二维过渡金属硫族化合物的相变和接触工程:机理、方法与前沿进展

doi:10.12066/j.issn.1007-2861.2681

摘要/Abstract

摘要： 二维过渡金属硫族化合物(transition metal dichalcogenides,TMDs)和金属界面之间的费米能级钉扎效应严重限制了载流子输运效率.二维TMDS的相变工程为金属-半导体接触的改善提供了突破性方案.从相变的物理机制出发,揭示晶格对称性破缺(2H→1T/1T)通过重构界面电子态与原子排布,实现3大功能协同优化:(1)抑制金属诱导间隙态(metal-induced gap states,MIGS);(2)调控能带对齐;(3)构筑原子级平滑界面.系统探讨了电荷掺杂、外场激励和热力学调控相变的策略:原子插层调控轨道电子填充以稳定金属相,外场(光、电、应力)通过能量-动量耦合触发晶格重构,而合金化与热力学合成则通过能垒设计实现异质相空间可控生长.这些方法揭示了“电子态-晶格序-界面输运”的多尺度关联,为低维器件高效接触提供理论支撑.进一步指出,相变动态过程的原子尺度解析、异质相界面稳定性提升及跨尺度集成工艺是未来核心挑战,需融合多学科手段推动二维电子器件从基础创新向高密度集成电路发展.

关键词: 相变工程, 接触电阻, 场效应晶体管, 欧姆接触, 肖特基势垒

Abstract: The Fermi level pinning effect at the interface between two-dimensional transition metal dichalcogenides（TMDs） and metals severely limits carrier transport efficiency.Phase transition engineering in 2D TMDs offers a breakthrough strategy for improving metal-semiconductor contacts. This work elucidates the physical mechanisms of phase transitions, revealing that lattice symmetry breaking（2H→1T/1T） synergistically optimizes three critical functionalities by reconfiguring interfacial electronic states and atomic arrangements:（1） suppression of metal-induced gap states（MIGS）,（2） modulation of band alignment, and（3） construction of atomically smooth interfaces. Systematic strategies for phase transition control are explored, including charge doping, external field stimuli, and thermodynamic regulation. Atomic intercalation stabilizes metallic phases by tailoring orbital electron filling, while external fields（optical, electrical, or strain） trigger lattice reconstruction through energy-momentum coupling. Alloying and thermodynamic synthesis enable spatially controlled growth of heterophases via energy barrier engineering. These approaches establish multiscale correlations among electronic states, lattice ordering, and interfacial transport, providing theoretical foundations for high-efficiency contacts in lowdimensional devices. Future challenges lie in achieving atomic-scale resolution of dynamic phase transitions, enhancing heterophase interfacial stability, and developing cross-scale integration processes. Addressing these issues will require multidisciplinary efforts to advance 2D electronic devices from fundamental innovation toward high-density integrated circuits.

Key words: phase engineering, contact resistance, field effect transistor, ohmic contact, schottky height

中图分类号:

O469

尹鑫茂, 陈攀, 高灿飞, 李桂. 二维过渡金属硫族化合物的相变和接触工程:机理、方法与前沿进展[J]. 上海大学学报(自然科学版), 2025, 31(3): 383-402.

YIN Xinmao, CHEN Pan, GAO Canfei, LI Gui. Phase transitions and contact engineering in two-dimensional transition metal dichalcogenides:mechanisms, methods, and frontier advances[J]. Journal of Shanghai University（Natural Science Edition）, 2025, 31(3): 383-402.

