Nanotechnology for colorectal cancer detection and treatment

Colorectal cancer (CRC) is the third most diagnosed cancer and the second leading cause of cancer-related mortality in the United States. Across the globe, people in the age group older than 50 are at a higher risk of CRC. Genetic and environmental risk factors play a significant role in the development of CRC. If detected early, CRC is preventable and treatable. Currently, available screening methods and therapies for CRC treatment reduce the incidence rate among the population, but the micrometastasis of cancer may lead to recurrence. Therefore, the challenge is to develop an alternative therapy to overcome this complication. Nanotechnology plays a vital role in cancer treatment and offers targeted chemotherapies directly and selectively to cancer cells, with enhanced therapeutic efficacy. Additionally, nanotechnology elevates the chances of patient survival in comparison to traditional chemotherapies. The potential of nanoparticles includes that they may be used simultaneously for diagnosis and treatment. These exciting properties of nanoparticles have enticed researchers worldwide to unveil their use in early CRC detection and as effective treatment. This review discusses contemporary methods of CRC screening and therapies for CRC treatment, while the primary focus is on the theranostic approach of nanotechnology in CRC treatment and its prospects. In addition, this review aims to provide knowledge on the advancement of nanotechnology in CRC and as a starting point for researchers to think about new therapeutic approaches using nanotechnology.     

经聚乙烯亚胺钝化的荧光碳点负载阿霉素抑制非小细胞肺癌细胞增殖、迁移侵袭的治疗研究

目的研究利用经聚乙烯亚胺（PEI）钝化的荧光碳点（CD）装载阿霉素（DOX）进行药物递送，旨在增加DOX对非小细胞肺癌的治疗作用，减少DOX的心肌毒性。 方法通过一步微波加热法将甘油和PEI的混合物制备成CD-PEI，并通过静电效应将DOX装载至CD-PEI。采用CCK8实验检测CD-PEI-DOX对非小细胞肺癌细胞A549的增殖能力的影响；Transwell实验评估CD-PEI-DOX对A549细胞迁移侵袭能力的影响；最后通过体内动物实验评估CD-PEI-DOX的心肌毒性以及对非小细胞肺癌皮下肿瘤生长的抑制效果。 结果体外细胞实验证实，对比单纯的DOX处理组，CD-PEI-DOX对非小细胞肺癌A549细胞增殖、迁移侵袭能力的抑制作用更为显著。体内实验证实，CD-PEI-DOX纳米复合物治疗组小鼠心肌细胞结构完整，并且能有效抑制小鼠皮下肺癌肿瘤的生长。 结论经PEI钝化的荧光碳点负载阿霉素能显著提高DOX对非小细胞肺癌的治疗效果，并减少DOX对心脏的毒性作用。运用CD-PEI纳米颗粒改善化疗药物递送的治疗方案取得了初步证实，这可为肺癌化学治疗提供新思路，具有广大的临床应用前景。     

Visualization of electrophysiological activity at the carpal tunnel area using magnetoneurography

ObjectiveTo establish a noninvasive method to measure the neuromagnetic fields of the median nerve at the carpal tunnel after electrical digital nerve stimulation and evaluate peripheral nerve function.MethodsUsing a vector-type biomagnetometer system with a superconducting quantum interference device, neuromagnetic fields at the carpal tunnel were recorded after electrical stimulation of the index or middle digital nerve in five healthy volunteers. A novel technique for removing stimulus-induced artifacts was applied, and current distributions were calculated using a spatial filter algorithm and superimposed on X-ray.ResultsA neuromagnetic field propagating from the palm to the carpal tunnel was observed in all participants. Current distributions estimated from the magnetic fields had five components: leading and trailing components parallel to the conduction pathway, outward current preceding the leading component, inward currents between the leading and trailing components, and outward current following the trailing component. The conduction velocity and peak latency of the inward current agreed well with those of sensory nerve action potentials.ConclusionRemoving stimulus-induced artifacts enabled magnetoneurography to noninvasively visualize with high spatial resolution the electrophysiological neural activity from the palm to the carpal tunnel.SignificanceThis is the first report of using magnetoneurography to visualize electrophysiological nerve activity at the palm and carpal tunnel.     

