Preparation and magnetic properties of chromium doped zinc sulfide and cadmium sulfide nanostructures by solvothermal method

Zhang Zhu-Feng; Ren Yin-Shuan

doi:10.7498/aps.70.20201963

Abstract

With the continuous development of nanotechnology, people have higher and higher requirements for the performances of nanomaterials. In the past few decades, researchers have used various methods to prepare nanomaterials with different dopants, and studied their optical and electrical properties. Nanomaterials with ferromagnetic properties have a wide range of applications, and there have been many reports about the ferromagnetic properties of doped magnetic elements. However, there have been few reports about Cr-doped ZnS and CdS. In order to obtain Cr-doped ZnS and CdS nanosheets with room temperature ferromagnetism, in this paper, using ethanolamine (EA) and ethylenediamine (EN) as mixed solvents, ZnS and CdS semiconductor nanostructures doped with different amounts of chromium are successfully prepared in S, ZnO and CdO sources by simple solvent thermal method. The X-ray diffraction (XRD) measurements show that the ZnS and CdS nanostructure have a wurtzite structure. Scanning electron microscopy (SEM) images show the morphologies of ZnS and CdS with different chromium content. When the content of Cr is 4.31 at% or 7.25 at%, the thickness of Cr-doped ZnS nanosheets is about 210–290 nm, and the morphology of undoped ZnS is composed of sub-morphologies of relatively thick nanosheets. The morphologies of CdS doped with different amounts of Cr are composed of sub-morphologies of snowflake like nanosheets with thickness of about 120–190 nm. Energy dispersive spectrometer (EDS) is used to observe the product composed of Cr, Zn, Cd, and S. The EDS measurement and calculation of the Cr content in Cr-doped ZnS nanosheets are 4.31 at% and 7.25 at% respectively, and those of the Cr content in Cr-doped CdS nanosheets are 1.84 at% and 2.12 at%. The vibration sample magnetometer(VSM) measurements show that ZnS doped with chromium exhibits ferromagnetism at room temperature, while the undoped ZnS exhibits diamagnetism at room temperature. The values of saturation magnetization M_s of Cr-doped ZnS nanosheets with Cr = 4.31 at% and 7.25 at% are 2.314 and 5.683 (10^–3 emu/g), and the coercivity values of H_c are 54.721 and 88.441 Oe, respectively. The ferromagnetism of pure CdS is weak, while that of Cr-doped CdS is enhanced at room temperature. The saturation magnetization M_s values of Cr-doped CdS nanosheets with Cr = 0, 1.84 at% and 2.12 at% are 0.854, 2.351 and 7.525(10^–3 emu/g), respectively, and the coercivity values of H_c are 74.631, 114.372 and 64.349 Oe, respectively. The values of saturation magnetization of ZnS and CdS increases with the Cr doping increasing. The ferromagnetism of Cr-doped ZnS at room temperature is confirmed by the experimental result, which is consistent with the ferromagnetism of Cr-doped ZnS calculated by the first principle. The origin of ferromagnetism of Cr-doped CdS is related to the doping of Cr in CdS lattice.

Keywords:

ZnS /
CdS /
Cr /
ferromagnetism

Authors and contacts

1.
College of Mobile Telecommunications, Chongqing University of Posts and Telecom, Chongqing 401520, China
2.
School of Physics and Electronics, Qian Nan Normal College for Nationalities, Duyun 558000, China

Corresponding author: Ren Yin-Shuan, renyinshuan319@163.com

Funds: Project supported by the Science and Technology Department of Guizhou Province, China (Grant No. [2020]1Y208), the Guizhou Provincial Department of Education Project, China (Grant No. KY[2020]208), the Project of Qiannan Normal College for Nationalities, China (Grant Nos. 2018XJG0530, QNSY2018002), and the Research Project of Teaching Reform in College of Mobile Telecommunications, Chongqing University of Posts and Telecom, China (Grant No. YTJG2019050)

