Research Progress of Monolayer Molecular Crystal Materials and Devices

doi:10.6023/A26050162

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (10): 1649-1663.DOI: 10.6023/A26050162 Previous Articles Next Articles

Review

单分子层分子晶体材料与器件的研究进展

樊艳伟, 江浪^*()

河北工业大学化工学院天津 300130

投稿日期:2026-05-14 发布日期:2026-07-08

作者简介:

樊艳伟, 2024年获中国科学院化学研究所博士学位, 现为河北工业大学博士后, 主要研究方向为有机半导体的掺杂调控及其电荷传输.

江浪, 教授, 2011年获中国科学院化学研究所博士学位, 同年任职该所助理研究员. 2013年赴英国剑桥大学卡文迪什实验室从事博士后研究, 2016年任中国科学院化学研究所有机固体实验室研究员, 2025年任河北工业大学教授. 主要从事分子晶体材料的输运机制和高性能光电器件与电路应用研究.

基金资助:
国家自然科学基金(T2225028); 国家自然科学基金(U22A6002); 国家自然科学基金(92577207); 河北省自然科学基金(B2025202087); 以及中国科学院战略性先导科技专项(XDB0520201); 基础研究青年科学家项目(YSBR-053)

Research Progress of Monolayer Molecular Crystal Materials and Devices

Yanwei Fan, Lang Jiang^*()

School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130

Received:2026-05-14 Published:2026-07-08
Contact: *E-mail: ljiang@hebut.edu.cn
Supported by:
National Natural Science Foundation of China(T2225028); National Natural Science Foundation of China(U22A6002); National Natural Science Foundation of China(92577207); Natural Science Foundation of Hebei Province(B2025202087); Strategic Priority Research Program of Sciences(XDB0520201); Young Scientists in Basic Research of Chinese Academy of Sciences(YSBR-053)

The construction of self-assembled monolayers (SAMs) serves as a crucial technical underpinning for realizing the core concept of molecular devices proposed in the 1970s. Early fabrication of molecular devices relied primarily on SAMs bonded to substrates via covalent linkages, with monolayer transistors as their typical representative. Nevertheless, random molecular disorder, grain boundaries, and structural defects intrinsically generated during self-assembly introduce abundant interfacial charge traps, severely suppressing carrier hopping transport and greatly limiting the improvement of carrier mobility, photoelectric responsiveness and overall device performance. In recent years, monolayer molecular crystals (MMCs) have demonstrated excellent charge transport properties due to their combination of the ultra-thin thickness characteristic of SAMs and the long-range ordered molecular arrangement typical of single crystals. They have gradually emerged as highly attractive building blocks for constructing optoelectronic devices and studying the physics of charge transport, exhibiting significant structural advantages and broad application prospects in various types of high-performance optoelectronic devices. When organic semiconductors are precisely thinned down to monolayer thickness, their atomically flat exposed surfaces can act as an ideal research platform to intuitively evaluate the practical effects of multiple optimization strategies, including contact resistance reduction, photoresponse modulation, and gas sensing sensitivity improvement. This structural feature provides a crucial research carrier to deeply decipher the microscopic intrinsic charge transport mechanism inside organic semiconductors, enabling researchers gain fundamental molecular-scale insights into carrier migration, trapping and recombination behaviors. This paper systematically reviews the evolutionary development of MMCs, summarizes their core structural and optoelectronic merits and typical application scenarios in high-performance organic devices, and comprehensively analyzes the intrinsic material limitations and environmental stability challenges that severely restrict their practical utilization. Corresponding targeted future research directions are also proposed, which are expected to provide valuable theoretical references and technical guidance, and further facilitate the in-depth exploration and scalable industrial applications of high-performance monolayer molecular electronic materials.

Key words: self-assembled monolayer, monolayer molecular crystal, organic field-effect transistor, optoelectronic device, sensor

Cite this article

Yanwei Fan, Lang Jiang. Research Progress of Monolayer Molecular Crystal Materials and Devices[J]. Acta Chimica Sinica, 2026, 84(10): 1649-1663.