以机油为分散剂高温热解人发合成新型碳点及其生物效应研究

目的以机油为分散剂高温热解人发后发现新型纳米碳点,通过动物实验评价了该碳点的生物效应。方法利用高温热解法对人发和机油进行炭化,对炭化产物进行萃取、过滤分离和透析得到一种具有水溶性的新型物质碳点,并命名为JYRF-CDs。利用透射电子显微镜(TEM)、高分辨透射电子显微镜(HR-TEM)、紫外-可见分光光谱、傅里叶变换红外光谱、荧光光谱、X射线光电子能谱分析(XPS)等多种方法对JYRF-CDs进行表征,利用小鼠单核巨噬细胞RAW264.7细胞进行CCK-8毒性实验来评价JYRF-CDs的安全性,并通过小鼠耳肿胀实验和小鼠醋酸扭体实验对JYRF-CDs的生物效应进行评价。结果 JYRF-CDs外形为类球形,粒径均匀分布在1.8～3.6 nm,晶格间距为0.219 7 nm。细胞毒性实验结果显示,JYRF-CDs具有低毒性,动物实验结果表明JYRF-CDs具有良好的抗炎和镇痛作用。结论首次以机油为分散剂高温热解人发后发现一种全新的碳点JYRF-CDs,以JYRF-CDs为突破口,更加明确阐释以机油为分散剂高温热解人发后炭化产物具有生物效应的物质基础,为纳米类成分的研究提供了一种新方法。     

经典名方物质基准研制的关键技术分析

中药经典名方开发已成为当下中医药界研究的热点之一,而其中经典名方物质基准的成功研制对于整个中药经典名方的申报极为关键。经典名方物质基准既是检测经典名方制剂质量的基准,同时又需反映整方的物质基础。中药成分众多而复杂,单成分的、化药式的研发与质量控制模式难以适用于整体药用的中药制剂的开发,亟需开辟一条中药专属的研发模式。以目前已有的现代科学技术,笔者建议将中药的遗传多态性、提取动力学、指纹图谱总量统计矩(相似度)法、超分子"印迹模板"等结合应用于经典名方物质基准的研制,探讨中药经典名方物质基准的质量控制技术,以期全面、准确地阐明药材-饮片-物质基准的成分群量值的传递规律,为推进中药经典名方的研制进程提供参考。     