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References

[1]	Xiang Q J, Cheng B, Yu J G 2015 Angew. Chem. Int. Ed. 54 11350 Google Scholar
[2]	Jin J, Yu J G, Guo D P, Cui C, Ho W K 2015 Small 11 5262 Google Scholar
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[7]	Hu Y, Hao X Q, Cui Z W, Zhou J, Chu S Q, Wang Y, Zou Z G 2020 Appl. Catal., B 260 118131 Google Scholar
[8]	Liu C H, Yu A F, Peng M Z, Song M, Liu W, Zhang Y, Zhai J Y 2016 J. Mater. Chem. C 120 6971
[9]	Purusothaman Y, Alluri N R, Chandrasekhar A, Kim S J 2017 J. Mater. Chem. C 5 415 Google Scholar
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[12]	Murugesan R, Sivakumar S, Karthik K, Anandan P, Haris M 2019 Appl. Phys. A 125 281 Google Scholar
[13]	Kumar B, Sinha N, Ray G, Godara S, Gupta M K 2014 Mater. Res. Bull. 59 267 Google Scholar
[14]	ChengY J, Brahma S, Liu C P, Huang J L 2017 J. Alloys Compd. 728 1248 Google Scholar
[15]	Sinha N, Goel S, Joseph A J, Yadav H, Batra K, Gupta M K, Kumar B 2018 Ceram. Int. 44 8582 Google Scholar
[16]	Shim Y, Mills M E, Borovikov V, Amar J G 2009 Phys. Rev. E 5 1604
[17]	Elango M, Gopalakrishnan K, Vairam S, Thamilselvan M 2012 J. Alloys Compd. 538 48 Google Scholar
[18]	Niwayama Y, Kura H, Sato T, Takahashi M, Ogawa T 2008 Phys. Rev. Lett. 92 202502
[19]	Haazen P P, Laloe J B, Nummy T J, Swagten J M, Herrero P J, Heiman D, Moodera J S 2012 Appl. Phys. Lett. 100 082404 Google Scholar
[20]	Park S O, Lee H J, Cho Y C, Jeong S Y 2002 Appl. Phys. Lett. 80 22 Google Scholar
[21]	Li Y F, Zhou Z, Jin P, Chen Y S, Zhang S B, Chen Z F 2010 J. Phys. Chem. C 114 12099
[22]	Madhu C, Sundaresan A, Rao C N R 2008 Phys. Rev. B 77 201306 Google Scholar
[23]	Zhang Z F, Li J, Jian J K, Wu R, Sun Y F, Wang S F, Ren Y S, Li J J 2013 J. Cryst. Growth 372 39 Google Scholar
[24]	Zhang Z F, Han L, Xie G Y, Liao Q L, Zhong B, Yu Y 2016 J. Mater. Sci.- Mater. Electron. 27 12490 Google Scholar
[25]	Elavarthi P, Kumar A A, Murali G, Reddy D A, Gunasekhar K R 2016 J. Alloys Compd. 656 510 Google Scholar
[26]	Zhang S X, Ogale S B, Kundaliya D C, Fu L F, Browning N D, Dhar S, Ramadan W, Higgins J S, Greene R L, Venkatesan T 2006 Appl. Phys. Lett. 89 012501 Google Scholar
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Cited By

图 1 Cr掺杂ZnS纳米片的XRD图谱, 三条曲线分别对应样本A (Cr原子百分比为4.31%, a), 样本B (Cr原子百分比为7.25%, b)和样本E (Cr原子百分比为0.00%, e)

Figure 1. Some of the powder XRD patterns of Cr-doped ZnS nanosheets. Three curves correspond to sample A (atomic percentages of Cr is4.31%, a), sample B (atomic percentages of Cr is 7.25%, b), sample E (atomic percentages of Cr is 0%, e), respectively.

DownLoad: Full-Size Img PowerPoint

图 2 Cr掺杂CdS纳米片的XRD图谱, 三条曲线分别对应样本C (Cr原子百分比为1.84%, c), 样本D (Cr原子百分比为2.12%, d)和样本F (Cr原子百分比为0.00%, f)

Figure 2. Some of the powder XRD patterns of the Cr-doped CdS nanosheets. Three curves correspond to sample C (atomic percentages of Cr is 1.84%, c), sample D (atomic percentages of Cr is 2.12%, d) and sample F (atomic percentages of Cr is 0.00%, f), respectively.

