† Corresponding author. E-mail:
Project supported by the National Key Research and Development Program of China (Grant Nos. 2017YFA0303302 and 2018YFA0305601) and the National Natural Science Foundation of China (Grant Nos. 61322407, 11474058, 61674040, and 11874116).
Cd3As2, as a three-dimensional (3D) topological Dirac semimetal, has attracted wide attention due to its unique physical properties originating from the 3D massless Dirac fermions. While many efforts have been devoted to the exploration of novel physical phenomena such as chiral anomaly and phase transitions by using bulk crystals, the development of high-quality and large-scale thin films becomes necessary for practical electronic and optical applications. Here, we report our recent progress in developing single-crystalline thin films with improved quality and their optical devices including Cd3As2-based heterojunctions and ultrafast optical switches. We find that a post-annealing process can significantly enhance the crystallinity of Cd3As2 in both intrinsic and Zn-doped thin films. With excellent characteristics of high mobility and linear band dispersion, Cd3As2 exhibits a good optical response in the visible-to-mid-infrared range due to an advantageous optical absorption, which is reminiscent of 3D graphene. It also behaves as an excellent saturable absorber in the mid-infrared regime. Through the delicate doping process in this material system, it may further open up the long-sought parameter space crucial for the development of compact and high-performance mid-infrared ultrafast sources.
In remembrance of the renowned Chinese physicist Professor Kun Huang, who made significant contributions to the development of solid-state physics, we start with a brief introduction of his pioneering achievement. Huangʼs research was mainly involved with many aspects of phonon physics in solids. He is widely known for his collaboration with Max Born in writing the classic monograph—Dynamical Theory of Crystal Lattices. His contributions include the concept of polaritons, Huang scattering of x-ray, the Huang–Rys factor used for describing electron–phonon interaction, and the Huang–Zhu model used for calculating electron–longitudinal phonon interaction in quantum wells and superlattices.[1–8] In recent years, Huangʼs research has been widely used to study various physical problems related to low-dimensional semiconductor materials and phonons, including transport phenomena, Raman scattering, phonon polaritons, and many other frontier problems.[9–11]
While the theoretical development of phonon dynamics has tremendously benefited the academia and semiconductor industries, the novel concept of topological matters was proposed and specific material systems were discovered in recent years. One representative example of topological systems is the topological insulator (TI), which features bulk states that have an energy bandgap and gapless surface states, allowing surface carriers to have zero effective mass.[12,13] Another intriguing example is topological Dirac semimetals (TDSs). They are a new kind of Dirac material that exhibits linear energy dispersion in the bulk and can be viewed as 3D graphene. It has been proposed that TDSs can be driven to other exotic phases like Weyl semimetals and topological insulators by breaking certain symmetries. One of the most exotic physical properties of these new materials is the chirality of electrons, where the spins of electrons are in parallel or antiparallel to the direction of their motion and thus develop the right-handed or left-handed chiral electrons (widely conceived as chiral anomaly). Theories also predict that topological Dirac semimetals can be driven into a quantum spin Hall insulator with a sizeable bandgap by reducing dimensionality. Driven by these exotic physical properties, extensive experiments on angle-resolved photoemission spectroscopy,[14–17] and scanning tunneling microscopy[18] were carried out to identify the 3D Dirac fermions in these materials.
The intriguing physics of these TDSs has motivated a surge of research activities towards the development of large-scale single-crystalline films for potential applications in electronics and optics. The Cd3As2 is considered to be an excellent 3D TDS due to its chemical stability in air, and it also possesses novel transport phenomena such as ultrahigh mobility,[19] large magnetoresistance (MR),[20] nontrivial π Berryʼs phase of Dirac fermions,[21] and chiral anomaly induced negative MR.[22,23] Previously, Cd3As2 bulk materials, amorphous films,[24] nanowires,[25] and platelets[26] were prepared by various growth methods, and most of magneto-transport measurements so far have focused on Cd3As2 bulk materials. However, few efforts were devoted to thin films[27–29] and nanostructures,[25,30] which may exhibit surface phase-coherent transport and quantum size limit effect,[31–33] leading to Aharonov–Bohm oscillations[34] and quantum Hall insulator states.[35] Importantly, a theoretically-predicted TI phase and thickness-dependent quantum oscillations may also eventually emerge when the dimensionality of the system is reduced.[35,36] Therefore, it is highly desirable to fabricate superb crystallinity Cd3As2 thin films for the transport study, and to develop the possible optoelectronic applications by using the Cd3As2 thin film system. Here we present a brief review of our recent progress in making such ultra-high mobility Cd3As2 thin films via the post-annealing process and in making heterojunction photodetectors and ultrafast optical switches.[37–40]
A series of wafer-scale Cd3As2 thin films were grown via a molecular beam ppitaxy (MBE) system at a base pressure lower than 2 ×10−10 mbar (1 bar = 105 Pa). Single-polished sapphire and clean cleaved mica substrates were selected for electrical transport measurements. Before growing the Cd3As2 layer, the substrates were degassed at 400 °C for 30 min to remove gas molecules absorbed on the surface. Especially, a buffer layer of CdTe was deposited on the substrates in order to achieve a better crystalline match. The Cd3As2 thin film deposition was carried out on the top of the buffer layer with high-purity Cd3As2 (99.999%) from dual-filament and valve-cracker effusion cells. The growth process and film thickness awere in situ monitored by the reflection high-energy electron diffraction (RHEED).
As displayed in Fig.