Conductance enlargement in picoscale electroburnt graphene nanojunctions

Provided the electrical properties of electroburnt graphene junctions can be understood and controlled, they have the potential to underpin the development of a wide range of future sub-10-nm electrical devices. We examine both theoretically and experimentally the electrical conductance of electroburnt graphene junctions at the last stages of nanogap formation. We account for the appearance of a counterintuitive increase in electrical conductance just before the gap forms. This is a manifestation of room-temperature quantum interference and arises from a combination of the semimetallic band structure of graphene and a cross-over from electrodes with multiple-path connectivity to single-path connectivity just before breaking. Therefore, our results suggest that conductance enlargement before junction rupture is a signal of the formation of electroburnt junctions, with a picoscale current path formed from a single sp² bond.Graphene nanojunctions are attractive as electrodes for electrical contact to single molecules (1–7), due to their excellent stability and conductivity up to high temperatures and a close match between their Fermi energy and the HOMO (highest occupied molecular orbital) or LUMO (lowest unoccupied molecular orbit) energy levels of organic materials. Graphene electrodes also facilitate electrostatic gating due to their reduced screening compared with more bulky metallic electrodes. Although different strategies for forming nanogaps in graphene such as atomic force microscopy, nanolithography (8), electrical breakdown (9), and mechanical stress (10) have been used, only electroburning delivers the required gap-size control below 10 nm (11–13). This new technology has the potential to overcome the challenges of making stable and reproducible single-molecule junctions with gating capabilities and compatibility with integrated circuit technology (14) and may provide the breakthrough that will enable molecular devices to compete with foreseeable developments in Moore’s law, at least for some niche applications (15–17).One set of such applications is likely to be associated with room-temperature manifestations of quantum interference (QI), which are enabled by the small size of these junctions. If such interference effects could be harnessed in a single-molecule device, this would pave the way toward logic devices with energy consumption lower than the current state-of-the-art. Indirect evidence for such QI in single-molecule mechanically controlled break junctions has been reported recently in a number of papers (18), but direct control of QI has not been possible because electrostatic gating of such devices is difficult. Graphene electroburnt junctions have the potential to deliver direct control of QI in single molecules, but before this can be fully achieved, it is necessary to identify and differentiate intrinsic manifestations of room-temperature QI in the bare junctions, without molecules. In the present paper, we account for one such manifestation, which is a ubiquitous feature in the fabrication of picoscale gaps for molecular devices, namely an unexpected increase in the conductance before the formation of a tunnel gap.Only a few groups in the world have been able to implement electroburning method to form nanogap-size junctions. In a recent study of electroburnt graphene junctions, Barreiro et al. (19) used real-time in situ transmission electron microscopy (TEM) to investigate this conductance enlargement in the last moment of gap formation and ruled out the effects of both extra edge scattering and impurities, which reduce the current density near breaking. Also, they showed that the graphene junctions can be free of contaminants before the formation of the nanogap. Having eliminated these effects, they suggested that the enlargement may arise from the formation of the seamless graphene bilayers. Here we show that the conductance enlargement occurs in monolayer graphene, which rules out an explanation based on bilayers. Moreover, we have observed the enlargement in a large number of nominally identical graphene devices and therefore we can rule out the possibility of device- or flake-specific features in the electroburning process. An alternative explanation was proposed by Lu et al. (20), who observed the enlargement in few-layer graphene nanoconstrictions fabricated using TEM. They attributed the enlargement to an improvement in the quality of few-layer graphene due to current annealing, which was simply ruled out by our experiments on electroburnt single-layer graphene. They also attributed this to the reduction of the edge scattering due to the orientation of the edges (i.e., zigzag edges). However, such edge effects have been ruled out by the TEM images of Barreiro et al. (19). Therefore, although this enlargement appears to be a common feature of graphene nanojunctions, so far the origin of the increase remains unexplained.In what follows, our aim is to demonstrate that such conductance enlargement is a universal feature of electroburnt graphene junctions and arises from QI at the moment of breaking. Graphene provides an ideal platform for studying room-temperature QI effects (21) because, as well as being a suitable material for contacting single molecules, it can serve as a natural 2D grid of interfering pathways. By electroburning a graphene junction to the point where only a few carbon bonds connect the left and right electrodes, one can study the effect of QI in ring- and chain-like structures that are covalently bonded to the electrodes. In this paper, we perform feedback-controlled electroburning on single-layer graphene nanojunctions and confirm that there is an increase in conductance immediately before the formation of the tunnel junction. Transport calculations for a variety of different atomic configurations using the nonequilibrium Green’s function (NEGF) method coupled to density functional theory (DFT) show a similar behavior. To elucidate the origin of the effect, we provide a model for the observed increase in the conductance based on the transition from multipath connectivity to single-path connectivity, in close analogy to an optical double-slit experiment. The model suggests that the conductance increase is likely to occur whenever junctions are formed from any sp²-bonded material.     

量子点荧光探针在人舌鳞状细胞癌组织中的应用研究

目的 通过免疫荧光技术,利用量子点荧光探针在人的舌鳞状细胞癌组织中检测特定蛋白,探讨量子点荧光探针在人舌鳞状细胞癌组织中的应用.方法 相同粒径的量子点通过问接免疫荧光技术分别对人舌鳞状细胞癌组织中的P53及Bcl-2蛋白进行特异荧光标记,荧光显微镜观察蛋白定位表达;不同粒径的量子点通过间接免疫荧光技术,在同一张舌鳞状细...     

荧光腹腔镜下小鼠胃癌可视化成像的实验研究

目的探讨荧光腹腔镜下小鼠胃癌可视化成像在鉴别肿瘤和正常组织中的价值。方法共20只3~4周龄,体重20 g裸鼠。2只裸鼠右后肢皮下注射0.2 ml高表达HER-2基因的NCI-N87胃癌细胞悬液用于观察背部成瘤情况,1周后当瘤体直径达1 cm左右进行下一步实验观察。将0.2 ml高表达HER-2基因的NCI-N87胃癌细胞悬液注射于12只裸鼠胃黏膜下,建立裸鼠胃癌模型。将量子点与HER-2的单抗结合制作量子点纳米荧光探针。将12只胃癌模型裸鼠分为A、B组,每组6只,A组裸鼠尾静脉注射量子点纳米荧光探针100μl与裸鼠胃癌模型进行体内结合,B组裸鼠尾静脉先注射HER-2单克隆抗体再注射量子点纳米荧光探针100μl,C组6只正常生长的裸鼠尾静脉直接注射量子点纳米荧光探针100μl。最后利用改装后的荧光腹腔镜分别以15、30 min和1、2、4、8、12、24、30 h时间点观察不同时期裸鼠体内胃癌组织及其他部位的荧光显像,标本送检。结果裸鼠种瘤成功,胃癌组织在荧光腹腔镜下完成可视化成像,荧光探针结合后稳定性良好,荧光强度在1 h后达到峰值,30 h后荧光消失。发光组织病理切片证实为胃癌组织,免疫组化证实该组织高表达HER-2蛋白。结论量子点纳米荧光探针性质稳定,荧光强度1 h达到峰值,然后逐渐衰减,荧光腹腔镜下可清晰看到高表达HER-2的NCI-N87胃恶性肿瘤的边界和周围组织及淋巴结的转移情况。     