DownLoad: Full-Size Img PowerPoint

图 3 (a), (b), (e) Cr掺杂ZnS纳米片的SEM图案; (c), (d), (f) Cr掺杂CdS纳米片的SEM图案, 掺杂Cr的原子百分比分别为(a) 4.31%, (b) 7.25%, (e) 0, (c) 1.84%, (d) 2.12%, (f) = 0

Figure 3. (a), (b), (e) The SEM patterns of the Cr-doped ZnS nanosheets; (c), (d), (f) the SEM patterns of the Cr-doped CdS nanosheets. The atomic percentages of Cr doping are (a) 4.31%, (b) 7.25%, (e) 0, (c) 1.84%, (d) 2.12%, (f) 0, respectively.

DownLoad: Full-Size Img PowerPoint

图 4 (a), (b) Cr掺杂ZnS纳米片的EDS图; (c), (d) Cr掺杂CdS纳米片的EDS图. 掺杂Cr的原子百分比分别为(a) 4.31%, (b) 7.25%, (c) 1.84%, (d) 2.12%

Figure 4. (a), (b) The EDS patterns of the Cr-doped ZnS nanosheets; (c), (d) the EDS patterns of the Cr-doped CdS nanosheets. The atomic percentages of Cr doping are (a) 4.31%, (b) 7.25%, (c) 1.84%, (d) 2.12%, respectively.

DownLoad: Full-Size Img PowerPoint

图 5 未掺杂ZnS纳米片在室温下的磁化强度和磁场强度(M-H)曲线

Figure 5. M-H curves of undoped ZnS nanosheets at room temperature.

DownLoad: Full-Size Img PowerPoint

图 6 未掺杂CdS纳米片在室温下的磁化强度和磁场强度(M-H)曲线

Figure 6. M-H curves of undoped CdS nanosheets at room temperature.

DownLoad: Full-Size Img PowerPoint

图 7 Cr掺杂ZnS和CdS纳米片在室温下磁化强度和磁场强度(M-H)曲线

Figure 7. M-H curves of Cr-doped ZnS and CdS nanosheets at room temperature.

DownLoad: Full-Size Img PowerPoint

图 8 Cr掺杂ZnS和CdS的饱和磁化强度(M_s)和矫顽力(H_c)的直方图

Figure 8. Histogram of saturation magnetization (M_s) and coercivity (H_c) of Cr-doped ZnS and CdS nanosheets.

DownLoad: Full-Size Img PowerPoint

表 1 制备样品(A—F)的反应条件(所有实验在200 ℃下反应24 h)

Table 1. Reaction conditions of the prepared products (All experments are carried out 200 ℃ for 24 h).

Sample	Compsition of solvent/mL	Sulfur, zinc and cadium source/mmol	Chromic chloride hexahydrate/mmol	Concentration of oxalic acid/mmol
A	10 EN + 20 EA	1 S + 1 ZnO	0.250	0.025
B	20 EN + 10 EA	1 S + 1 ZnO	0.500	0.025
E	15 EN + 15 EA	1 S + 1 ZnO	0	0.025
C	10 EN + 20 EA	1 S + 1 CdO	0.250	0.025
D	20 EN + 10 EA	1 S + 1 CdO	0.500	0.025
F	15 EN + 15 EA	1 S + 1 CdO	0	0.025

DownLoad: CSV

表 2 SEM, EDS和VSM计算Cr掺杂的ZnS和CdS纳米片的Cr含量、形貌、尺寸、磁性、矫顽力和饱和磁化强度图

Table 2. Measured chromium content, morphology, size, magnetic properties, coercivity and saturation magnetization of Cr doped ZnS and CdS nanosheets using SEM, EDS and VSM.

	Cr content/%	Morphologies	Size/nm	Magnetic properties	Coercivity/Oe	Saturation magnetization/ (10^–3 emu·g^–1)
ZnS	0	Hexagonal flake	310—390	Diamagnetism	—	—
	4.31	flower-like sheet	210—290	Ferromagnetism	54.721	2.314
	7.25	Flower-like sheet	200—250	Ferromagnetism	88.441	5.683
CdS	0	Snowflake	110—160	Weak ferromagnetism	74.631	0.854
	1.84	Snowflake	100—170	strong ferromagnetism	114.372	2.351
	2.12	Snowflake	100—200	Strong ferromagnetism	64.349	7.525