In order to further enhance the crystalline quality, the as-grown films were annealed at elevated temperatures after depositing a 120-nm-thick Al2O3 capping layer on the top. It can protect the underlying thin films from being oxidized in the annealing process. Figure
The post-annealing process brings about a significant enhancement of quantum oscillations. Figure
The small upturn in the R–T curves at low temperatures could have two origins. One is electron–electron interaction, and the other is weak localization. Both of the two mechanisms will lead to a very similar upturn feature in the R–T curve, i.e., the R–T curve will be linear in the logarithmic scale at low temperatures. We examine the linear behaviors of several samples and suggest that the contribution from localization is the main contribution to the metallic-insulating transition. We then study the MRs of these samples at 2 K. As shown in Figs.
Further, Zn is doped into Cd3As2 to reduce the Fermi level. The size of Fermi surface can be extracted from the SdH oscillations. With the Zn concentration increasing, the oscillation frequency (SF) decreases and the Fermi level decreases as summarized in Table
In short, the rapid annealing process can enhance the crystal quality by reducing defects via developing a recrystallization process. After annealing, the mobility of thin films rises, while the SdH oscillations become strikingly stronger.
Based on the high-quality Cd3As2 thin films, a Cd3As2/pentacene heterojunction photodetector is fabricated as shown in Fig.
For heterojunction-based photodetectors, the I–V curve shows a rectification characterisitics of the photodetector with or without illumination, and we select the appropriate bias voltage (Vbias) which is exhibited in Fig.
As shown in Fig.
Compared with the pure Cd3As2 photodetector, the Cd3As2/pentacene photodetectors achieve an obvious improvement of Ri. The pentacene layer plays important roles in both the visible band and the infrared band. It has a good absorption in the visible spectrum, which means that it can absorb the light and then produce charges when the light is incident in the junction area of pentacene and Cd3As2. Thus, the Ri of the Cd3As2/pentacene heterostructure detector is much higher than that of the pure Cd3As2 thin film detector in the visible band. Since pentacene has proved to have a single peak exciton fission effect at about 660 nm, more conductive charges are generated when the light irradiates, which causes Ri to reach a maximum value at 650 nm. As a result, the Ri value of the Cd3As2/pentacene detector is also higher than that of the pure Cd3As2 thin film detector in the infrared band.
Since the early 1990 s, semiconductor saturable absorber mirrors (SESAMs) have been an important approach in the near-infrared field. Flexibility and preciseness make SESAMs one of the most important saturating absorber technologies, and it can be adapted into various laser formats, such as fibre, solid-state or semiconductor chip lasers.[43–45] By detecting the mid-infrared optical response of the bulk Dirac fermions, it is found that MBE-grown Cd3As2 thin films can act as an excellent ultra-fast (
We carry out pump-probe measurements on the intrinsic and Cr-doped Cd3As2 thin films. The non-degenerate transient transmission spectroscopy reveals photo-bleaching characteristics caused by Pauli blockage, according to which we show that Cd3As2 has a saturated absorption characteristics over the entire spectral range (Fig.
To illustrate the benefits of expanding the parameter space through a delicate Cr doping, we demonstrate on-demand access to different pulse states for domestic 3-
As the pump power further increases, the duration and period of the Q-switched envelope both shorten as expected. As displayed in Fig.
Cd3As2, as a topological Dirac semimetal in three-dimensionality, has shown a quantum Hall effect (QHE) in both nanostructures and thin films.[49–51] Particularly, our group has reported the 3D Weyl-orbit-based QHE in Cd3As2 nanoplates.[52] Hence, with the mobility increasing, it is hopeful to achieve high-quality thin films in the quantum Hall regime. In this regard, the Zn doping can validly reduce the Fermi level, which makes the films easier to reach the quantum limit. Therefore, the electron–electron interactions can be significantly enhanced as demonstrated by several recent experiments on the phase transitions of several topological semimetals.[53,54] Thus, it is quite exciting to continue improving the crystalline quantity of Cd3As2 films as well as the effective Zn doping, to envisage the exotic 3D quantum behavior in topological semimetal systems.
While the fundamental research on new topological physics and the various emergent phenomena continue to be conducted, we attempt the potential utilization of topological properties in practice. The Cd3As2 has proved to have an extraordinary optical response. Since the Cd3As2/pentacene heterojunction device can raise the responsivity and external quantum efficiency in a broad range from visible light to far-infrared light, it is feasible to use the heterostructures of Cd3As2 and organic molecules to construct the photodetectors. Along this route, we expect to realize the devices with higher responsivity and external quantum efficiency with different organic molecules, and make the responsive range much broader (towards THz).[55] Considering the excellent broadband responsiveness of these Cd3As2/organic thin film photodetectors, our work provides a new approach to applying the 3D TDSs to optoelectronic devices.
Furthermore, the attempt of using Cd3As2 as a saturable absorber in the field of pulsed lasers seems to be quite successful. The key characteristics including comprehensive scalability, broadband operation, and flexible parameter control effectively establish Cd3As2 as a highly adaptable near-infrared SESAM.[56–58] In development, we anticipate the proposed electrically contacted saturable absorber device. It can be further extended to active photonic devices operating in the near- to far-infrared range, including optical modulators and tunable light-emitting devices.
In short, our research on high-quality Cd3As2 thin films paves the way for applying the 3D TDSs to photodetectors and presents a feasible approach to preparing the large-scale array photodetectors. Meanwhile, our work represents a step forward in the development of compact mid-infrared ultrafast sources for advanced sensing, communication, spectroscopy, and medical diagnostics using topological Dirac semimetal materials.
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