二硒化铂

二硒化铂
英文名	Platinum(IV) selenide; Platinum diselenide
别名	硒化铂(IV)
识别
CAS号	12038-26-5
PubChem	101946448
SMILES	[Se]=[Pt]=[Se];
性质
化学式	PtSe2
摩尔质量	353 g·mol−1
外观	不透明的黄白色金属光泽固体
密度	9.54
熔点	（分解）
溶解性（水）	难溶
能隙	0 (粒状) 1.3 eV (单层) eV
结构
晶体结构	空间群 P3m1 164 hexagonal
晶格常数	a = 3.728, c = 5.031
配位几何	八面体
相关物质
其他阴离子	二氧化铂; 二硫化铂; 二碲化铂
其他阳离子	二硒化钯
相关化合物	Pt5Se4
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

二硒化铂是一种无机化合物，化学式为PtSe₂。它是层状物质，可以分成薄层至三原子厚的单层。厚度不同，PtSe₂可以展现出半金属或半导体特性。

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二硒化铂在自然界中以硒铂矿（Sudovikovite）的形式存在，该矿以俄罗斯石油学家N.G. Sudovikov（1903 - 1966）命名。矿石的硬度在2到2.5之间。硒铂矿发现于俄罗斯卡累利阿共和国的Zaonezhie半岛的Velikaya Guba铀钒矿床的Srednyaya Padma矿区中。^[2]

制备

在1909年，Minozzi第一个报道了通过相应的元素单质制备二硒化铂。^[3]

将铂薄箔在400℃时与硒蒸气加热可以得到二硒化铂。^[4]^[5]

铂的111晶面暴露于硒蒸气中，270℃可以形成单层PtSe₂.^[6]

除了这些硒化法外，PtSe₂也可以通过在水溶液中用硒化氢处理Pt(IV)得到，或者是加热四氯化铂和硒的混合物。^[3]

性质

二硒化铂的晶体结构为CdI₂，形成的是层状结构。每个单层有铂原子中心，硒原子在铂的上方和下方。这种结构也称为“1T”，属于三角晶系。每层仅由弱键结合在一起，因此可以将片剥离为双层或单层。^[7]

块状的PtSe₂是半金属材料，单层是半导体材料。^[7]块状材料的电导率为620,000 S/m。^[8]

XPS光谱显示了在Pt 4f处有72.3eV的峰，在Pt 5p_3/2有55.19和54.39eV的峰^[7]；Se 3d_3/2和3d_5/2分别有55.19和54.39eV的峰。^[6]

声子振动由红外活性A_2u（Se在Pt面外振动）、E_u（层振动，Se相对于Pt）和拉曼活性A_1g（Se顶部和底部原子沿相反方向205cm^-1移动）、E_g（在平面Se原子相对于顶部和底部移动175cm⁻¹）。在拉曼光谱中，当测量与入射光线垂直偏振的受激发射时，A_1g被减弱。堆叠更多的层时，E_g模式发生红移。（双层材料为166cm⁻¹，块状材料为155cm⁻¹）。当厚度变化时，A_lg排放仅略有变化。^[7]

对于单层，带隙为1.2eV（计算值），双层的为0.21eV（计算值）。对于三层或更厚的物质，会失去一个带隙并变为半金属性质。^[6]

PtSe₂可以在特定气体（如二氧化氮）存在下改变其电导性。在几秒钟内，NO₂吸附在PtSe₂材料的表面，降低了电阻。当气体不存在时，大约一分钟内会回到高电阻的状态。^[4]PtSe₂的塞贝克系数（英语：Seebeckcoefficient）为40 μV/K。^[9]

虽然二硒化铂是非磁性的，但是当存在高达10%的铂空位并且其被置于5％的应变下时，它预计将变为铁磁性。^[10]

二硒化铂的单层显示螺旋旋转纹理，对诸如此类的中心对称材料来说，这一性质并不是我们想要的。这个性质可能是由于局部偶极诱导的拉什巴效应（英语：Rashba effect），这意味着PtSe₂是潜在的自旋电子材料。^[11]

化学反应

目前已知的是水和氧在室温下仅与二硒化铂发生物理吸附，所对应的能量分别为−0.19 eV和−0.13 eV，远低于室温下发生反应所需的能量。^[8]

