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Abstract
Here, we systematically report on the preparation of high-quality few-layered MnPS3 nanosheets (NSs) by chemical vapor transport (CVT) and mechanical stripping method, and its carrier dynamics and third-order nonlinear optical properties were studied. Using the classical technique of open aperture Z-scan, a typical phenomenon of saturable absorption (SA) was observed at 475 nm, which indicates that the material is expected to be used as a saturable absorber in ultrafast lasers. The typical phenomenon of reverse saturation absorption (RSA) is observed at 800 and 1550 nm, which shows its potential in the field of broadband optical limiting. Compared with graphene, BP, MXene, MoS2 and other typical two-dimensional materials, MnPS3 NSs has a higher modulation depth. Using the non-degenerate transient absorption spectroscopy technology at room temperature, a slower cooling process of thermal carrier of MnPS3 was observed. Moreover, the carrier lifetime can be tuned according to the wavelength. This work is of great significance to the improvement of MnPS3 based devices, and lays a foundation for the application of MnPS3 in short-wavelength photovoltaic cell, photoelectric detection and other fields.
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1. Introduction
MPX3 is a class of new two-dimensional layered intrinsic magnetic semiconductor material, which is cheap, non-toxic, easy to synthesize, and has good stability. [1–3] Because of its unique and excellent physical properties, it has attracted wide attention in spintronics, photocatalysts, optoelectronics and other fields. [4–10] This kind of material has a typical layered structure like graphene, with weak van der Waals forces between layers, so it is easier to peel off, and it is easier to control its optical properties by changing the number of layers and stacking different layered materials. [11] However, different from the zero-bandgap characteristics of graphene, MPX3 has a wind bandgap of 1.3 eV to 3.5 eV. [12] The wide bandgap makes it suitable for a variety of optical or electronic devices. [4] The fascinating photoelectric properties of MPX3 have been widely reported. Chen et al. used MnPSe3 as a saturated absorber to realize a stable pulsed laser in long band with the maximum single pulse energy of 1.18 nJ. [13] Chen et al. found that NiPS3 nanosheets have lower saturable absorption strength than graphene and black phosphorus, which fully demonstrates that NiPS3 can be used as an excellent saturable absorber material, and achieve a mode-locked laser with a maximum single pulse energy of 0.85 nJ. [14] Liu et al. prepared a self-powered photo-electrochemical photodetector using NiPS3 nanosheets as electrodes, Liu et al. prepared a self-powered photochemical photodetector using NiPS3 nanosheets as electrodes, showing a photocurrent signal much higher than that of black phosphorus and InSe. [15–17] Ou et al. found that the positive and negative optical conductivity of FePS3 could be controlled by modulating the excitation wavelength, which provides us with the possibility to control the electronic properties of two-dimensional magnetic semiconductor materials by optical means [18,19] Therefore, MPX3 materials show great application prospects in the field of photoelectric.
MnPS3 is one of the representatives of the MPX3, which has a direct bandgap of 3.0 eV and is an intrinsic antiferromagnetic semiconductor. [20,21] Magdalena Birowska et al. theoretically calculated that the exciton binding energy of Neel-MnPS3 is twice that of TMDCs, indicating that they have great potential in magneto-optical research and applications. [22] Shifa et al. discovered that it had good photocatalytic properties and Carmen C. Mayorga-Martinez et al. proved that it could be used as an efficient electrocatalyst, which demonstrate its potential in energy and environmental issues. [23,24] Rajat Kumar et al. invented the field-effect transistor based on it, which proved to be an excellent ultraviolet photodetector. [25] Moreover, MnPS3 has very good stability in air. [26,27] Therefore, MnPS3 shows great potential in the photoelectric field, which has attracted extensive attention recently. The above performance shows that it has excellent performance in photoelectric, magneto-optical, photocatalytic and other aspects. To our knowledge, the third-order nonlinear optical properties and carrier dynamics of two-dimensional of MnPS3 have not been studied. [28]
Here, via the method of CVT, high-quality MnPS3 were prepared. [29] The classical z-scan measurement system was chosen to study the third-order nonlinear optical effect of MnPS3 at different wavelengths (475,800 and 1550nm). The typical SA phenomenon is observed at 475nm, which indicates that the material can be used as a saturated absorption material for ultrafast lasers. Its wide band RSA characteristics was found, which shows its potential as a composite optical limiting material. Furthermore, the carrier dynamics of MnPS3 was studied by transient absorption (TA) spectroscopy at room temperature. Its decay time reaches the order of nanosecond, which indicates that MnPS3 has a slow thermal carrier cooling process. The slow cooling process of hot carriers helps to extract them before cooling and realize efficient utilization of hot carrier energy. This work provides insights into new solar cell materials and photoelectric detection and other fields.
