle X-ray-scattering (GIWAXS) to study the growth process of metastable TIPS-pentacene polymorphs during solution shear[
Figure 5.(Color online) In-situ X-ray characterization techniques. (a) Conceptual representation of the in-situ solution-shearing system. (b) Scattering regions captured by the high-speed GIWAXS detector for a representative solution-sheared TIPS-pentacene thin film[
In addition to the study of the growth and crystallization of organic films, the in-situ X-ray technique can also explore the mechanical behavior under mechanical tests. Aliouat et al. used in-situ grazing-incidence X-ray diffraction (GIXRD) to study the influence of tensile strain on structural characteristics of PffBT4T-2OD π-conjugated polymer (PCE11)[
3.2. In-situ ultraviolet photoelectron spectroscopy
To fabricate high-performance organic electronic devices, it is necessary to improve the interface stability between different materials and control the crystallinity of organic semiconducting films[
Recently, Yun et al. used in-situ UPS to study the denaturation and stability of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS) and multiwalled carbon nanotubes (MWNT)/PEDOT:PSS films after high-temperature annealing[
Figure 6.(Color online) In-situ ultraviolet photoelectron spectroscopy. (a) Experimental design to examine the behavior of PE and MWNT/PEDOT:PSS films before and after high-temperature annealing[
Furthermore, Yun et al. studied the relationship between the crystal phase of organic materials and the substrate by in-situ UPS[
4. Conclusion
The development and research of new-generation organic electronics and optoelectronics require a deeper understanding on the film growth mechanism of organic semiconductors, as well as the exploration of electronic states and structure-property relationship in complex device structures, which guide the optimization of film morphologies and electrical performance. In recent years, a series of in-situ/operando characterizations methods based on optical, scanning probe microscopy, and spectroscopy techniques have been employed to address these challenges in advanced organic electronic devices. In this review, we summarize these significant in-situ techniques: (i) in-situ optical and scanning probe microscopy for real-time observation of crystallization of organic films, and characterization of local morphologies and structure properties of organic devices from micro to nano scales; and (ii) in-situ spectroscopy techniques to probe the structure-property relationships and the electronic states of organic devices in-operando. This in-depth understanding of organic materials and devices will facilitate the exploration of new organic materials and growth methods, as well as the optimization of organic devices for advanced applications.
Despite recent progress in the in-situ characterization of organic devices, there are still many technological challenges and opportunities. First, the emerging ultrathin molecular crystals, especially 2D crystals[
In-situ characterization techniques will undoubtedly boost our understanding of the intrinsic structure-property relationships of organic devices. This will then provide guidance for the design of the next generation of organic materials and advanced organic devices for application in electronics, chemistry, energy, and bioscience.
Acknowledgements
We acknowledge support from Natural Science Foundation of Jiangsu Province (grant number BK20211507), National Natural Science Foundation of China (grant number 61774080), and the start-up funds from Changzhou University.
References
[1] A Tsumura, H Koezuka, T Ando. Macromolecular electronic device: Field-effect transistor with a polythiophene thin film. Appl Phys Lett, 49, 1210(1986).
[2] L Q Li, P Gao, W C Wang et al. Growth of ultrathin organic semiconductor microstripes with thickness control in the monolayer precision. Angew Chem Int Ed, 52, 12530(2013).
[3] Y B Yuan, G Giri, A L Ayzner et al. Ultra-high mobility transparent organic thin film transistors grown by an off-centre spin-coating method. Nat Commun, 5, 3005(2014).
[4] Y H Zhang, J S Qiao, S Gao et al. Probing carrier transport and structure-property relationship of highly ordered organic semiconductors at the two-dimensional limit. Phys Rev Lett, 116, 016602(2016).
[5] P Lin, F Yan. Organic thin-film transistors for chemical and biological sensing. Adv Mater, 24, 34(2012).
[6] Y van de Burgt, A Melianas, S T Keene et al. Organic electronics for neuromorphic computing. Nat Electron, 1, 386(2018).
[7] H Minemawari, T Yamada, H Matsui et al. Inkjet printing of single-crystal films. Nature, 475, 364(2011).
[8] C L Wang, H L Dong, L Jiang et al. Organic semiconductor crystals. Chem Soc Rev, 47, 422(2018).
[9] Q J Wang, J Qian, Y Li et al. 2D single-crystalline molecular semiconductors with precise layer definition achieved by floating-coffee-ring-driven assembly. Adv Funct Mater, 26, 3191(2016).