参考文献

[1]
Guo, G Y; Liang, W Y. The electronic structures of platinum dichalcogenides: PtS2 , PtSe2 and PtTe2. Journal of Physics C: Solid State Physics. 1986-03-10, 19 (7): 995–1008. doi:10.1088/0022-3719/19/7/011.
[2]
Sudovikovite: Sudovikovite mineral information and data.. www.mindat.org. [2017-03-19]. （原始内容存档于2020-11-04）.
[3]
Grønvold, Fredrik; Haakon, Haraldsen; Kjekshus, Arne. On the sulfides, selenides and tellurides of platinum (PDF). Acta Chemica Scandinavica. 1960, 14 (9) [2017-07-02]. （原始内容存档 (PDF)于2018-07-22）.
[4]
Ultra-fast, ultra-sensitive PtSe2 gas sensors. PhysOrg. 2017-01-13 [2017-03-17]. （原始内容存档于2020-11-12）.
[5]
Yim, Chanyoung; Lee, Kangho; McEvoy, Niall; O’Brien, Maria; Riazimehr, Sarah; Berner, Nina C.; Cullen, Conor P.; Kotakoski, Jani; Meyer, Jannik C.; Lemme, Max C.; Duesberg, Georg S. High-Performance Hybrid Electronic Devices from Layered PtSe2 Films Grown at Low Temperature. ACS Nano. 2016-10-25, 10 (10): 9550–9558. doi:10.1021/acsnano.6b04898.
[6]
Wang, Yeliang; Li, Linfei; Yao, Wei; Song, Shiru; Sun, J. T.; Pan, Jinbo; Ren, Xiao; Li, Chen; Okunishi, Eiji; Wang, Yu-Qi; Wang, Eryin; Shao, Yan; Zhang, Y. Y.; Yang, Hai-tao; Schwier, Eike F.; Iwasawa, Hideaki; Shimada, Kenya; Taniguchi, Masaki; Cheng, Zhaohua; Zhou, Shuyun; Du, Shixuan; Pennycook, Stephen J.; Pantelides, Sokrates T.; Gao, Hong-Jun. Monolayer PtSe2, a New Semiconducting Transition-Metal-Dichalcogenide, Epitaxially Grown by Direct Selenization of Pt. Nano Letters. 2015-06-10, 15 (6): 4013–4018. doi:10.1021/acs.nanolett.5b00964.
[7]
O’Brien, Maria; McEvoy, Niall; Motta, Carlo; Zheng, Jian-Yao; Berner, Nina C; Kotakoski, Jani; Elibol, Kenan; Pennycook, Timothy J; Meyer, Jannik C; Yim, Chanyoung; Abid, Mohamed; Hallam, Toby; Donegan, John F; Sanvito, Stefano; Duesberg, Georg S. Raman characterization of platinum diselenide thin films. 2D Materials. 2016-04-13, 3 (2): 021004. doi:10.1088/2053-1583/3/2/021004.
[8]
Zhao, Yuda; Qiao, Jingsi; Yu, Zhihao; Yu, Peng; Xu, Kang; Lau, Shu Ping; Zhou, Wu; Liu, Zheng; Wang, Xinran; Ji, Wei; Chai, Yang. High-Electron-Mobility and Air-Stable 2D Layered PtSe2 FETs. Advanced Materials. February 2017, 29 (5): 1604230. doi:10.1002/adma.201604230.
[9]
Hulliger, F. Electrical properties of some nickel-group chalcogenides. Journal of Physics and Chemistry of Solids. March 1965, 26 (3): 639–645. doi:10.1016/0022-3697(65)90140-X.
[10]
Zulfiqar, Muhammad; Zhao, Yinchang; Li, Geng; Nazir, Safdar; Ni, Jun. Tunable Conductivity and Half Metallic Ferromagnetism in Monolayer Platinum Diselenide: A First-Principles Study. The Journal of Physical Chemistry C. 2016-11-03, 120 (43): 25030–25036. doi:10.1021/acs.jpcc.6b06999.
[11]
Yao, Wei; Wang, Eryin; Huang, Huaqing; Deng, Ke; Yan, Mingzhe; Zhang, Kenan; Miyamoto, Koji; Okuda, Taichi; Li, Linfei; Wang, Yeliang; Gao, Hongjun; Liu, Chaoxing; Duan, Wenhui; Zhou, Shuyun. Direct observation of spin-layer locking by local Rashba effect in monolayer semiconducting PtSe2 film. Nature Communications. 2017-01-31, 8: 14216. doi:10.1038/ncomms14216.

[1] [1]
Guo, G Y; Liang, W Y. The electronic structures of platinum dichalcogenides: PtS2 , PtSe2 and PtTe2. Journal of Physics C: Solid State Physics. 1986-03-10, 19 (7): 995–1008. doi:10.1088/0022-3719/19/7/011.