参考文献

[1] Schaller R R. Moore's law:past, present and future[J]. IEEE Spectrum, 1997, 34(6):52-59.
[2] Lundstrom M. Moore's law forever?[J]. Science, 2003, 299(5604):210-211.
[3] Manzeli S, Ovchinnikov D, Pasquier D, et al. 2D transition metal dichalcogenides[J]. Nature Reviews Materials, 2017, 2(8):17033.
[4] Allain A, Kang J H, Banerjee K, et al. Electrical contacts to two-dimensional semiconductors[J]. Nature Materials, 2015, 14(12):1195-1205.
[5] Wang Y, Chhowalla M. Making clean electrical contacts on 2D transition metal dichalcogenides[J]. Nature Reviews Physics, 2021, 4(2):101-112.
[6] Voiry D, Mohite A, Chhowalla M. Phase engineering of transition metal dichalcogenides[J]. Chemical Society Reviews, 2015, 44(9):2702-2712.
[7] Yin X, Tang C S, Zheng Y, et al. Recent developments in 2D transition metal dichalcogenides:phase transition and applications of the (quasi-)metallic phases[J]. Chemical Society Reviews, 2021, 50(18):10087-10115.
[8] Duerloo K A N, Li Y, Reed E J. Structural phase transitions in two-dimensional Mo- and W-dichalcogenide monolayers[J]. Nature Communications, 2014, 5:4214.
[9] Kuc A, Heine T. The electronic structure calculations of two-dimensional transition-metal dichalcogenides in the presence of external electric and magnetic flelds[J]. Chemical Society Reviews, 2015, 44(9):2603-2614.
[10] Xu M, Liang T, Shi M, et al. Graphene-like two-dimensional materials[J]. Chemical Reviews, 2013, 113(5):3766-3798.
[11] Nevill Francis Mott. The theory of crystal rectiflers[J]. Proceedings of the Royal Society of London Series A:Mathematical and Physical Sciences, 1939, 171(944):27-38.
[12] Schottky W. Zur halbleitertheorie der sperrschicht- und spitzengleichrichter[J]. Zeitschrift für Physik, 1939, 113(5):367-414.
[13] Bardeen J. Surface states and rectiflcation at a metal semi-conductor contact[J]. Physical Review, 1947, 71(10):717-727.
[14] Kim C, Moon I, Lee D, et al. Fermi level pinning at electrical metal contacts of monolayer molybdenum dichalcogenides[J]. ACS Nano, 2017, 11(2):1588-1596.
[15] Liu X, Choi M S, Hwang E, et al. Fermi level pinning dependent 2D semiconductor devices:challenges and prospects[J]. Advanced Materials, 2022, 34(15):2108425.
[16] Gong C, Colombo L, Wallace R M, et al. The unusual mechanism of partial Fermi level pinning at metal{MoS₂ interfaces[J]. Nano Letters, 2014, 14(4):1714-1720.
[17] Das S, Chen H Y, Penumatcha A V, et al. High performance multilayer MoS₂ transistors with scandium contacts[J]. Nano Letters, 2013, 13(1):100-105.
[18] Wang Y, Kim J C, Wu R J, et al. Van der Waals contacts between three-dimensional metals and two-dimensional semiconductors[J]. Nature, 2019, 568(7750):70-74.
[19] Shen P C, Su C, Lin Y, et al. Ultralow contact resistance between semimetal and monolayer semiconductors[J]. Nature, 2021, 593(7858):211-217.
[20] Li W, Gong X, Yu Z, et al. Approaching the quantum limit in two-dimensional semiconductor contacts[J]. Nature, 2023, 613(7943):274-279.
[21] Liu Y, Guo J, Zhu E, et al. Approaching the Schottky{Mott limit in van der Waals metal{ semiconductor junctions[J]. Nature, 2018, 557(7707):696-700.
[22] Jain A, Szabó Á, Parzefall M, et al. One-dimensional edge contacts to a monolayer semiconductor[J]. Nano Letters, 2019, 19(10):6914-6923.
[23] Wang J, Yao Q, Huang C W, et al. High mobility MoS₂ transistor with low Schottky barrier contact by using atomic thick h-BN as a tunneling layer[J]. Advanced Materials, 2016, 28(37):8302-8308.
[24] Ouyang B, Xiong S, Jing Y. Tunable phase stability and contact resistance of monolayer transition metal dichalcogenides contacts with metal[J]. npj 2D Materials and Applications, 2018, 2(1):13.