2. Morphology characterizations
The structure diagram of MnPS3 nanosheets (NSs) is given in Fig. 1(a). Sulfur atoms form a neat surface, Mn2+ can be seen embedded in the (P2S6)4- double cone. The absorption spectrum of MnPS3 in visible near infrared band was measured by spectrometer, as shown in Fig. 1(b). It can be seen from the figure that there is strong absorption of wavelengths below 500nm. As shown in Fig. 1(c), the bandgap of MnPS3 NSs obtained by Tauc plot method is about 2.9 eV, which is similar to previous data. [20] The atomic force microscopy (AFM) technique was used to measure the size and thickness of MnPS3 NSs. Figure 1(d) displays a typical AFM plot of an exfoliated MnPS3 NSs. The exfoliated MnPS3 NSs is quadrilateral with a thickness of about 20nm (around 20 layers).
Fig. 1. (a) Schematic representation of MnPS3 (top view and side view). (b) Steady-state absorption spectra of MnPS3 NSs. (c) Corresponding Tauc plot of the linear optical absorption spectrum. (d) AFM image of an exfoliated MnPS3 NSs. (e) Raman spectroscopy of MnPS3. (f) XRD spectra of MnPS3. (g) TEM micrograph of a randomly selected MnPS3 NSs. (h) Crystal fringes shown by HRTEM image. (i) SAED pattern of the MnPS3 NSs.
The Raman spectra of the MnPS3 bulk (blue line) and nanosheet (red line) are displayed in Fig. 1(e). A small peak around 155 cm−1 is attribute to Eu mode of vibration, which is typical features of MnPS3 [30]. The Raman peaks originating from P2S6 units with D3d symmetry are identified as A1g (246, 382) and Eg (225.5 and 581 cm−1) [26,31–33]. The out-of plane vibrations of P2S6 units can be ascertained from the strongly polarized A1g mode appearing at 382 cm−1. Prominent Raman modes at 246 and 491 cm−1 are due to the P-S bond symmetric stretching vibration. Meanwhile, peaks related to the in-plane vibrations of P2S6 units are locating at 274 and 581 cm−1 and represented by Eg mode. Similar Raman modes can be observed in the bulk and few-layered MnPS3 NSs, which means a weaker interlayer van der Waals forces compared to most other two-dimensional materials [34].
Using X-ray diffraction (XRD) measurement, the phase purity and crystal structure of MnPS3 were analyzed. Figure 1(f) shows the results of XRD of MnPS3 bulk (blue line) and nanosheets (red line). These peaks correspond to the space group C2/m of hexagonal phase. The diffraction peak at about 13.5, 27.4, 41.6, and 56.6°can be well indexed to the (001), (002), (003), and (004) periodic diffraction peaks, respectively [35]. Four sharp peaks indicate that the crystallinity of MnPS3 bulk and MnPS3 NSs is good. (001) peak is higher than the other peaks, indicating that both MnPS3 NSs and MnPS3 bulk have preferred orientations in the (001) direction.
The microstructure of the MnPS3 NSs were thoroughly probed by transmission electron microscopy (TEM) and selected area electron diffraction (SAED). Figure 1(g) is the TEM of a randomly selected MnPS3 NSs, exhibiting a triangular shape with lateral size of ∼300 nanometers, which matches well with the corresponding AFM plot. As show in Fig. 1(h), the high-resolution TEM (HRTEM) revealed lattice fringes with interatomic space of 0.26, 0.3 and 0.35 nm, pointing towards (−202), (201) and (111) crystal planes, respectively. Figure 1(i) displays the corresponding SAED pattern of the MnPS3 NSs, shows that MnPS3 has single crystal property in the whole region, and the obvious and intense diffraction spots in SAED pattern testify to its high crystallinity. he SAED pattern shows a refined hexagonal structure, which is consistent with the corresponding crystal planes in the HRTEM image in Fig. 1(h) and XRD data.
3. Results and discussion
3.1 Third-order nonlinear optical response of few-layer MnPS3 NSs
The third-order nonlinear effects of two-dimensional materials have important applications in ultra-short pulse, optical modulator, optical limiting and other fields. The well-developed open- aperture Z-scan technique was chosen to detect the nonlinear optical coefficient of MnPS3 NSs [36,37]. As shown in Fig. 2, MnPS3 NSs exhibit a typical trace of SA at 475nm, while a typical trace of RSA was found at 800 and 1550 nm.
Fig. 2. OA Z-scan curves for (a) 475 nm, (b) 800 nm, and (c) 1550 nm. Changes of normalized transmittance versus incident light intensity for (d) 475 nm, (e) 800 nm, and (f) 1550 nm.
