Photonics and optoelectronics using nano-structured hybrid perovskite media and their optical cavities
Introduction
Metal-halide perovskite semiconductors generally have a crystal structure in the form of ABX3 with A designating a monovalent inorganic or organic cation [e.g., cesium, Cs; methylammonium (MA), CH3NH; or formamidinium (FA), CH(NH2)], B as a bivalent metal cation (e.g., Pb, Sn or Ge) and X as a halide anion (e.g., I, Br or Cl) [1], [2]. The cations have very different sizes and fit into different coordination sites of the crystal lattice. In addition to their possessing a high absorption coefficient (5 104 cm−1) [3], an optical band-gap that is tunable across the entire visible spectrum to near infrared region, is easily realized in metal-halide perovskite crystals by compositional substitution via solution, vapor and solution-vapor hybrid processing [4], [5], [6], [7], [8]. The halide perovskites also exhibit unique electronic properties [9], [10], [11] such as electron–hole diffusion lengths longer than in CH3NH3PbI3 bulk single-crystals [12], but longer than in perovskite polycrystalline films [13], and strong charge depletion characteristics with a depletion width over in CH3NH3PbI3 nanosheet-based p-n junctions [14].
Perovskite compounds have been studied for decades, but awareness of their unusual properties rapidly spread with the recent discovery of high-efficiency solar cells achieving validated efficiencies exceeding 23% with potential for more than 30% [15]. Due to their outstanding optical and electronic properties, in association with ease of thin film preparation, research and development in halide perovskite-based photonics and optoelectronics related applications have evolved quickly in the past decade, achieving continually various exciting landmarks each year. The increased interest in perovskite properties and applications is revealed by the timeline of publication records (Fig. 1). The number of publications per year has increased drastically since 2009, with the sharpest increase being after 2013 following the report of high solar cell efficiency.
In the solar field, significant research efforts reported high-performance photovoltaic cells with power conversion efficiency increasing from 3.8% in 2009 to 23.3% reported very recently [16], [17]; this rapid progress in high-efficiency solar cells is unprecedented. In fact, the efficiency has already exceeded that of multi-crystalline silicon solar cells (22.3%) [17], clearly demonstrating the tremendous potential for optoelectronic applications of the perovskite family.
While energy harvesting is a notable field of research, considerable attention is drawn toward much broader and more significant photonic and optoelectronic applications. For instance, light-emitting devices (LEDs) employing metal-halide perovskite emitters have demonstrated excellent performance with photoresponsivity beyond 62 cd A−1 and external quantum efficiency of 14% [18]; these performance values are already comparable to the state-of-the-art organic LEDs. Similarly, ultrasensitive photodetectors with responsivity over 104 AW−1 and detectivity higher than 1015 Jones have been achieved by using single-crystalline layered metal-halide perovskites, far exceeding the performance of commercial Si-based photodiodes [19].
In addition to the above-mentioned exciting progress in materials engineering and device fabrication, metal-halide perovskites can achieve additional improvements by hybridizing devices incorporating several areas of nanophotonics, namely plasmonics and nanoscale cavity structures [20], [21], [22]. There is a myriad of established design tools that researchers bring to bear in resolving technical issues and for performance improvements. There are unprecedented possibilities in photonics and optoelectronics by joining the perovskite’s optoelectronic characteristics with advanced optical cavities, to accelerate the development of more efficient devices.
Particularly, low-dimensional halide perovskites including zero-dimensional (0D), one-dimensional (1D) and two-dimensional (2D) crystals are rapidly emerging as new types of nanoscale photonic and optoelectronic components [23], [24], [25], [26]. A photonic cavity generally utilizes multiple reflection, absorption or diffraction of light in a confined space and can provide useful enhanced light–matter interactions. Nanostructured hybrid perovskite crystals including nanowires and nanoplatelets have been demonstrated recently with an active wave-guiding performance for optical modulators [27], [28], as well as with low lasing thresholds and high-quality factors [29], [30], [31]. Nanopatterning perovskite films into periodic arrays increase the light coupling efficiency in the device; for instance, periodic patterns and perovskite metasurfaces assist in enhancing light absorption in solar cells and light extraction for LEDs [32], [33]. Coupled with external optical cavities including distributed Bragg reflector (DBR) and photonic crystal, halide perovskites also show improved light emission performance (e.g., polariton condensation and lasing in a CsPbCl3-DBR cavity) [34], [35], [36].