Distinctive signature of indium gallium nitride quantum dot lasing in microdisk cavities

Low-threshold lasers realized within compact, high-quality optical cavities enable a variety of nanophotonics applications. Gallium nitride materials containing indium gallium nitride (InGaN) quantum dots and quantum wells offer an outstanding platform to study light−matter interactions and realize practical devices such as efficient light-emitting diodes and nanolasers. Despite progress in the growth and characterization of InGaN quantum dots, their advantages as the gain medium in low-threshold lasers have not been clearly demonstrated. This work seeks to better understand the reasons for these limitations by focusing on the simpler, limited-mode microdisk cavities, and by carrying out comparisons of lasing dynamics in those cavities using varying gain media including InGaN quantum wells, fragmented quantum wells, and a combination of fragmented quantum wells with quantum dots. For each gain medium, we use the distinctive, high-quality (Q∼5,500) modes of the cavities, and the change in the highest-intensity mode as a function of pump power to better understand the dominant radiative processes. The variations of threshold power and lasing wavelength as a function of gain medium help us identify the possible limitations to lower-threshold lasing with quantum dot active medium. In addition, we have identified a distinctive lasing signature for quantum dot materials, which consistently lase at wavelengths shorter than the peak of the room temperature gain emission. These findings not only provide better understanding of lasing in nitride-based quantum dot cavity systems but also shed insight into the more fundamental issues of light−matter coupling in such systems.The family of III-nitrides materials is promising for the realization of photonic devices including light-emitting diodes and lasers (1–6). These systems have also been explored to engineer quantum emitters based on nitride quantum dots (QDs) that are active at room temperature and are suitable for applications in quantum information science (7). The increased control of the growth of isolated InGaN QDs in a high-quality GaN matrix has also resulted in fabrication of high-quality nitride microcavities including microdisks and photonic crystal cavities with emission at wavelengths in the blue spectral range (320−470 nm) (8, 9). Subsequently, electrically excited emitters and low-threshold lasers based on QDs as the gain medium have been studied (10, 11). However, despite the theoretical advantages of QD lasers, related to the density of electronic states for QDs (12–15), QD microcavity devices still have higher thresholds than quantum well (QW) microcavity devices for the nitride materials (8, 9, 16). Furthermore, InGaN QDs formed through a modified droplet epitaxy (MDE) method are always associated with an accompanying fragmented quantum well (fQW) layer. It is thus important to determine the possible influence of the fQW layer on lasing properties to achieve a better understanding of the unique contribution from the QDs to the lasing mechanism.This work studies the lasing dynamics and the correlation between lasing threshold and lasing wavelength of microdisk lasers whose active areas comprise either QWs, fQWs, or a combination of QDs with fQWs. Through a detailed comparison of lasing in devices with the same geometries but with different active areas, we find that the distinctive signature of QD-facilitated gain is lasing at shorter wavelengths than the average of the background emission. The short wavelength emission is further confirmed by low-temperature, low-power photoluminescence (PL) measurements.     

