
- Chinese Optics Letters
- Vol. 20, Issue 3, 032701 (2022)
Abstract
Keywords
1. Introduction
Over the past decades, the field of non-classical light sources has expanded exponentially, tightly related to the fields of quantum photonics, super-resolution imaging technology, and quantum information science, which specifically includes quantum key distribution, quantum computation, quantum communication, and precision sensing. In the experimental foundation of quantum mechanics[
Although there is still no ideal quantum emitter satisfying industrial production, quite a few quantum emitters in solid-state systems have been transformed from theoretical prediction to engineering design and optimized performance, such as color centers in crystals, quantum dots, carbon nanotubes, 2D materials, and other solid-state host materials[
Since the first observation of the quantum emission from hexagonal boron nitride (hBN) monolayers at room temperature[
In this review, research on the generation, properties, control, and applications of the quantum emitters in hBN is reviewed. Recent progress towards mechanism research of quantum emission in hBN is introduced. Multi-angle fabrication and coordination of SPEs in hBN are discussed. Next, the progress towards related applications is enumerated, respectively, such as integrating SPEs in hBN with photonic or plasmonic nanostructures, dielectric optical cavities, and waveguides. Lastly, the opportunities and challenges for SPEs in hBN are summarized, and new possibilities that are being explored at present and may be explored in the future are discussed.
2. Mechanism of Quantum Emission in hBN
The ideal SPE, as an isolated quantum system, that emits one photon at a time per excitation cycle needs to be satisfied, which is triggered optically or electrically[
Figure 1.Measurement of quantum emission and structures of hBN. (a) Simple energy level diagram for quantum emission. When a quantum system is excited by light or electricity, the energy conversion between the excited state and the ground state can produce a single photon. (b), (c) The top-down and side views illustrating the in-plane honeycomb structure of hBN as well as the interlayer distance and stacking mode. B atoms and nitrogen atoms are represented in green and gray spheres. Within the (0001) plane, each N atom is threefold coordinated to B and vice versa in a honeycomb pattern that is a result of sp2 bonding. Out of the plane, hBN exhibits AA’-type stacking with alternating B and N atoms along with the [0001] direction. The interlayer separation is determined by the van der Waals interaction[
In order to design high-quality quantum emitters in hBN, it is necessary to have a clear understanding of the atomic structure in hBN and the associated excitation processes that give rise to the quantum emission. hBN is a highly anisotropic crystal, consisting of B and N atoms strongly bonded in the in-plane direction. The B–N bond is polar covalent because of the difference in electronegativity between B and N[
2.1. 2 eV luminescence
When quantum emission at 623 nm from localized defects in hBN monolayers and multilayers at room temperature was first discovered, it showed extremely high brightness (
Density function theory (DFT) was used to investigate the origin of the defect responsible for the observed single-photon emission, by analyzing energy levels and the optical responses of the defects. In the beginning, the related study put forward that the
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Figure 2.Optical characterization of SPEs in hBN. (a) PL spectrum from hBN on different substrates. Each sample used CW excitation light at 532 nm. Although substrates may change the peaks of the PL spectrum, significant quantum emission can be observed[
Some studies have shown that strain can induce modification of the optical characteristics of SPEs in hBN[
2.2. 4.1 eV luminescence
Using a custom-built CL + HBT system, a new extremely bright UV SPE (4.1 eV) in hBN[
To sum up, even though research into hBN SPEs has been expanding rapidly in the last decade, the defects causing these SPEs and the sources of the defects are still under debate. In particular, some new technologies, such as nanobeam electron diffraction[
3. Fabrication and Regulation of Quantum Emitters in hBN
As discussed before, hBN is considered a promising candidate for hosting bright, linearly polarized, and optically stable quantum emitters operating at room temperature and under harsh chemical conditions with high photon purity. However, the emission wavelength of fluorescence defects in hBN is uncontrolled yet, with ZPL energies widely distributed over a wide spectral range (hundreds of nanometers), hindering the potential development of related devices and applications. Besides, as they are located in atomically thin 2D materials, these SPEs have the unique potential to be solidly coupled to electronic and optoelectronic devices. To reliably integrate these SPEs into the hybrid devices, there is an urgent need for nanomanufacturing methods that control the generation and location of SPEs in hBN. In this section, different approaches to the fabrication and regulation of SPEs in hBN are introduced. On the one hand, growth techniques of hBN, such as CVD, are optimized, and a series of processing methods are employed, such as electron beam irradiation, annealing treatment, plasma etching, chemical etching, ion irradiation, proper surface passivation, laser processing, and UV ozone processing. On the other hand, external fields can be introduced for engineering SPEs in hBN, such as stress field, electrostatic field, and magnetic field.
