hcp金属的高压拉曼散射光谱研究

刘静仪; 陶雨; 范春梅; 吴彬彬; 雷力

doi:10.11858/gywlxb.20220522

hcp金属的高压拉曼散射光谱研究

doi: 10.11858/gywlxb.20220522

四川大学原子与分子物理研究所, 四川成都　610065

基金项目: 国家自然科学基金（11774247，U2030107）；四川大学理科创新研究项目（2020SCUNL107）

详细信息

作者简介:
刘静仪（1997－），女，硕士研究生，主要从事凝聚态物质在高压下的行为研究.E-mail：liujingyi201903@ 163.com

通讯作者:
雷　力（1980－），男，博士，研究员，主要从事极端条件光谱学与高压物理研究.E-mail：lei@scu.edu.cn

中图分类号: O521.3; O521.2
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出版历程
- 收稿日期: 2022-02-26
- 修回日期: 2022-03-18
- 录用日期: 2022-03-18
- 网络出版日期: 2022-09-16
- 刊出日期: 2022-10-11

High-Pressure Raman Spectroscopy of hcp Metals

Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, Sichuan, China

摘要

摘要: 通过高压拉曼光谱可以从微观角度研究高压下材料的晶格动力学行为。然而，受金刚石荧光与金属样品强反射的影响，高压下金属样品的拉曼光谱信号较难获得。为此，发展了一种简易的金刚石对顶砧倾角散射高压拉曼光谱技术，可实现六角密排结构（hcp）金属样品的高压拉曼光谱信号测量。以hcp金属Be为例，通过测量最高压力达73 GPa时的剪切拉曼模E_2g，获得了其弹性常数C₄₄随压力的变化关系。所提出的金刚石对顶砧倾角散射高压拉曼光谱技术为研究金属材料的成键状态、电子结构、声子-电子耦合效应提供一种新手段。
- hcp金属 /
- 高压 /
- 拉曼散射 /
- 弹性性质
Abstract: The lattice dynamics behavior of materials under high pressure can be studied by high-pressure Raman spectroscopy. However, Raman spectroscopic signal of metal samples at high pressure is difficult to obtain due to the fluorescence of the diamond in diamond anvil cell (DAC) and the strong reflection of the samples. In this work, we use DAC inclination scattering method to mitigate background noise. As a consequence, Raman spectroscopic signal of the hcp metal samples (Be, Re, Os) under high pressure have been achieved. In the case of Be, the pressure dependence of elastic constant C₄₄ is obtained by measuring the shear Raman mode E_2g at pressure up to 73 GPa. The proposed high-pressure Raman spectroscopy technique provides a new method to study bonding state, electronic structure, and phonon-electron coupling effects of metallic materials under high pressure.
- hcp metals /
- high pressure /
- Raman scattering /
- elastic properties

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图 1 高压下hcp金属单质的拉曼谱学信息

Figure 1. Raman spectrum information of the hcp metals under high pressure

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图 2 hcp金属的E_2g拉曼模的原子振动示意图

Figure 2. Schematic diagram of the atomic vibration of the E_2g Raman mode of the hcp metals

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图 3 四川大学ESL实验室的高压金属拉曼实验光路

Figure 3. Optical system layout used for the study of metals under pressure designed by ESL Lab of Sichuan University

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图 4 金属样品拉曼信号的不同测量方法：(a) 背散射，(b) 侧向激发散射，(c) DAC倾角散射

Figure 4. Different measuring methods for Raman signal of metal samples: (a) backscattering, (b) sidescattering, (c) DAC inclination scattering

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图 5 DAC倾角散射原理 (a) 和实验布置 (b)

Figure 5. (a) Schematic diagram and (b) experimental set-up image of DAC inclination scattering

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图 6 采用背散射法测量得到的 (a) Re在195 GPa下、(b) Os在73 GPa下、(c) Be在48 GPa下的拉曼光谱，以及采用DAC倾角散射法测量得到的 (d) Re在195 GPa下、(e) Os在73 GPa下、(f) Be在48 GPa下的拉曼光谱

Figure 6. Backscattering method obtained Raman scattering spectra of (a) Re at 195 GPa, (b) Os at 73 GPa and (c) Be at 48 GPa; DAC inclination scattering method obtained Raman scattering spectra of (d) Re at 195 GPa, (e) Os at 73 GPa and (f) Be at 48 GPa

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图 7 (a) 金属Be在不同压力下的拉曼散射光谱（曲线采用Lorentz拟合），(b) 金属Be的拉曼频移随压力的变化关系

Figure 7. (a) Raman scattering spectra of Be at different pressures (curves fitted by Lorentz method); (b) Raman shift of Be versus pressure

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图 8 金属Be的弹性剪切参数C₄₄随压力的变化关系

Figure 8. Elastic shear parameter C₄₄ of Be versus pressure

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表 1 不同的hcp金属零压下的拉曼声子频率ω₀及压力系数α和β

Table 1. Zero-pressure Raman phonon frequency ω₀ and pressure coefficients α and β for different hcp metals