The absorption coefficient $\alpha$ of the MnPS3 NSs can be written as:
${\alpha _0}$ is the linear absorption coefficient and ${\alpha _{NL}} = \beta I$ is the nonlinear absorption part. In order to calculate its nonlinear absorptive coefficient, we use the function to fit the Z-scan curve [38,39]:
Table 1. Nonlinear optical parameters of the MnPS3 NSs at different wavelengths
Table 2 summarizes nonlinear optical parameters of different two-dimensional materials. Compared with other typical two-dimensional materials such as graphene, BP, MXene and MoS2, the order of magnitude of ${I_s}$ of MnPS3 NSs is slightly smaller than graphene and MoS, but slightly larger than these materials in the order of magnitude of $\beta $, and much higher than these two-dimensional materials on $\varDelta T$, and higher modulation depth means better optical modulation capacity. This indicates that the material is expected to be used in ultrafast laser as a saturable absorber. In optical limiting field, the most studied and the best performance is the application of nonlinear RSA materials. The RSA characteristic of MnPS3 NSs shows that it has a broad prospect for application in broadband optical limiting field [41–44].
Table 2. Nonlinear optical parameters of the MnPS3 NSs at different wavelengths
The mechanism of SA can be explained by the model in Fig. 3. When the energy of the incident light is slightly higher than the bandgap of MnPS3 NSs, the electrons in the valence band will absorb the photon and transition to the conduction band, leaving holes in the valence band. The electrons and holes are carriers. Then the electrons occupy the lower energy state and the holes occupy the higher energy state, resulting in a Fermi-Dirac distribution. Hot carriers cool further due to intraband phonon scattering, and electron-hole pairs recombine until the electron and hole distributions return to equilibrium. This is a linear optical effect at low excitation intensity. But when the light intensity increases to a certain value, the optical carrier density increases rapidly until it completely occupies the edge states of the conduction band and valence band. Due to the Pauli blocking principle, these photons can directly pass through MnPS3 NSs without being absorbed, which leads to its SA. When the incident wavelength is increased to 800 and 1550 nm, the photon energy is less than the bandgap of MnPS3 NSs and the electron can hardly be excited. Therefore, if the intensity of incident light increases, two-photon absorption or multi-photon absorption may be triggered, which leads to its RSA phenomenon.
3.2 Photoexcited carrier dynamics of MnPS3 NSs
The photophysical process of photoexcitation and recombination of carriers in materials is a key in various optoelectronic devices. The study of their dynamics and regulatory properties of optical materials is important for understanding the operation of photoelectronic devices and optimizing their performance. In order to study the photocarriers dynamics in the MnPS3 NSs, the non-degenerate fs-resolved transient absorption (TA) spectrum technology was used.
In this work, the pump wavelength was selected to be 400 nm to provide enough energy to excite ground state particle transforms into an excited state. The probe wavelength ranges from 480 to 770 nm.
Figure 4(a) shows the two-dimensional color TA spectra plot of MnPS3 NSs, which contains temporally and spectrally resolved TA signals. As can be seen in the two-dimensional color TA spectra plot, MnPS3 NSs exhibit a long lifetime ultrabroad photoinduced absorption (PIA) signal, which is attributed to the excited state absorption (ESA) process. This is because the sample transitions to the excited state after absorbing the pump light, and the particles in the excited state can absorb some light that cannot be absorbed by the original ground state and transition to a higher excited state. So that the detector detects A positive $\varDelta A$ signal. Carrier cooling refers to the cooling of photoexcited charge carriers of a sample to their initial equilibrium state within a few hundred picoseconds after light absorption. Figure 4(b) shows the TA spectra of MnPS3 NSs at different time delays, which suggests the carrier undergoes a rapid cooling and then evolves into a relatively slow cooling process. When the pump light incident on the sample, the electrons placed at the valence band of MnPS3 NSs quickly absorb the photon energy within a short time of about 200 fs and established a nonthermal equilibrium distribution, the sample produces a large number of carriers. Then the carriers and optical phonons interact within tens to hundreds of picoseconds. Finally, there is a long cooling process of the nanosecond order, which can be attributed to optical phonon couplings. The Bose-Einstein distribution of electrons in thermal equilibrium is restored. The long lifetime is significance of the effective separation of electron and hole. For the solar cell absorption layer, the long carrier lifetime and diffusion length are very beneficial to the effective collection of photoelectric current. It can be seen that MnPS3 has potential application value in photovoltaic field.