3.1. Fabrication and optimization of SPEs in hBN
3.1.1. Chemical vapor deposition growth method
In a recent investigation of CVD, a bottom-up fabrication of hBN using low-pressure CVD (LPCVD) is proposed[
Figure 3.Schematics of optimized CVD growth methods. (a) Schematics of low-pressure CVD setup and hBN film on Cu[
Based on that, a further study puts forward an effective method to produce quantum emitters in hBN with the desired emission properties in different spectral regions by B diffusion through Cu via B during atmospheric pressure CVD (APCVD)[
Besides, a recent investigation demonstrated that the CVD process based on Pt catalyst can realize the controlled growth of large monolayer hBN and can also peel off the grown films directly from the catalyst to realize the cleaning process[
Another recent study demonstrates a positive approach to spatially control generation of hBN SPEs and provides an effective way to create large-scale SPE arrays[
3.1.2. Electron beam irradiation
The use of electron beam irradiation to fabricate and locate SPEs is attractive because this process does not require annealing and irradiation of 15 keV electrons in
Figure 4.Engineering of quantum emitters in hBN. (a) Confocal map of the irradiated zone on a high-purity hBN flake of about 15 µm × 20 µm and 60 nm thickness, with eight irradiation spots (orange dashed lines)[
3.1.3. Ion irradiation and neutron irradiation
Ion implantation was explored using B, B nitrogen (BN) complexes, silicon (Si), and O ions. B and BN were chosen to determine whether the probability of forming native defects would increase because these atoms mainly produce vacancies and interstitials. Si and O were selected to test whether the emission source is related to common foreign impurities such as O. Figure 4(b) shows the PL spectra of hBN flakes implanted with B, BN, O, and Si ions, respectively[
3.1.4. Plasma etching
The reported manufacturing techniques prove that O plasma etching can form color centers in the peeling multilayer hBN. To maximize the yield per flake of the SPEs and optimize the spectrum characteristics, plasma power and plasma time were changed. Figure 4(c) shows the functional relationship between the linear density per unit edge length and plasma power[
3.1.5. Chemical etching
Two methods of chemical etching are introduced here[
3.1.6. Proper surface passivation
A recent work explored a novel method based on atomic layer deposition (ALD) of a 2 nm thin
3.1.7. Focused ion beam
As mentioned above, SPEs tend to occur randomly at edges[
3.1.8. Ultraviolet ozone processing
The low-temperature ozone treatment also can be used to generate high-quality SPEs in hBN effectively. Ozone processing is an applicable low-temperature choice when some on-chip devices are not manufactured in a manner compatible with high-temperature annealing[
3.2. Introduced external fields to regulate the quantum emission of hBN
3.2.1. Strain engineering
Strain engineering is used to regulate the physical properties of materials by controlling the elastic strain fields applied to them[
Because of the strong in-plane atomic bonds in 2D materials, external strains can be applied to change the electronic energy levels of fluorescent defect states. For instance, the biaxial strain affects the electronic properties of carbon defects in hBN monolayers. When either B or nitrogen is replaced with a carbon atom, donor and acceptor states, respectively, are induced. By applying tensile strain and compression strain, the ionization energy of the donor and acceptor states can be controlled[
Bending of a flexible substrate is a common technique to induce strain. After post-growth processing (irradiation and annealing), hBN films are transferred onto a 1.5-mm-thick polycarbonate beam to control strain[
Figure 5.Strain engineering of SPEs in hBN. (a) Experimental scheme used to apply strain to hBN flakes sitting onto a bendable polycarbonate (PC) beam clamped at one edge. When the vertical force is applied to the free side, the color shows the simulated strain strength along the length (top panel) and width (bottom panel) of the beam. When tensile strain is generated in the length direction (x axis), the compressive strain is generated in the beam width direction (y axis) due to the PC Poisson’s ratio of 0.37[
Lately, new advances have been made in applying tensile strain to SPEs embedded in several layers of hBN films and achieving both red and blue spectral shifts with tuning amplitudes up to 65 meV[
In addition to tuning the ZPL spectrum of hBN, strain engineering can also be used to determinatively activate SPEs in the hBN[
It has been reported that the density of SPEs in hBN is related to the perimeter, so quasi-one-dimensional B-nitride nanotubes (BNNTs) with rich curvature have received much attention[
3.2.2. Acoustical modulation
Lately, the effect of surface acoustic waves (SAWs) on light emission from the defect center in the hBN was investigated[
3.2.3. Electrical control
The Stark effect, which describes the regulation of the emitted photon energy via shifting the electron energy level by an external electric field, is easily integrated into a quantum system, which has advantages over other tuning methods such as strain field. However, since most emission sources, such as quantum dots, atomic emitters such as
As mentioned above, due to high internal quantum efficiency, the hBN SPEs can work at room temperature with high brightness and light stability. Besides, the layered structure of the hBN may result in an in-plane dipole moment, which enables the applied in-plane electric field to be well aligned with the dipole direction. Based on that, a nanoscale four-electrode device is designed, which can not only control the direction of the electric field but also achieve an unprecedented in-plane field on the order of 0.1 V/nm, orders of magnitude higher than previous reports using a similar in-plane electrode design[