Anomalously robust valley polarization and valley coherence in bilayer WS2

We report the observation of anomalously robust valley polarization and valley coherence in bilayer WS₂. The polarization of the photoluminescence from bilayer WS₂ follows that of the excitation source with both circular and linear polarization, and remains even at room temperature. The near-unity circular polarization of the luminescence reveals the coupling of spin, layer, and valley degree of freedom in bilayer system, and the linearly polarized photoluminescence manifests quantum coherence between the two inequivalent band extrema in momentum space, namely, the valley quantum coherence in atomically thin bilayer WS₂. This observation provides insight into quantum manipulation in atomically thin semiconductors.Tungsten sulfide WS₂, part of the family of group VI transition metal dichalcogenides (TMDCs), is a layered compound with buckled hexagonal lattice. As WS₂ thins to atomically thin layers, WS₂ films undergo a transition from indirect gap in bulk form to direct gap at monolayer level with the band edge located at energy-degenerate valleys (K, K′) at the corners of the Brillouin zone (1–3). Like the case of its sister compound, monolayer MoS₂, the valley degree of freedom of monolayer WS₂ could be presumably addressed through nonzero but contrasting Berry curvatures and orbital magnetic moments that arise from the lack of spatial inversion symmetry at monolayers (3, 4). The valley polarization could be realized by the control of the polarization of optical field through valley-selective interband optical selection rules at K and K′ valleys as illustrated in Fig. 1A (4–6). In monolayer WS₂, both the top of the valence bands and the bottom of the conduction bands are constructed primarily by the d orbits of tungsten atoms, which are remarkably shaped by spin–orbit coupling (SOC). The giant spin–orbit coupling splits the valence bands around the K (K′) valley by 0.4 eV, and the conduction band is nearly spin degenerated (7). As a result of time-reversal symmetry, the spin splitting has opposite signs at the K and K′ valleys. Namely, the Kramer’s doublet |K ↑ ? and |K′ ↓ ? is separated from the other doublet |K′ ↑ ? and |K ↓ ? by the SOC splitting of 0.4 eV. The spin and valley are strongly coupled at K (K′) valleys, and this coupling significantly suppresses spin and valley relaxations as both spin and valley indices have to be changed simultaneously.Open in a separate windowFig. 1.(A) Schematic of valley-dependent optical selection rules and the Zeeman-like spin splitting in the valence bands of monolayer WS₂. (B) Diagram of spin–layer–valley coupling in 2H stacked bilayer WS₂. Interlayer hopping is suppressed in bilayer WS₂ owing to the coupling of spin, valley, and layer degrees of freedom.In addition to the spin and valley degrees of freedom, in bilayer WS₂ there exists an extra index: layer polarization that indicates the carriers’ location, either up-layer or down-layer. Bilayer WS₂ follows the Bernal packing order and the spatial inversion symmetry is recovered: each layer is 180° in plane rotation of the other with the tungsten atoms of a given layer sitting exactly on top of the S atoms of the other layer. The layer rotation symmetry switches K and K′ valleys, but leaves the spin unchanged, which results in a sign change for the spin–valley coupling from layer to layer (Fig. 1B). From the simple spatial symmetry point of view, one might expect that the valley-dependent physics fades at bilayers owing to inversion symmetry, as the precedent of bilayer MoS₂ (8). Nevertheless, the inversion symmetry becomes subtle if the coupling of spin, valley, and layer indices is taken into account. Note that the spin–valley coupling strength in WS₂ is around 0.4 eV (the counterpart in MoS₂ ∼ 0.16 eV), which is significantly higher than the interlayer hopping energy (∼0.1 eV); the interlayer coupling at K and K′ valleys in WS₂ is greatly suppressed as indicated in Fig. 1B (7, 9). Consequently, bilayer WS₂ can be regarded as decoupled layers and it may inherit the valley physics demonstrated in monolayer TMDCs. In addition, the interplay of spin, valley, and layer degrees of freedom opens an unprecedented channel toward manipulations of quantum states.Here we report a systemic study of the polarization-resolved photoluminescence (PL) experiments on bilayer WS₂. The polarization of PL inherits that of excitations up to room temperature, no matter whether it is circularly or linearly polarized. The experiments demonstrate the valley polarization and valley coherence in bilayer WS₂ as a result of the coupling of spin, valley, and layer degrees of freedom. Surprisingly, the valley polarization and valley coherence in bilayer WS₂ are anomalously robust compared with monolayer WS₂.For comparison, we first perform polarization-resolved photoluminescence measurements on monolayer WS₂. Fig. 2A shows the photoluminescence spectrum from monolayer WS₂ at 10 K. The PL is dominated by the emission from band-edge excitons, so-called “A” exciton at K and K′ valleys. The excitons