[2] [2]
Sudovikovite: Sudovikovite mineral information and data.. www.mindat.org. [2017-03-19]. （原始内容存档于2020-11-04）.

[gron-3] [3]
Grønvold, Fredrik; Haakon, Haraldsen; Kjekshus, Arne. On the sulfides, selenides and tellurides of platinum (PDF). Acta Chemica Scandinavica. 1960, 14 (9) [2017-07-02]. （原始内容存档 (PDF)于2018-07-22）.

[ultra-4] [4]
Ultra-fast, ultra-sensitive PtSe2 gas sensors. PhysOrg. 2017-01-13 [2017-03-17]. （原始内容存档于2020-11-12）.

[5] [5]
Yim, Chanyoung; Lee, Kangho; McEvoy, Niall; O’Brien, Maria; Riazimehr, Sarah; Berner, Nina C.; Cullen, Conor P.; Kotakoski, Jani; Meyer, Jannik C.; Lemme, Max C.; Duesberg, Georg S. High-Performance Hybrid Electronic Devices from Layered PtSe2 Films Grown at Low Temperature. ACS Nano. 2016-10-25, 10 (10): 9550–9558. doi:10.1021/acsnano.6b04898.

[wang-6] [6]
Wang, Yeliang; Li, Linfei; Yao, Wei; Song, Shiru; Sun, J. T.; Pan, Jinbo; Ren, Xiao; Li, Chen; Okunishi, Eiji; Wang, Yu-Qi; Wang, Eryin; Shao, Yan; Zhang, Y. Y.; Yang, Hai-tao; Schwier, Eike F.; Iwasawa, Hideaki; Shimada, Kenya; Taniguchi, Masaki; Cheng, Zhaohua; Zhou, Shuyun; Du, Shixuan; Pennycook, Stephen J.; Pantelides, Sokrates T.; Gao, Hong-Jun. Monolayer PtSe2, a New Semiconducting Transition-Metal-Dichalcogenide, Epitaxially Grown by Direct Selenization of Pt. Nano Letters. 2015-06-10, 15 (6): 4013–4018. doi:10.1021/acs.nanolett.5b00964.

[raman-7] [7]
O’Brien, Maria; McEvoy, Niall; Motta, Carlo; Zheng, Jian-Yao; Berner, Nina C; Kotakoski, Jani; Elibol, Kenan; Pennycook, Timothy J; Meyer, Jannik C; Yim, Chanyoung; Abid, Mohamed; Hallam, Toby; Donegan, John F; Sanvito, Stefano; Duesberg, Georg S. Raman characterization of platinum diselenide thin films. 2D Materials. 2016-04-13, 3 (2): 021004. doi:10.1088/2053-1583/3/2/021004.

[fets-8] [8]
Zhao, Yuda; Qiao, Jingsi; Yu, Zhihao; Yu, Peng; Xu, Kang; Lau, Shu Ping; Zhou, Wu; Liu, Zheng; Wang, Xinran; Ji, Wei; Chai, Yang. High-Electron-Mobility and Air-Stable 2D Layered PtSe2 FETs. Advanced Materials. February 2017, 29 (5): 1604230. doi:10.1002/adma.201604230.

[9] [9]
Hulliger, F. Electrical properties of some nickel-group chalcogenides. Journal of Physics and Chemistry of Solids. March 1965, 26 (3): 639–645. doi:10.1016/0022-3697(65)90140-X.

[10] [10]
Zulfiqar, Muhammad; Zhao, Yinchang; Li, Geng; Nazir, Safdar; Ni, Jun. Tunable Conductivity and Half Metallic Ferromagnetism in Monolayer Platinum Diselenide: A First-Principles Study. The Journal of Physical Chemistry C. 2016-11-03, 120 (43): 25030–25036. doi:10.1021/acs.jpcc.6b06999.

[11] [11]
Yao, Wei; Wang, Eryin; Huang, Huaqing; Deng, Ke; Yan, Mingzhe; Zhang, Kenan; Miyamoto, Koji; Okuda, Taichi; Li, Linfei; Wang, Yeliang; Gao, Hongjun; Liu, Chaoxing; Duan, Wenhui; Zhou, Shuyun. Direct observation of spin-layer locking by local Rashba effect in monolayer semiconducting PtSe2 film. Nature Communications. 2017-01-31, 8: 14216. doi:10.1038/ncomms14216.

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