[10] J Qian, S Jiang, S L Li et al. Solution-processed 2D molecular crystals: Fabrication techniques, transistor applications, and physics. Adv Mater Technol, 4, 1800182(2019).
[11] A Yamamura, S Watanabe, M Uno et al. Wafer-scale, layer-controlled organic single crystals for high-speed circuit operation. Sci Adv, 4, eaao5758(2018).
[12] S Jiang, J Qian, Y Duan et al. Millimeter-sized two-dimensional molecular crystalline semiconductors with precisely defined molecular layers via interfacial-interaction-modulated self-assembly. J Phys Chem Lett, 9, 6755(2018).
[13] Z W Wang, S J Guo, H W Li et al. The semiconductor/conductor interface piezoresistive effect in an organic transistor for highly sensitive pressure sensors. Adv Mater, 1805630(2018).
[14] W Sun, B Gao, M F Chi et al. Understanding memristive switching via
[15] B J Leever, C A Bailey, T J Marks et al.
[16] J Surgailis, A Savva, V Druet et al. Mixed conduction in an N-type organic semiconductor in the absence of hydrophilic side-chains. Adv Funct Mater, 31, 2010165(2021).
[17] S R Walter, J Youn, J D Emery et al.
[18] P Chulkin.
[19] D J Yun, S Lee, K Yong et al.
[20] R Giridharagopal, L Q Flagg, J S Harrison et al. Electrochemical strain microscopy probes morphology-induced variations in ion uptake and performance in organic electrochemical transistors. Nat Mater, 16, 737(2017).
[21] N Hosono, A Terashima, S Kusaka et al. Highly responsive nature of porous coordination polymer surfaces imaged by
[22] J C Lee, M Lee, H J Lee et al. Flow patterns: Numerical simulations and in situ optical microscopy connecting flow pattern, crystallization, and thin-film properties for organic transistors with superior device-to-device uniformity. Adv Mater, 32, 2070357(2020).
[23] K S Wienhold, C L Weindl, S S Yin et al. Following
[24] J L Yang, D H Yan. Weak epitaxy growth of organic semiconductor thin films. Chem Soc Rev, 38, 2634(2009).
[25] Y F Yao, H L Dong, W P Hu. Charge transport in organic and polymeric semiconductors for flexible and stretchable devices. Adv Mater, 28, 4513(2016).
[26] Y Diao, L Shaw, Z N Bao et al. Morphology control strategies for solution-processed organic semiconductor thin films. Energy Environ Sci, 7, 2145(2014).
[27] T Minari, C Liu, M Kano et al. Controlled self-assembly of organic semiconductors for solution-based fabrication of organic field-effect transistors. Adv Mater, 24, 299(2012).
[28] A Furchner, D Aulich. Organic materials for optoelectronic applications. Springer Ser Surf Sci, 52, 529(2018).
[29] Y Li, H B Sun, Y Shi et al. Patterning technology for solution-processed organic crystal field-effect transistors. Sci Technol Adv Mater, 15, 024203(2014).
[30] X D Gu, L Shaw, K Gu et al. The meniscus-guided deposition of semiconducting polymers. Nat Commun, 9, 534(2018).
[31] K S Park, J J Kwok, R Dilmurat et al. Tuning conformation, assembly, and charge transport properties of conjugated polymers by printing flow. Sci Adv, 5, eaaw7757(2019).
[32] Z C Zhang, B Y Peng, X D Ji et al. Marangoni-effect-assisted bar-coating method for high-quality organic crystals with compressive and tensile strains. Adv Funct Mater, 27, 1703443(2017).
[33] B Y Peng, Z R Wang, P K L Chan. A simulation-assisted solution-processing method for a large-area, high-performance C10-DNTT organic semiconductor crystal. J Mater Chem C, 4, 8628(2016).
[34] J C Lee, H Seo, M Lee et al. Investigation of the effect of 3D meniscus geometry on fluid dynamics and crystallization via
[35] S Chiodini, A Straub, S Donati et al. Morphological transitions in organic ultrathin film growth imaged by in situ step-by-step atomic force microscopy. J Phys Chem C, 124, 14030(2020).
[36] S Y Lang, Y Shi, Y G Guo et al. Insight into the interfacial process and mechanism in lithium-sulfur batteries: An in situ AFM study. Angew Chem Int Ed, 55, 15835(2016).
[37] A Kyndiah, M Checa, F Leonardi et al. Nanoscale mapping of the conductivity and interfacial capacitance of an electrolyte-gated organic field-effect transistor under operation. Adv Funct Mater, 31, 2008032(2021).