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Fig. & Tab. 12

Figure 1. Chemical structures involved in this review

分子	方法	电极	电介质	构型	接触电阻/(Ω•cm)	迁移率/(cm²•V^－1•s^－1)	时间	Ref
HTEB	滴注	Au	300 nm SiO₂	底栅顶电极(BGTC)	—	1.0	2011	[13]
HTEB	滴注法	Au	30 nm HfO₂	BGTC	540	0.26	2013	[14]
C8-BTBT	范德华外延	Au	285 nm SiO₂	BGTC	—	10	2014	[15]
pentacene	范德华外延	Au	—	BGTC	—	1.6	2016	[32]
C8-BTBT	范德华外延	Au	285 nm SiO₂	BGTC	100	30	2017	[16]
C10-DNTT	二次溶液剪切	Au	SiO₂	BGTC	—	10.4	2017	[33]
CMUT	空间限域	Au	BCB/SiO₂	BGTC	—	1.24	2018	[28]
C10-DNTT	溶液剪切	Au	300 nm SiO₂	BGTC	40	12.5	2020	[34]
C8-DNBDT-NW	溶液剪切	Au	100 nm SiO₂	BGTC	—	10	2020	[35]
C8-DNBDT-NW	溶液剪切	Au	100 nm SiO₂	BGTC	175	10	2020	[36]
C10-DNTT	溶液剪切	Au	HZO/Al₂O₃	BGTC	59.4±5.3	8.44±1.61	2021	[37]
C6-DPA	空间限域	Au	300 nm SiO₂	BGTC	—	1.61	2021	[29]
C10-DNTT	溶液剪切	Au	HfO₂	BGTC	2.2×10^－2 (V_DS =－1 mV)	11.7	2022	[38]
C6-DPA	空间限域	Au	300 nm SiO₂	BGTC	—	1.3	2022	[39]
C10-DNTT	溶液剪切	Pt	HfO₂	BGTC	14.0	18	2023	[30]
C8-DNTT	溶液剪切	Au	300 nm SiO₂	BGTC	79.00±7.00	12.36±0.45	2023	[40]
C8-DNTT	溶液剪切	Au	SiO₂	BGTC	—	13.23	2024	[31]
C10-DNTT	溶液剪切	Ti₃C₂T_x	HfO₂	BGTC	165	9.5	2024	[17]

Table 1. Summary of contact resistance and mobility of MMC OFET

Figure 2. (a) Schematic diagram of the drop-casting method for preparing p-MSB crystals, (b) molecular structure of p-MSB, (c) schematic diagrams of the arrangement of 1-layer, 2-layer and 3-layer molecules on the SiO2/Si substrate[41] (Reproduced with permission. An open access journal under a Creative Commons Attribution 4.0 International License), (d) schematic diagram of drop-casting method for preparing NDI MMC, (e, f) cross-polarization microscopic photos of non-porous NDI MMC, and (g) NH3 sensitivity of porous and non-porous MMC OFET[42] (Reproduced with permission. Copyright 2020, Wiley-VCH)

Figure 3. (a) Schematic diagram of the gravity-assisted method for preparing CMUT MMC, (b) optical image of the CMUT MMC fabricated on BCB/SiO2 substrate, (c) transfer curve of CMUT MMC-OFET[28] (An open access journal under a Creative Commons Attribution 4.0 International License), (d) mixed spin-coating two-dimensional space phase separation method, (e) fluorescence microscopic image of large-area C6-DPA MMC, (f) transfer curve of C6-DPA MMC OFET[29] (Reproduced with permission. An open access journal under a Creative Commons Attribution 4.0 International License), (g) schematic diagram of the STAA method for preparing C6-DPA MMC, (h) C6-DPA MMC array, and (i) mobility statistics of C6-DPA MMC[39] (Reproduced with permission. Copyright 2022, Wiley-VCH)

Figure 4. (a, b) Schematic diagram of the DSS method for preparing C10-DNTT MMC[33] (Reproduced with permission. Copyright 2017, Wiley-VCH), (c) schematic image of the meniscus-driven crystal growth method, (d) microscope images of monolayer and bilayer C8-DNBDT-NW crystals, (e) transfer curves of different-layer C8-DNBDT-NW OFETs[47] (An open access journal under a Creative Commons Attribution 4.0 International License), (f) POM images, (g) photograph of a single-layer C10-DNTT film, and (h) transfer curves of C10-DNTT MMC OFETs at Vds=－0.1 V (blue) and －1 V (red)[37] (An open access journal under a Creative Commons Attribution 4.0 International License)