carry a clear circular dichroism under near-resonant excitation (2.088 eV) with circular polarization as a result of valley-selective optical selection rules, where the left-handed (right handed) polarization corresponds to the interband optical transition at K (K′) valley. The PL follows the helicity of the circularly polarized excitation optical field. To characterize the polarization of the luminescence spectra, we define a degree of circular polarization as P=I(σ+)−I(σ−)I(σ+)+I(σ−), where I(σ±) is the intensity of the right- (left-) handed circular-polarization component. The luminescence spectra display a contrasting polarization for excitation with opposite helicities: P = 0.4 under σ+ excitation and P = −0.4 under σ− excitation on the most representative monolayer. For simplicity, only the PL under σ+ excitation is shown. The degree of circular polarization P is insensitive to PL energy throughout the whole luminescence as shown in Fig. 2A, Inset. These behaviors are fully expected in the mechanism of valley-selective optical selection rules (3, 4). The degree of circular polarization decays with increasing temperature and drops to 10% at room temperature (Fig. 2B). It decreases as the excitation energy shifts from the near-resonance energy of 2.088 to 2.331 eV as illustrated in Fig. 2C. The peak position of A exciton emission at band edges shifts from 2.04 eV at 10 K to 1.98 eV at room temperature. The energy difference between the PL peak and the near-resonance excitation (2.088 eV) is around 100 meV at room temperature, which is much smaller than the value 290 meV for the low temperature off-resonance excitation at 2.331 eV. However, the observed polarization for off-resonance excitation at 10 K (P = 16%) is much higher than the near-resonance condition at room temperature (P = 10%). It clearly shows that the depolarization cannot be attributed to single process, namely the off-resonance excitation or band-edge phonon scattering only (10).Open in a separate windowFig. 2.Photoluminescence of monolayer WS₂ under circularly polarized excitation. (A) Polarization resolved luminescence spectra with σ+ detection (red) and σ− detection (black) under near-resonant σ+ excitation (2.088 eV) at 10 K. Peak A is the excitonic transition at band edges of K (K′) valleys. Opposite helicity of PL is observed under σ− excitation. Inset presents the degree of the circular polarization at the prominent PL peak. (B) The degree of the circular polarization as a function of temperature. The curve (red) is a fit following a Boltzmann distribution where the intervalley scattering by phonons is assumed. (C) Photoluminescence spectrum under off-resonant σ+ excitation (2.33 eV) at 10 K. The red (black) curve denotes the PL circular components of σ+ (σ−).Next we study the PL from bilayer WS₂. Fig. 3 shows the PL spectrum from bilayer WS₂. The peak labeled as “I” denotes the interband optical transition from the indirect band gap, and the peak A corresponds to the exciton emission from direct band transition at K and K′ valleys. Although bilayer WS₂ has an indirect gap, the direct interband optical transition at K and K′ valleys dominates the integrated PL intensity as the prerequisite of phonon/defect scattering is waived for direct band emission and the direct gap is just slightly larger than the indirect band gap in bilayers. Fig. 3A displays surprisingly robust PL circular dichroism of A exciton emission under circularly polarized excitations of 2.088 eV (resonance) and 2.331 eV (off resonance). The degree of circular polarization of A exciton emission under near-resonant σ± excitation is near unity (around 95%) at 10 K and preserves around 60% at room temperature. In contrast, the emission originating from indirect band gap is unpolarized in all experimental conditions.Open in a separate windowFig. 3.Photoluminescence of bilayer WS₂ under circularly polarized excitations. (A) Polarization-resolved luminescence spectra with components of σ+ (red) and σ− (black) under near-resonant σ+ excitation (2.088 eV) at 10 K. Peak A is recognized as the excitonic transition at band edge of direct gap. Peak I originates from the indirect band-gap emission, showing no polarization. Inset presents the circular polarization of the A excitonic transition around the PL peak. Opposite helicity of PL is observed under σ− excitation. (B) The degree of circular polarization as a function of temperature (black). The curve (red) is a fit following a Boltzman distribution where the intervalley scattering by phonons is assumed. (C) Photoluminescence spectrum of components of σ+ (red) and σ− (black) under off-resonance σ+ excitation (2.33 eV) at 10 K. A nonzero circular polarization P is only observed at emissions from A excitons.To exclude the potential cause of charge trapping or substrate charging effect, we study the polarization-resolved PL of bilayer WS₂ with an out-plane electric field. Fig. 4A shows the evolution of PL spectra in a field-effect-transistor-like device under circularly polarized excitations of 2.088 eV and an electric gate at 10 K. The PL spectra dominated