[38] H L Chen, M L Li, Z Y Lu et al. Multistep nucleation and growth mechanisms of organic crystals from amorphous solid states. Nat Commun, 10, 3872(2019).
[39] J Rivnay, S Inal, A Salleo et al. Organic electrochemical transistors. Nat Rev Mater, 3, 17086(2018).
[40] J Y Gerasimov, R Gabrielsson, R Forchheimer et al. An evolvable organic electrochemical transistor for neuromorphic applications. Adv Sci, 6, 1801339(2019).
[41] G D Spyropoulos, J N Gelinas, D Khodagholy. Internal ion-gated organic electrochemical transistor: A building block for integrated bioelectronics. Sci Adv, 5, eaau7378(2019).
[42] Z H Yi, G Natale, P Kumar et al. Ionic liquid–water mixtures and ion gels as electrolytes for organic electrochemical transistors. J Mater Chem C, 3, 6549(2015).
[43] H T Yuan, H Shimotani, J T Ye et al. Electrostatic and electrochemical nature of liquid-gated electric-double-layer transistors based on oxide semiconductors. J Am Chem Soc, 132, 18402(2010).
[44] A Giovannitti, C B Nielsen, D T Sbircea et al. N-type organic electrochemical transistors with stability in water. Nat Commun, 7, 13066(2016).
[45] P Lin, X T Luo, I M Hsing et al. Organic electrochemical transistors integrated in flexible microfluidic systems and used for label-free DNA sensing. Adv Mater, 23, 4035(2011).
[46] L H Jimison, S A Tria, D Khodagholy et al. Measurement of barrier tissue integrity with an organic electrochemical transistor. Adv Mater, 24, 5919(2012).
[47] A Campana, T Cramer, D T Simon et al. Electrocardiographic recording with conformable organic electrochemical transistor fabricated on resorbable bioscaffold. Adv Mater, 26, 3874(2014).
[48] P Leleux, C Johnson, X Strakosas et al. Ionic liquid gel-assisted electrodes for long-term cutaneous recordings. Adv Healthcare Mater, 3, 1377(2014).
[49] P Gkoupidenis, D A Koutsouras, G G Malliaras. Neuromorphic device architectures with global connectivity through electrolyte gating. Nat Commun, 8, 15448(2017).
[50] P Lin, F Yan, J J Yu et al. The application of organic electrochemical transistors in cell-based biosensors. Adv Mater, 22, 3655(2010).
[51] X D Ji, H Y Lau, X C Ren et al. Bioelectronics: highly sensitive metabolite biosensor based on organic electrochemical transistor integrated with microfluidic channel and poly(N-vinyl-2-pyrrolidone)-capped platinum nanoparticles. Adv Mater Technol, 1, 1(2016).
[52] H D Sun, J Gerasimov, M Berggren et al. N-Type organic electrochemical transistors: Materials and challenges. J Mater Chem C, 6, 11778(2018).
[53] S H Kim, K Hong, W Xie et al. Electrolyte-gated transistors for organic and printed electronics. Adv Mater, 25, 1822(2013).
[54] X Strakosas, M Bongo, R M Owens. The organic electrochemical transistor for biological applications. J Appl Polym Sci, 132, 1(2015).
[55] T Yokota, P Zalar, M Kaltenbrunner et al. Ultraflexible organic photonic skin. Sci Adv, 2, 1(2016).
[56] Y L Wu, P Liu, Y N Li et al. Enabling materials for printed electronics. 2006 IEEE LEOS Annual Meeting Conference Proceedings, 434(2006).
[57] O Ostroverkhova. Organic optoelectronic materials: Mechanisms and applications. Chem Rev, 116, 13279(2016).
[58] S R Forrest. Electronic appliances on plastic. Nature, 428, 911(2004).
[59] J Rivnay, L H Jimison, J E Northrup et al. Large modulation of carrier transport by grain-boundary molecular packing and microstructure in organic thin films. Nat Mater, 8, 952(2009).
[60] D J Yun, J Chung, C Jung et al. Pentacene orientation on source/drain electrodes and its effect on charge carrier transport at pentacene/electrode interface, investigated using in situ ultraviolet photoemission spectroscopy and device characteristics. J Electrochem Soc, 160, H436(2013).
[61] M Sanyal, B Schmidt-Hansberg, M F G Klein et al. In situ X-ray study of drying-temperature influence on the structural evolution of bulk-heterojunction polymer-fullerene solar cells processed by doctor-blading. Adv Energy Mater, 1, 363(2011).