Figure 5. (a) Schematic diagram of molecular stacking on the graphene surface, (b) AFM image of graphene on the SiO2 surface, (c) AFM of the nucleation and growth of C8-BTBT MMC, (d, e) Optical microscopy image of a plasma-patterned graphene before and after C8-BTBT growth, respectively, (f) POM of C8-BTBT MMC, (g) room temperature double-sweep Ids-Vg characteristics, (h) Ids-Vds characteristics of the device in g, and (i) extracted μ-n relationship at room temperature[15] (An open access journal under a Creative Commons Attribution 4.0 International License)

Figure 6. (a) TEM image of single-layer graphene[15] (An open access journal under a Creative Commons Attribution 4.0 International License), (b) cross-sectional transmission electron microscope (TEM) image of C6-DPA/NDI MMC[29] (Reproduced with permission. An open access journal under a Creative Commons Attribution 4.0 International License), (c) GIWAXS pattern of the monolayer CMUT[28] (An open access journal under a Creative Commons Attribution 4.0 International License), (d) HR-AFM image and fast Fourier transform graph of C6-DPA MMC[39] (Reproduced with permission. Copyright 2022, Wiley-VCH), (e~h) TOF-SIMS images of C6-DPA MMC, and (i) molecular dynamics simulations of the formation of MMCs[29] (Reproduced with permission. An open access journal under a Creative Commons Attribution 4.0 International License)

Figure 7. (a) Contact resistance diagram, (b) ratio of Rc/Rtotal for different thickness HTEB at different channel lengths[14] (Reproduced with permission. Copyright 2019, Royal Society of Chemistry), (c) Rc•W of 40 nm thick and MMC OFETs at different VG[28] (Reproduced with permission. An open access journal under a Creative Commons Attribution 4.0 International License), (d) Rc•W of 2-layer and 3-layer C8-DNBDT-NW[47] (An open access journal under a Creative Commons Attribution 4.0 International License), (e) transfer curve of C10-DNTT MMC-OFET, (f) Rc•W extracted by TLM method, and (g) statistical distribution of contact resistance[30] (An open access journal under a Creative Commons Attribution 4.0 International License)

Figure 8. (a) Variation of sub-threshold slope SS with respect to Ids, (b) statistical distributions of SS for 50 devices [37] (An open access journal under a Creative Commons Attribution 4.0 International License), (c) statistical analysis of mobility (μ), sub-threshold swing (SS), on/off ratio (Ion/Ioff), and threshold voltage (Vth)[30] (An open access journal under a Creative Commons Attribution 4.0 International License)

Figure 9. (a) Schematic illustration of a biological synapse, (b) EPSC of HTEB synaptic transistors stimulated by light pulses, (c) PPF behavior of HTEB transistors, and (d) learning and forgetting processes stimulated by continuous optical pulses[62] (Reproduced with permission. Copyright 2022, Tsinghua University Press and Springer)

Figure 10. (a) Schematic diagram of the lateral p-n junction based on MMC, (b) fluorescent mapping of p-n diode, (c) rectification curve of the p-n diode in CMUT MMC/DPA at VDS=±60 V[28] (Reproduced with permission. An open access journal under a Creative Commons Attribution 4.0 International License), (d) schematic diagram of the vertical p-n junction and inverter device, (e) transfer curve of p-n heterojunction device, (f) characteristics of the inverter at VDD=－60 V[29] (Reproduced with permission. An open access journal under a Creative Commons Attribution 4.0 International License), (g) schematic diagram of the 2.0 nm F16CuPc/C6-DPA MMC heterojunction, and (h) transfer curve of the p-n junction, (i) characteristics of the inverter[39] (Reproduced with permission. Copyright 2022, Wiley-VCH)

Figure 11. (a) Schematic diagram of porous and non-porous NDI MMC sensors, (b) optical microscope images and AFM images of porous MMC, (c) NH3 sensor performance of porous NDI MMC at different NH3 concentrations, (d) current responses of non-porous NDI MMC based sensors upon exposure to dopamine powders[42] (Reproduced with permission. Copyright 2020, Wiley-VCH), (e) amplifier electrocardiogram (ECG) sensor application based on C10-DNTT MMC, (f) photograph of human chest, and (g) the amplified electrocardiogram signal of the tested human body[37] (An open access journal under a Creative Commons Attribution 4.0 International License)

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单分子层分子晶体材料与器件的研究进展

Research Progress of Monolayer Molecular Crystal Materials and Devices

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