Plasmonic coupled metal-halide perovskite systems possess great potential in enhancing the optical response of perovskites. Plasmonic effects are classified into two categories: localized surface plasmon resonance (LSPR) and propagating (or delocalized) surface plasmon polariton (SPP) [20]. Extensive efforts are made to exploit the coupling effect between conventional semiconductors and plasmonic structures, and understand the coupling mechanisms that can enable researchers to develop high-efficiency plasmonic-enhanced optoelectronic devices [37], [38], [39], [40]. Similarly, plasmonic nanostructures can be incorporated into metal-halide perovskite-based devices in order to evoke plasmonic enhancement of specific optical phenomena [41], [42], [43]. For instance, preliminary studies that combine perovskites with plasmonic metal nanoparticles (e.g., Au, Ag) have demonstrated a 28% improvement in solar cell power conversion efficiency [44] and 40% improvement in external quantum efficiency of LEDs [45]. Periodic arrays of metallic nanostructures can also be used to modulate the responsive optical spectra and boost the photon/electron conversion efficiency in perovskite optoelectronic devices [46], [47], [48]. For example, the external quantum efficiency of a perovskite photodetector functionalized by arrays of Au nanostructures exhibits 2.5 times enhancement due to the huge localized electric field induced by the surface plasmon resonance [46].
A conceptual roadmap of the substance of this review is illustrated in Fig. 2. On the top level, broad bandwidth optical radiation can be absorbed to produce a current response or photon emission can be elicited from electron/hole recombination to create efficient light emission devices. On the lower tier, plasmonic structures or photonic (crystal) cavities can boost electron/photon interactions for useful devices. Here we focus on the physics of optical excitation dynamics, band gap engineering and charge carrier dynamics in metal-halide perovskites. The role of plasmonic coupling and photonic cavities in enhancing light–matter interactions and manipulating carrier dynamics is presented by examples of studies of perovskites hybrid plasmonic and perovskites nanostructure cavities. We further discuss how photonic communication between perovskite and optical gain structures contributes to new designs for novel photonic devices.
In this review, we make an attempt to capture the recent advances in nanostructured metal-halide perovskite media and their optical cavities, discuss the fundamental physical and photonic mechanisms and summarize the potential device applications in photonics and optoelectronics. Future research scopes in this field are also presented. It is therefore anticipated that this review will strengthen the understanding of halide perovskite-based optical cavities and stimulate research and development of high-performance photonic and optoelectronic devices.
Section snippets
Optical properties of metal-halide perovskites materials
A metal-halide perovskite crystal can be viewed as an anion corner-shared 3D network of (BX6) octahedra, with B cations at their centers and A cations between them. Generally, the designated A cation is supposed to have no direct contribution to the electronic properties of perovskites, and the band structures of perovskites are mainly correlated with the largest metal-halide-metal bond angle, which according to theoretical investigations can be adjusted by the BX6 octahedral tilting [49].
Optical properties of metal-halide perovskites cavities and their hybrid platforms
Optical cavities confine light within a small volume by resonant recycling. Metal-halide perovskite devices based on cavities have become indispensable for various applications and explorations. In metal-halide perovskite devices, cavities produce perovskite materials emitting spontaneous emission in a desired direction, or they can provide an environment where dissipative mechanisms, such as spontaneous emission, are overcome such that quantum entanglement between radiation and matter becomes
Metal-halide perovskites with coupled plasmonic cavities
This section describes the effects which can manifest to impact on the device performance of an optical medium comprised of perovskites coupled to a metallic nanostructure plasmonic cavity. For the sake of clarity, we first introduce basic concepts on optical excitations in metals and their nanostructures as well as on interactions, energy transfer and charge transfer processes in semiconductors couple with a plasmonic cavity. Much of this area is still relatively unexplored in relation to
Low dimensional metal-halide perovskites with -conjugated organic cation
In the primary form of 3D metal-halide perovskites, ABX3, the radius of the organic cation (A) is restricted by its steric constraints between cubic lattices of BX6 octahedra. Thus, the function of cation A is also limited to only a structural role. However, when bulkier organic cations participate in the perovskite composition, the 3D structure of perovskites is divided into lower dimensional structures providing the potential for the photonic/optoelectronic communication between a
Applications of perovskite photonic structures
Light and electron transitions are coupled via nanostructures that can enhance the desired optical emission or absorption properties. Strategies to improve photonic or optoelectronic device performance by resonance nanostructures (cavities, nanoparticles, and photonic crystals) have been amply discussed in prior sections. Recently metasurface structures are added to the research literature [195], [196], [197], [198]. A metasurface is a subwavelength thick nanostructured interface with the
Conclusions
In the past few years, there has been tremendous progress in understanding the chemistry of metal-halide perovskites and their applications mainly in thin-film solar cells. The significance of photonics and optoelectronics in low-dimensional perovskites has already been recognized for nanophotonics applications. However, the nanostructured perovskite materials integrated with optical cavities still remain to be an intriguing yet less-investigated topic.
In this review,we have comprehensively
Acknowledgments
This study was supported by the Science and Technology Development Fund, China (Nos. 007/2017/A1 and 132/2017/A3), Macao SAR, China, the National Natural Science Foundation of China (NSFC) (61435010, 51702219, 61875138, 51601131), and the Science and Technology Innovation Commission of Shenzhen, China (JCYJ20170818093453105,JCYJ20180206121837007). Financial support at Buffalo by the Air Force Office of Scientific Research, USA, Grant #FA9550-18-1-0042, is also acknowledged. Valuable technical
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