Sample	Pressure range/GPa	ω₀/cm⁻¹	α_p=0	β_p=0	Ref.
Be	0−73	463.4	2.622	−6.6×10⁻³	This work
	0−77	459	2.806	−1.1×10⁻²	Evans, et al.^[41]
	0−23	455.8	3.559	−3.51×10⁻²	Olijnyk, et al.^[24]
	0	463			Frass, et al.^[42]
	0	455			Feldman, et al.^[39]
Os	0−211	164.2	0.591	−1.05×10⁻³	Liu, et al.^[34]
Os	0−13	164.8	0.739	−7.82×10⁻³	Ponosov, et al.^[43]
Re	0−205	121.3	0.438	−4.94×10⁻⁴	Liu, et al.^[34]
	0−20	120	0.56	−7.8×10⁻⁴	Qi, et al.^[44]
	0−63	121.3	0.573	−1.54×10⁻³	Olijnyk, et al.^[25]
	0−43	119	0.694	−4.25×10⁻³	Goncharov, et al.^[45] (under hydrostatic)
	0−138	119.9	0.468	−9.04×10⁻⁴	Goncharov, et al.^[45] (under nonhydrostatic)

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A1 不同压力下Be的拉曼峰频率

A1. Raman shifts of Be under different pressures

Exp. No.	p/GPa	ω/cm⁻¹	Exp. No.	p/GPa	ω/cm⁻¹	Exp. No.	p/GPa	ω/cm⁻¹
1	0	456.0	1	16.8	502.2	2	25.8	529.3
	0.1	456.9		17.3	503.8		27.0	528.0
	1.6	460.8		17.4	505.5		29.1	534.4
	2.8	473.5		18.6	507.7		31.8	540.0
	4.2	469.7		20.0	509.4		34.0	542.3
	5.9	473.5		21.0	512.7		34.6	548.7
	6.4	478.8		21.6	511.2		36.3	550.0
	10.3	489.3		22.0	513.2		39.3	557.2
	10.7	493.3		22.8	516.0		44.8	566.6
	13.3	493.0		23.4	515.6		48.6	573.3
	13.4	494.8		23.6	516.0		50.0	577.9
	14.1	497.0		26.4	515.6		53.5	581.2
	14.3	497.4		28.8	523.0		55.0	590.2
	14.5	499.5		30.0	534.9		58.0	592.9
	15.1	496.4	1	0	463.6		60.0	597.8
	15.2	496.3		13.1	497.1		62.0	603.3
	15.9	499.4		16.6	505.0		68.0	614.4
	16.4	503.8		21.0	514.0		69.0	610.5
	16.5	501.6		23.9	521.6		73.0	617.1

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A2 Be在不同压力下的弹性剪切参数及其误差

A2. Elastic shear parameter and their errors at different pressures of Be

p/GPa	ω/cm⁻¹	a/Å	δ_a/Å	c/Å	δ_c/Å	C₄₄/GPa	$\delta{_{C_{44}} }$/GPa	Error/%
0	463.6	2.258	±0.004	3.519	±0.011	113.7	±0.07	0.06
13.1	497.1	2.210	±0.006	3.453	±0.015	133.9	±0.11	0.09
16.6	505.0	2.198	±0.006	3.436	±0.016	139.1	±0.13	0.09
21.0	514.0	2.182	±0.007	3.415	±0.017	145.2	±0.15	0.10
23.9	521.6	2.173	±0.007	3.402	±0.018	150.3	±0.16	0.11
25.8	529.3	2.166	±0.007	3.393	±0.019	155.3	±0.17	0.11
27.0	528.0	2.162	±0.007	3.388	±0.019	154.8	±0.18	0.11
29.1	534.4	2.155	±0.008	3.378	±0.020	159.2	±0.19	0.12
31.8	540.0	2.147	±0.008	3.366	±0.021	163.2	±0.20	0.12
34.0	542.3	2.140	±0.008	3.357	±0.022	165.2	±0.21	0.13
34.6	548.7	2.138	±0.008	3.354	±0.022	169.3	±0.22	0.13
36.3	550.0	2.132	±0.009	3.347	±0.022	170.6	±0.23	0.14
39.3	557.2	2.123	±0.009	3.334	±0.024	176.0	±0.25	0.14
44.8	566.6	2.107	±0.010	3.311	±0.026	183.6	±0.29	0.16
48.6	573.3	2.095	±0.010	3.296	±0.027	189.1	±0.32	0.17
50.0	577.9	2.091	±0.011	3.291	±0.028	192.6	±0.33	0.17
53.5	581.2	2.081	±0.011	3.277	±0.029	195.8	±0.35	0.18
55.0	590.2	2.077	±0.011	3.271	±0.030	202.4	±0.38	0.19
58.0	592.9	2.069	±0.012	3.260	±0.031	205.2	±0.40	0.19
60.0	597.8	2.064	±0.012	3.253	±0.032	209.2	±0.42	0.20
62.0	603.3	2.058	±0.012	3.246	±0.032	213.7	±0.44	0.21
68.0	614.4	2.043	±0.013	3.224	±0.035	223.6	±0.50	0.23
69.0	610.5	2.040	±0.014	3.221	±0.035	221.1	±0.51	0.23
73.0	617.1	2.030	±0.014	3.207	±0.037	227.2	±0.55	0.24

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