二硒化鉑

二硒化鉑
英文名	Platinum(IV) selenide; Platinum diselenide
別名	硒化鉑(IV)
識別
CAS號	12038-26-5
PubChem	101946448
SMILES	[Se]=[Pt]=[Se];
性質
化學式	PtSe2
摩爾質量	353 g·mol−1
外觀	不透明的黃白色金屬光澤固體
密度	9.54
熔點	（分解）
溶解性（水）	難溶
能隙	0 (粒狀) 1.3 eV (單層) eV
結構
晶體結構	空間群 P3m1 164 hexagonal
晶格常數	a = 3.728, c = 5.031
配位幾何	八面體
相關物質
其他陰離子	二氧化鉑; 二硫化鉑; 二碲化鉑
其他陽離子	二硒化鈀
相關化合物	Pt5Se4
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

二硒化鉑是一種無機化合物，化學式為PtSe₂。它是層狀物質，可以分成薄層至三原子厚的單層。厚度不同，PtSe₂可以展現出半金屬或半導體特性。

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二硒化鉑在自然界中以硒鉑礦（Sudovikovite）的形式存在，該礦以俄羅斯石油學家N.G. Sudovikov（1903 - 1966）命名。礦石的硬度在2到2.5之間。硒鉑礦發現於俄羅斯卡累利阿共和國的Zaonezhie半島的Velikaya Guba鈾釩礦床的Srednyaya Padma礦區中。^[2]

製備

在1909年，Minozzi第一個報道了通過相應的元素單質製備二硒化鉑。^[3]

將鉑薄箔在400℃時與硒蒸氣加熱可以得到二硒化鉑。^[4]^[5]

鉑的111晶面暴露於硒蒸氣中，270℃可以形成單層PtSe₂.^[6]

除了這些硒化法外，PtSe₂也可以通過在水溶液中用硒化氫處理Pt(IV)得到，或者是加熱四氯化鉑和硒的混合物。^[3]

性質

二硒化鉑的晶體結構為CdI₂，形成的是層狀結構。每個單層有鉑原子中心，硒原子在鉑的上方和下方。這種結構也稱為「1T」，屬於三角晶系。每層僅由弱鍵結合在一起，因此可以將片剝離為雙層或單層。^[7]

塊狀的PtSe₂是半金屬材料，單層是半導體材料。^[7]塊狀材料的電導率為620,000 S/m。^[8]

XPS光譜顯示了在Pt 4f處有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分別有55.19和54.39eV的峰。^[6]

聲子振動由紅外活性A_2u（Se在Pt面外振動）、E_u（層振動，Se相對於Pt）和拉曼活性A_1g（Se頂部和底部原子沿相反方向205cm^-1移動）、E_g（在平面Se原子相對於頂部和底部移動175cm⁻¹）。在拉曼光譜中，當測量與入射光線垂直偏振的受激發射時，A_1g被減弱。堆疊更多的層時，E_g模式發生紅移。（雙層材料為166cm⁻¹，塊狀材料為155cm⁻¹）。當厚度變化時，A_lg排放僅略有變化。^[7]

對於單層，帶隙為1.2eV（計算值），雙層的為0.21eV（計算值）。對於三層或更厚的物質，會失去一個帶隙並變為半金屬性質。^[6]

PtSe₂可以在特定氣體（如二氧化氮）存在下改變其電導性。在幾秒鐘內，NO₂吸附在PtSe₂材料的表面，降低了電阻。當氣體不存在時，大約一分鐘內會回到高電阻的狀態。^[4]PtSe₂的塞貝克係數（英語：Seebeckcoefficient）為40 μV/K。^[9]

雖然二硒化鉑是非磁性的，但是當存在高達10%的鉑空位並且其被置於5％的應變下時，它預計將變為鐵磁性。^[10]

二硒化鉑的單層顯示螺旋旋轉紋理，對諸如此類的中心對稱材料來說，這一性質並不是我們想要的。這個性質可能是由於局部偶極誘導的拉什巴效應（英語：Rashba effect），這意味着PtSe₂是潛在的自旋電子材料。^[11]

化學反應

目前已知的是水和氧在室溫下僅與二硒化鉑發生物理吸附，所對應的能量分別為−0.19 eV和−0.13 eV，遠低於室溫下發生反應所需的能量。^[8]

參考文獻

[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]. （原始內容存檔於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]. （原始內容存檔 (PDF)於2018-07-22）.
[4]
Ultra-fast, ultra-sensitive PtSe2 gas sensors. PhysOrg. 2017-01-13 [2017-03-17]. （原始內容存檔於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]. （原始內容存檔於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]. （原始內容存檔 (PDF)於2018-07-22）.

[ultra-4] [4]
Ultra-fast, ultra-sensitive PtSe2 gas sensors. PhysOrg. 2017-01-13 [2017-03-17]. （原始內容存檔於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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