[25] Schulman D S, Arnold A J, Das S. Contact engineering for 2D materials and devices[J]. Chemical Society Reviews, 2018, 47(9):3037-3058.
[26] Dines M B. Lithium intercalation via n-Butyllithium of the layered transition metal dichalcogenides[J]. Materials Research Bulletin, 1975, 10(4):287-291.
[27] Py M A, Haering R R. Structural destabilization induced by lithium intercalation in MoS₂ and related compounds[J]. Canadian Journal of Physics, 1983, 61(1):76-84.
[28] Kappera R, Voiry D, Yalcin S E, et al. Metallic 1T phase source/drain electrodes for fleld efiect transistors from chemical vapor deposited MoS₂ [J]. APL Materials, 2014, 2(9):092516.
[29] Ma Y, Liu B, Zhang A, et al. Reversible semiconducting-to-metallic phase transition in chemical vapor deposition grown monolayer WSe₂ and applications for devices[J]. ACS Nano, 2015, 9(7):7383-7391.
[30] Lee E K, Abdullah H, Torricelli F, et al. Boosting the optoelectronic properties of molybdenum diselenide by combining phase transition engineering with organic cationic dye doping[J]. ACS Nano, 2021, 15(11):17769-17779.
[31] Nourbakhsh A, Zubair A, Sajjad R N, et al. MoS₂ fleld-efiect transistor with sub-10 nm channel length[J]. Nano Letters, 2016, 16(12):7798-7806.
[32] Yu J, Fu J, Ruan H, et al. Tailoring lithium intercalation pathway in 2D van der Waals heterostructure for high-speed edge-contacted floating-gate transistor and artiflcial synapses[J]. InfoMat, 2024, 6(10):e12599.
[33] Lim J, Lee J I, Wang Y, et al. Photoredox phase engineering of transition metal dichalcogenides[J]. Nature, 2024, 633(8028):83-89.
[34] Kochat V, Apte A, Hachtel J A, et al. Re doping in 2D transition metal dichalcogenides as a new route to tailor structural phases and induced magnetism[J]. Advanced Materials, 2017, 29(43):1703754.
[35] Yang S Z, Gong Y, Manchanda P, et al. Rhenium-doped and stabilized MoS₂ atomic layers with basal-plane catalytic activity[J]. Advanced Materials, 2018, 30(51):1803477.
[36] Li S, Hong J, Gao B, et al. Tunable doping of rhenium and vanadium into transition metal dichalcogenides for two-dimensional electronics[J]. Advanced Science, 2021, 8(11):2004438.
[37] Lee H J, Choe M, Yang W, et al. Phase-engineered WS2 monolayer quantum dots by rhenium doping[J]. ACS Nano, 2023, 17(24):25731-25738.
[38] Rhodes D, Chenet D A, Janicek B E, et al. Engineering the structural and electronic phases of MoTe₂ through W substitution[J]. Nano Letters, 2017, 17(3):1616-1622.
[39] Zeng Y, Wu S, Xu X, et al. One-step synthesis of two-dimensional metal{semiconductor circuitry based on W-triggered spatial phase engineering[J]. ACS Materials Letters, 2023, 5(9):2324-2331.
[40] Zheng Y, Xiang D, Zhang J, et al. Controlling phase transition in WSe₂ towards ideal n-type transistor[J]. Nano Research, 2021, 14(8):2703-2710.
[41] Jiang J, Xu L, Qiu C, et al. Ballistic two-dimensional InSe transistors[J]. Nature, 2023, 616(7957):470-475.
[42] Jiang J, Xu L, Du L, et al. Yttrium-doping-induced metallization of molybdenum disulflde for ohmic contacts in two-dimensional transistors[J]. Nature Electronics, 2024, 7(7):545-556.
[43] Cho S, Kim S, Kim J H, et al. Phase patterning for ohmic homojunction contact in MoTe₂[J]. Science, 2015, 349(6248):625-628.
[44] Ryu H, Lee Y, Jeong J H, et al. Laser-induced phase transition and patterning of hBNEncapsulated MoTe₂[J]. Small, 2023, 19(17):2205224.
[45] Katagiri Y, Nakamura T, Ishii A, et al. Gate-tunable atomically thin lateral MoS₂ Schottky junction patterned by electron beam[J]. Nano Letters, 2016, 16(6):3788-3794.
[46] Zhu J, Wang Z, Yu H, et al. Argon plasma induced phase transition in monolayer MoS₂ [J]. Journal of the American Chemical Society, 2017, 139(30):10216-10219.
[47] Sharma C H, Surendran A P, Varghese A, et al. Stable and scalable 1T MoS₂ with low temperature-coe-cient of resistance[J]. Scientiflc Reports, 2018, 8:12463.