Fig. 4. (a) Two-dimensional color plot of TA Spectra. (b) TA decay spectrum from 200fs to 2ns. (c) Carrier dynamics of MnPS3 NSs at different probe wavelengths. (d) The relationship between time constants and probe wavelength
After normalization, several dynamic curves of 480, 540, 600, 700 and 760 nm were analyzed for further discussion. As shown in Fig. 4(c), the cooling process is semblable at different wavelengths. For MnPS3 NSs, the multi-exponential functions are used to fit the carrier dynamics:
4. Experimental section
Material preparation: MnPS3 bulk single crystals were prepared through CVT method in a double-temperature-zone furnace. Manganese powder (Mn, 99.99%, Energy Chemical), red phosphorus (RP, 99.999%, Aladdin) and sulphur (S, 99.999%, Alfa Aesar) with the total quality of 1 g were used as precursors with a stoichiometric ratio of 1:1:3. Catalytic amount of iodine (I2, 5 mg/mL) was used as transport agent. All the precursors were evenly mixed in a quartz tube (diameter: 20 mm, length: 120 mm) and placed in a vacuum (less than 1 × 10−4 Pa) and sealed environment. Then, the sealed vacuum quartz tube was placed horizontally in the furnace and programmed to be heated to 700°C in 12 hours, kept at 700°C for 12 days, and then cooled to room temperature. The temperature gradient was set to ∼70 °C. After the end of the growth, yellow green translucent crystals could be obtained at the low temperature end of the quartz tube. MnPS3 NSs were obtained by mechanical exfoliation and then transferred to the SiO2/Si substrate.
Z-scan system: Open aperture Z-scan is a typical and excellent measurement to measure the nonlinear optical coefficient of 2D materials [38]. It also was used in this work, as shown in Fig. 5(a). The system is based on a Ti:Sapphire femtosecond laser with a wavelength of 800 nm (100 fs, 1 kHz) and an optical parametric amplifier (both manufactured by Spectra physics Corporation of America). The splitter divides the laser beam into two. MnPS3 nanosheets were mixed with polyvinylpyrrolidone (PVP) to obtain MnPS3 NSs/PVP films as the sample. A small proportion of the light collected by detector 1 was used as reference light, and the remaining light irradiated the sample. Using a len (f = 500 mm), a parallel beam passing through len1 will form a beam that focuses first and then diverges. As the spot size will first decrease and then increase along the Z-axis, its light intensity will also change along the Z-axis. The sample was placed on an electric translation platform and moved, and the relationship between transmission power and z-axis change was detected. The third-order nonlinear parameters of the sample can be derived from the relationship between transmission power and Z-axis.
Fig. 5. (a) Experiment installing of the Z-scan. (b) Experiment installing of the employed non-degenerate TA spectrometer.
Transient absorption system: The photocarrier cooling behavior of MnPS3 NSs was studied by non-degenerate transient absorption (TA) spectroscopy. Figure 5(b) shows a schematic diagram of TA system. The system is still based on the Ti:Sapphire femtosecond laser with wavelength of 800 nm. The pump wavelength is selected according to the material bandwidth and excitation mode, and is generated by the 800 nm laser through the optical parametric amplifier. The probe light is continuous spectrum, which is generated by the 800 nm laser incident into different nonlinear crystals. An 800 nm laser incident into a CaF2 crystal produces a continuous spectrum of 330-720 nm; the 800 nm laser incident into the sapphire crystal produces a continuous spectrum of 420-780 nm.
5. Conclusion
In conclusion, we synthesized MnPS3 NSs via CVT method and studied its third-order nonlinear optical properties and hot carriers cooling dynamics. Using Z-scan measurement, the SA phenomenon of MnPS3 NSs was observed at 475nm, and RSA phenomenon was observed at 800 and 1550nm. The $\beta $, $\varDelta T$, ${I_s}$ and ${T_{ns}}$ at different wavelengths were obtained by nonlinear fitting. Compared with other common two-dimensional materials, it has moderate saturation strength and excellent modulation depth. This work suggests that MnPS3 NSs are expected to be used in ultrafast laser as a saturable absorber, and it can be a potential candidate for application in the broadband optical limiting system. We studied the carrier dynamics in MnPS3 NSs by femtosecond transient absorption spectroscopy technology. It is found that MnPS3 NSs has a slow hot carrier cooling process, and the carrier lifetime can be regulated by changing the wavelength. The slow carrier cooling process facilitates the transfer and extraction of hot carriers, which shows good application prospect of hot carrier battery. Our work demonstrates the potential of MnPS3 in ultrafast lasers, optical limiting and photovoltaic devices, and has implications for MPX3 materials in the optical field.
Funding
Natural Science Foundation of Shandong Province (ZR2021LLZ008); National Natural Science Foundation of China (11974220).
Acknowledgments
We thank the support from the Vacuum Interconnected Nanotech Workstation of Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences.
Disclosures
The authors declare no conflicts of interest.
Data availability
Data underlying the results presented in this paper are not publicly available at this time but may be obtained from the authors upon reasonable request.
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