by A exciton show negligible change under the gate bias in the range of −40 to 20 V. The electric-conductance measurements show that the bilayer WS₂ stays at the electrically intrinsic state under the above bias range. The PL spectra can be safely recognized as emissions from free excitons. As the gate bias switches further to the positive side (>20 V), the PL intensity decreases, and the emission from electron-bounded exciton “X⁻,” the so-called trion emerges and gradually raises its weight in the PL spectrum (11, 12). The electron–exciton binding energy is found to be 45 meV. Given only one trion peak in PL spectra, the interlayer trion (formed by exciton and electron/hole in different layers) and intralayer trion (exciton and electron/hole in the same layer) could not be distinguished due to the broad spectral width (13). Both the free exciton and trion show slight red shifts with negative bias, presumably as a result of quantum-confined stark effect (14). At all of the bias conditions, the degree of circular polarization of the free exciton and trion stays unchanged within the experiment sensitivity as shown in Fig. 4C.Open in a separate windowFig. 4.Electric-doping-dependent photoluminescence spectrum of bilayer WS₂ field-effect transistor. (A) Luminescence spectra of bilayer WS₂ at different gate voltage under near-resonant σ+ excitation (2.088 eV) at 10 K. X and X⁻ denote neutral exciton and trion, respectively. Green curve is a fitting consisting of two Lorentzian peak fits (peak I and X⁻) and one Gaussian peak fit (peak X). (B) Intensity of exciton and trion emissions versus gate. (Upper) The gate-dependent integral PL intensity consisting of exciton (X) and trion (X⁻). (Lower) The ratio of the integral PL intensity of exciton versus that of trion, as a function of the gate voltage. (C) Degree of circular polarization of exciton (X, red) and trion (X⁻, blue) versus the gate.It is also unlikely that the high polarization in bilayers results from the isolation of the top layer from the environments, as similar behaviors are observed in monolayer and bilayer WS₂ embedded in polymethyl methaccrylate (PMMA) matrix or capped with a 20-nm-thick SiO₂ deposition. The insensitivity of the circular-polarization degree on bias and environments rules out the possibility that the effects of Coulomb screening, charge traps, or charge transfers with substrates are the major causes for the robust circular dichroism in bilayers against monolayers.One potential cause may result from the shorter lifetime of excitons at K (K′) valley for bilayer system. The band gap shifts from K and K′ points of the Brillouin zone in monolayers to the indirect gap between the top of the valence band at Γ points and the bottom of the conduction band in the middle of K and Γ points in bilayers. Combining our time-resolved pump-probe reflectance experiments (Supporting Information) and the observed relative PL strength between monolayer and bilayer (10:1), we infer the exciton lifetime at K (K′) valleys around 10 ps, a fraction of that at monolayers. If we assume (i) the PL circular polarization P=P01+2ττk, where P₀ is the theoretical limit of PL polarization, and τ_k and τ denote the valley lifetime and exciton lifetime respectively; and (ii) the valley lifetime is the same for both monolayers and bilayers, the shorter exciton lifetime will lead to significantly higher PL polarization. However, the difference in exciton lifetime between bilayers and monolayers is not overwhelming enough to be the major cause of robust polarization observed in the time-integrated PL in bilayers.In monolayer WS₂ under circularly polarized resonant excitations, the depolarization mainly comes from the K ? K′ intervalley scattering. In bilayers, the depolarization could be either via K ? K′ intervalley scattering within the layer in a similar way as in monolayers, or via interlayer hopping, which also requires spin flip. As we discussed above, the interlayer hopping at K valley is suppressed in WS₂ as a result of strong SOC in WS₂ and spin–layer–valley coupling, which were experimentally proved by the circular dichroism in PL from bilayers. The robust polarization in bilayers implies that the intervalley scattering within a layer is diminished compared with that in monolayers. There are two prerequisites for intervalley scattering within layers: conservation of crystal momentum and spin flip of holes. The crystal momentum conservation could be satisfied with the involvement of phonons at K points in the Brillouin zone or atomic size defects, presumably sharing the similar strength in monolayers and bilayers. Spin-flip process could be realized by three different spin scattering mechanisms, namely D’yakonov–Perel (DP) mechanism (15), Elliot–Yaffet (EY) mechanism (16), and Bir–Aronov–Pikus (BAP) mechanism (17, 18). The DP mechanism acts through a Lamor precession driven by electron wavevector k dependent spin–orbit coupling. It is thought to be negligible for spin flip along out-plane direction as the mirror symmetry with respect to the plane of W atoms secures a zero out-plane crystal