[48] Cheng Z, He S, Han X, et al. Improving electron mobility in MoS₂ fleld-efiect transistors by optimizing the interface contact and enhancing the channel conductance through local structural phase transition[J]. Journal of Materials Chemistry C, 2024, 12(8):2794-2802.
[49] Zhang J, Liu G, Yuan J, et al. Enhanced photoresponse in PdSe₂ via local plasma treatment:Implication for advanced optoelectronic devices[J]. ACS Applied Nano Materials, 2025, 8(7):3511-3518.
[50] Xiao M, Wu Z, Liu G, et al. Spatially controlled phase transition in MoTe₂ driven by focused ion beam irradiations[J]. ACS Applied Materials & Interfaces, 2024, 16(24):31747-31755.
[51] Chaudhary M, Anbalagan A K, Chuang K W, et al. Phase transition in two-dimensional monolayer (1L)-molybdenum disulflde induced by atomic S-basal plane gliding via synchrotron X-ray monochromatic beam radiation for superior electronic performance[J]. Materials Today, 2025, 84:28-38.
[52] Wang Y, Xiao J, Zhu H, et al. Structural phase transition in monolayer MoTe₂ driven by electrostatic doping[J]. Nature, 2017, 550(7677):487-491.
[53] Zhang F, Zhang H, Krylyuk S, et al. Electric-fleld induced structural transition in vertical MoTe₂ -and Mo_1-xWxTe₂-based resistive memories[J]. Nature Materials, 2018, 18(1):55-61.
[54] Zakhidov D, Rehn D A, Reed E J, et al. Reversible electrochemical phase change in monolayer to bulk-like MoTe₂ by ionic liquid gating[J]. ACS Nano, 2020, 14(3):2894-2903.
[55] He H K, Jiang Y B, Yu J, et al. Ultrafast and stable phase transition realized in MoTe₂-based memristive devices[J]. Materials Horizons, 2022, 9(3):1036-1044.
[56] Chi Z H, Zhao X M, Zhang H, et al. Pressure-induced metallization of molybdenum disulflde[J]. Physical Review Letters, 2014, 113(3):036802.
[57] Awate S S, Xu K, Liang J, et al. Strain-induced 2H to 1T0 phase transition in suspended MoTe₂ using electric double layer gating[J]. ACS Nano, 2023, 17(22):22388-22398.
[58] Manzanares-Negro Y, Quan J, Rassekh M, et al. Low resistance electrical contacts to few-layered MoS₂ by local pressurization[J]. 2D Materials, 2023, 10(2):021003.
[59] Yoo Y, DeGregorio Z P, Su Y, et al. In-plane 2H-1T0 MoTe₂ homojunctions synthesized by flux-controlled phase engineering[J]. Advanced Materials, 2017, 29(16):1605461.
[60] Zhang X, Jin Z, Wang L, et al. Low contact barrier in 2H/1T0 MoTe₂ in-plane heterostructure synthesized by chemical vapor deposition[J]. ACS Applied Materials & Interfaces, 2019, 11(13):12777-12785.
[61] Ma R, Zhang H, Yoo Y, et al. MoTe₂ lateral homojunction fleld-efiect transistors fabricated using flux-controlled phase engineering[J]. ACS Nano, 2019, 13(7):8035-8046.
[62] Yang S, Xu X, Xu W, et al. Large-scale vertical 1T0/2H MoTe₂ nanosheet-based heterostructures for low contact resistance transistors[J]. ACS Applied Nano Materials, 2020, 3(10):10411- 10417.
[63] Zhang Q, Wang X F, Shen S H, et al. Simultaneous synthesis and integration of twodimensional electronic components[J]. Nature Electronics, 2019, 2(4):164-170.
[64] Xu X, Liu S, Han B, et al. Scaling-up atomically thin coplanar semiconductor{metal circuitry via phase engineered chemical assembly[J]. Nano Letters, 2019, 19(10):6845-6852.
[65] Song S, Yoon A, Jang S, et al. Fabrication of p-type 2D single-crystalline transistor arrays with Fermi-level-tuned van der Waals semimetal electrodes[J]. Nature Communications, 2023, 14(1):4747.
[66] Wang Y, Zhai W, Ren Y, et al. Phase-controlled growth of 1T0-MoS₂ nanoribbons on 1H-MoS₂ nanosheets[J]. Advanced Materials, 2024, 36(17):2307269.
[67] Liu X, Shan J, Cao T, et al. On-device phase engineering[J]. Nature Materials, 2024, 23(10):1363-1369.