Figure 6.Electrical control of SPEs in hBN. (a) Device of the Stark effect in hBN SPE at room temperature. A, B, C, and D (yellow) denote the four Au electrodes where voltages are applied to generate external electric fields[
Besides, a method of effectively introducing electrostatic field and realizing large and reversible Stark-shift tuning of SPEs in hBN is introduced[
3.2.4. Temperature dependence
Figures 7(a)–7(d) show the temperature dependence of the spectral ZPLs caused by point defects in multilayer hBN. Although the ZPL transition energies differ by about 340 meV, they all redshift in a similar manner with temperature increase. The measured linewidth increases exponentially, and the relative strength of each ZPL decreases exponentially with temperature. A lattice vibration model that considers piezoelectric coupling to in-plane phonons can well explain these phenomena[
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Figure 7.Temperature dependence of SPEs in hBN. (a)–(d) Temperature-dependent energy shift, line width, lifetime, and relative intensity for two ZPLs centered at 575 nm (green triangles) and 682 nm (red circles). Each ZPL shows nearly identical behavior, though the ZPL at 682 nm decreases in intensity more rapidly as temperature is increased[
Based on the sensitive temperature correlation in hBN, a deterministic optical temperature measurement technique based on SPEs in hBN is proposed in the subsequent research[
3.2.5. Magnetic field dependence
The magneto-optical effect is the main method to solve single spin and coupling to light. Electron paramagnetic resonance is known for bulk hBN[
Figure 8.Magnetic-field control of SPEs in hBN. (a) Illustration of the coordinate system for magnetic fields concerning the microscope objective and sample. β, in the x
3.2.6. Photoinduced modification
Two recent studies on optical tuning hBN quantum emission are presented. The work of optical doping by using ionic liquid devices is first introduced[
Figure 9.Photoinduced modification of SPEs in hBN. (a) Schematic of the electrical PEO:LiClO4 device used to modulate the single-photon emission[
4. Integration and Application Based on hBN
4.1. Photonic and plasmonic nanostructures
In the pioneering work of a hybrid quantum 2D material system integrated with plasmonic nanocavity arrays, the quantum emitters in the hBN were determinatively coupled to plasmonic Au and Ag arrays with high quality, and the coupled emitters showed better performance[
Figure 10.Optical coupling systems between SPEs and plasmonic nanostructures. (a) PL confocal map and PL spectra of a flake containing SPEs (red circled). Inset, SEM image of part of the flake on top of the Au plasmonic lattice[
4.2. Dielectric optical cavities and waveguides
In this section, the progress made in integrating the hBN SPEs with dielectric optical cavities and waveguides is briefly introduced. As shown in Fig. 11(a), an array of whispering gallery mode resonators in the form of Si nitride (
Figure 11.Optical coupling systems based on SPEs in hBN. (a) Confocal fluorescence image of an array of hBN/Si3N4, 3.5-µm-diameter microdisk cavities upon 510 nm laser excitation[
In addition to the short waveguides on the nano- and micro-scale mentioned above, the research on the integration of hBN emitters with optical fibers has made great progress in recent years, which is more important for remote applications such as quantum communication. The light emitted by an SPE into the optical fiber can be collected effectively, and it is proved that when the light is guided through the optical fiber, the quantum properties of light remain unchanged[
Recent progress of SPEs in an hBN monolayer provides a platform for optomechanical experiments in which SPEs can be coupled to the motion of a free-floating hBN membrane[
In addition to 2D material systems, there have been several studies looking at lower dimensional systems. For example, bright visible light SPEs have been found in a zero-dimensional B nitride allotrope (the B nitride nanococoon, BNNC)[
4.3. Future applications based on hBN
Besides the sensing experiments mentioned in Section 3.2 above, there is also some attractive work related to real quantum experiments[
Some of the fundamental principles of quantum theory, such as Born’s rule, are based on postulates that need to be tested experimentally. Any deviation from these postulates will show up in the results observed in experiments[
5. Conclusion
In this review, we focus on the progress of SPEs in hBN materials. The measurement method of quantum emission and the possible defects related to quantum emission in hBN are introduced. The origin of hBN quantum emission is still under debate. In actual scenarios, the heterogeneity of the hBN structure leads to the diversity of hBN defects, which makes it more difficult to explore the emission mechanism of hBN. As the basic unit of quantum information science, the regulation of hBN SPEs is a thriving field. From the two directions of various physical and chemical fabrication methods and introduction to the external field, the deterministic fabrication and effective engineering of hBN SPEs at the present stage are introduced in detail. In the future, more attention should be paid to how to adapt SPEs in hBN to large-scale or industrial applications with more accessible processes. On the technological side, methods need to be worked out that allow each irradiation point to be determined to obtain a single SPE[
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