DownLoad: CSV

[1]	Xiang Q J, Cheng B, Yu J G 2015 Angew. Chem. Int. Ed. 54 11350 Google Scholar
[2]	Jin J, Yu J G, Guo D P, Cui C, Ho W K 2015 Small 11 5262 Google Scholar
[3]	Zhang J, Xu Q L, Qiao S Z, Yu J G 2013 Chem. Sum. Chem. Full. Papers 6 2009
[4]	Diroll B T, Koschitzky A, Murray C B 2014 J. Phys. Chem. Lett. 5 85 Google Scholar
[5]	Diroll B T, Murray C B 2014 American Chem. Soc. Nano Lett. 8 6466
[6]	Zhong W W, Shen S J, He M, Wang D, Wang Z P, Lin Z P, Tu W G, Yu J G 2019 Appl. Catal., B 258 117967 Google Scholar
[7]	Hu Y, Hao X Q, Cui Z W, Zhou J, Chu S Q, Wang Y, Zou Z G 2020 Appl. Catal., B 260 118131 Google Scholar
[8]	Liu C H, Yu A F, Peng M Z, Song M, Liu W, Zhang Y, Zhai J Y 2016 J. Mater. Chem. C 120 6971
[9]	Purusothaman Y, Alluri N R, Chandrasekhar A, Kim S J 2017 J. Mater. Chem. C 5 415 Google Scholar
[10]	Yang D C, Qiu Y, Wang T Y, Song W B, Wang Z Z, Xu J, Feng Q X, Zong Y, Sun X L 2016 J. Mater. Sci.-Mater. Electron. 27 6708 Google Scholar
[11]	Junaid M, Imran M, Ikram M, Naz M, Aqeel M, Afzal H, Maeed H, All S 2019 Appl. Nano Sci. 18 0933
[12]	Murugesan R, Sivakumar S, Karthik K, Anandan P, Haris M 2019 Appl. Phys. A 125 281 Google Scholar
[13]	Kumar B, Sinha N, Ray G, Godara S, Gupta M K 2014 Mater. Res. Bull. 59 267 Google Scholar
[14]	ChengY J, Brahma S, Liu C P, Huang J L 2017 J. Alloys Compd. 728 1248 Google Scholar
[15]	Sinha N, Goel S, Joseph A J, Yadav H, Batra K, Gupta M K, Kumar B 2018 Ceram. Int. 44 8582 Google Scholar
[16]	Shim Y, Mills M E, Borovikov V, Amar J G 2009 Phys. Rev. E 5 1604
[17]	Elango M, Gopalakrishnan K, Vairam S, Thamilselvan M 2012 J. Alloys Compd. 538 48 Google Scholar
[18]	Niwayama Y, Kura H, Sato T, Takahashi M, Ogawa T 2008 Phys. Rev. Lett. 92 202502
[19]	Haazen P P, Laloe J B, Nummy T J, Swagten J M, Herrero P J, Heiman D, Moodera J S 2012 Appl. Phys. Lett. 100 082404 Google Scholar
[20]	Park S O, Lee H J, Cho Y C, Jeong S Y 2002 Appl. Phys. Lett. 80 22 Google Scholar
[21]	Li Y F, Zhou Z, Jin P, Chen Y S, Zhang S B, Chen Z F 2010 J. Phys. Chem. C 114 12099
[22]	Madhu C, Sundaresan A, Rao C N R 2008 Phys. Rev. B 77 201306 Google Scholar
[23]	Zhang Z F, Li J, Jian J K, Wu R, Sun Y F, Wang S F, Ren Y S, Li J J 2013 J. Cryst. Growth 372 39 Google Scholar
[24]	Zhang Z F, Han L, Xie G Y, Liao Q L, Zhong B, Yu Y 2016 J. Mater. Sci.- Mater. Electron. 27 12490 Google Scholar
[25]	Elavarthi P, Kumar A A, Murali G, Reddy D A, Gunasekhar K R 2016 J. Alloys Compd. 656 510 Google Scholar
[26]	Zhang S X, Ogale S B, Kundaliya D C, Fu L F, Browning N D, Dhar S, Ramadan W, Higgins J S, Greene R L, Venkatesan T 2006 Appl. Phys. Lett. 89 012501 Google Scholar
[27]	Ozaki N, Nishizawa N, Marcet S, Kuroda S, Eryu O, Takita K 2006 Phys. Rev. Lett. 97 037201 Google Scholar

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