[62] R P Li, H U Khan, M M Payne et al. Heterogeneous nucleation promotes carrier transport in solution-processed organic field-effect transistors. Adv Funct Mater, 23, 291(2013).
[63] P H Fang, F C Wu, H S Sheu et al. Analysis of ultrathin organic inverters by using in situ grazing incidence X-ray diffraction under high bending times and low voltage. Org Electron, 88, 106002(2021).
[64] D Yang, F C Löhrer, V Körstgens et al. In-operando study of the effects of solvent additives on the stability of organic solar cells based on PTB7-Th:PC71BM. ACS Energy Lett, 4, 464(2019).
[65] G H Wang, K Q Huang, Z Liu et al. Flexible, low-voltage, and n-type infrared organic phototransistors with enhanced photosensitivity via interface trapping effect. ACS Appl Mater Interfaces, 10, 36177(2018).
[66] Z Q Song, Y H Tong, X L Zhao et al. A flexible conformable artificial organ-damage memory system towards hazardous gas leakage based on a single organic transistor. Mater Horiz, 6, 717(2019).
[67] K Myny. The development of flexible integrated circuits based on thin-film transistors. Nat Electron, 1, 30(2018).
[68] T Someya, Y Kato, T Sekitani et al. Conformable, flexible, large-area networks of pressure and thermal sensors with organic transistor active matrixes. PNAS, 102, 12321(2005).
[69] J W Borchert, B Y Peng, F Letzkus et al. Small contact resistance and high-frequency operation of flexible low-voltage inverted coplanar organic transistors. Nat Commun, 10, 1119(2019).
[70] H Sirringhaus. Device physics of solution-processed organic field-effect transistors. Adv Mater, 17, 2411(2005).
[71] G Giri, R P Li, D M Smilgies et al. One-dimensional self-confinement promotes polymorph selection in large-area organic semiconductor thin films. Nat Commun, 5, 3573(2014).
[72] M Y Aliouat, S Escoubas, M C Benoudia et al. In situ measurements of the structure and strain of a π-conjugated semiconducting polymer under mechanical load. J Appl Phys, 127, 045108(2020).
[73] L S Grodd, E Mikayelyan, T Dane et al. Local scale structural changes of working OFET devices. Nanoscale, 12, 2434(2020).
[74] C L Wang, H L Dong, W P Hu et al. Semiconducting π-conjugated systems in field-effect transistors: A material odyssey of organic electronics. Chem Rev, 112, 2208(2012).
[75] H Bässler, A Köhler. Charge transport in organic semiconductors. Top Curr Chem, 312, 1(2012).
[76] Y Olivier, V Lemaur, J L Brédas et al. Charge hopping in organic semiconductors: Influence of molecular parameters on macroscopic mobilities in model one-dimensional stacks. J Phys Chem A, 110, 6356(2006).
[77] D J Yun, J Chung, Y Kim et al. Direct comparative study on the energy level alignments in unoccupied/occupied states of organic semiconductor/electrode interface by constructing
[78] S Braun, W R Salaneck, M Fahlman. Energy-level alignment at organic/metal and organic/organic interfaces. Adv Mater, 21, 1450(2009).
[79] N Koch, A Kahn, J Ghijsen et al. Conjugated organic molecules on metal versus polymer electrodes: Demonstration of a key energy level alignment mechanism. Appl Phys Lett, 82, 70(2002).
[80] D J Yun, S H Park, J Hwang et al. In situ photoelectron spectroscopy study on the buffer role of multiwalled carbon nanotubes against thermal degradation in organic conducting composite films with PEDOT:PSS. J Phys Chem C, 123, 2238(2019).
[81] D J Yun, Y Yun, J Lee et al. In-depth investigation of the correlation between organic semiconductor orientation and energy-level alignment using in situ photoelectron spectroscopy. ACS Appl Mater Interfaces, 12, 50628(2020).
[82] C Wang, X C Ren, C H Xu et al. Organic single crystals: N-type 2D organic single crystals for high-performance organic field-effect transistors and near-infrared phototransistors. Adv Mater, 30, 1870114(2018).
[83] S L Cai, W G Zhang, R N Zuckermann et al. The organic flatland-recent advances in synthetic 2D organic layers. Adv Mater, 27, 5762(2015).
[84] F X Yang, S S Cheng, X T Zhang et al. 2D organic materials for optoelectronic applications. Adv Mater, 30, 1702415(2018).
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