electric field. Another possible driving force behind the DP mechanism could be the asymmetry owing to the interface with the substrate. This can be excluded by the similar behaviors, where the monolayers and bilayers WS₂ are embedded in PMMA matrix or capped with a thin layer of SiO₂. The negligible effect of electric gating on polarization also implies that the DP mechanism is weak in monolayer and bilayer WS₂; the EY mechanism originates from scattering with phonons and defects. Its strength in bilayers and monolayers is likely to be at similar scale, and bilayers even have more low-frequency collective vibrational modes (19). Therefore, EY mechanism is unlikely to be the cause here; the BAP mechanism originates from the electron–hole exchange interaction. In monolayer and bilayer TMDCs, the optical features are dominated by the Wannier type, yet giant excitonic effect, and the exciton-binding energy in such intrinsic 2D semiconductors is estimated to be 0.6 ∼ 1 eV (20, 21). This giant exciton-binding energy indicates a mixture of electron and hole wavefunctions and, consequently, strong exchange interaction, which may contribute to the spin flip and intervalley scattering (5, 22). As the conduction band has a band mixing at K points, the spin flip of the electron would be a quick process. An analogous scenario is that the spin of holes relaxes in hundreds of femtoseconds or fewer in GaAs as a result of band mixing and spin–orbit coupling. The electron spin flip could lead to hole spin flip via strong exchange interaction accompanying intervalley scattering, which is realized by the virtual annihilation of a bright exciton in the K valley and then generation in the K′ valley or vice versa (22). This non-single-particle spin relaxation leads to valley depolarization instead of the decrease of luminescence intensity that results from coupling with dark excitons. Generally, the exciton-binding energy decreases with the relaxation of spatial confinement. However, first principle calculation shows that monolayer and bilayer WS₂ share the similar band dispersion and effective masses around K valley in their Brillouin zone as a result of spin–valley coupling (7). It implies that the binding energy of excitons around K valley in bilayer WS₂ is similar to or slightly less than that in monolayer WS₂. As the exchange interaction is roughly proportional to the square of exciton binding energy, the spin-flip rate and consequently intervalley scattering via exciton exchange interactions is presumably comparable or smaller to some extent in bilayer WS₂ (Supporting Information). Nevertheless, this is unlikely the major cause of the anomalously robust valley polarization in bilayer WS₂.Another possibility includes extra spin-conserving channels via intermediate intervalley-interlayer scatterings in bilayer WS₂, which are absent in monolayers (23). The extra spin-conserving channel may compete with the spin-flip process and reduce the relative weight of spin-flip intervalley scattering to some extent. However, the mechanism and the strength are unclear so far. Overall, the robust circular polarization in bilayers likely results from combined effects of the shorter exciton lifetime, smaller exciton-binding energy, extra spin-conserving channels, and the coupling of spin, layer, and valley degrees of freedom, indicating the relatively weak intervalley scattering in bilayer system. Further quantitative study is necessary to elaborate the mechanism.We also investigated the PL from bilayer WS₂ under a linearly polarized excitation. A linearly polarized light could be treated as a coherent superposition of two opposite-helicity circularly polarized lights with a certain phase difference. The phase difference determines the polarization direction. In semiconductors, a photon excites an electron–hole pair with the transfer of energy, momentum, and phase information. The hot carriers energetically relax to the band edge in a quick process around 10⁻¹ ∼ 10¹ ps through runs of inelastic and elastic scatterings, e.g., by acoustic phonons. During the quick relaxation process, generally the phase information randomizes and herein coherence fades. In monolayer TMDCs, the main channel for carrier relaxation is through intravalley scatterings including Coulomb interactions with electron (hole) and inelastic interactions with phonons, which are valley independent and preserve the relative phase between K and K′ valleys (24). In bilayer WS₂, the suppression of intervalley scattering consequently leads to the suppression of inhomogeneous broadening in carrier’s phase term. Subsequently, the valley coherence demonstrated in monolayer WSe₂ (24) is expected to be enhanced in bilayers (13). The valley coherence in monolayer and bilayer WS₂ could be monitored by the polarization of PL under linearly polarized excitations.Fig. 5A shows the linearly polarized components of PL under a linearly polarized excitation of 2.088 eV at 10 K. The emission from indirect band gap is unpolarized and A exciton displays a pronounced linear polarization following the excitation. The degree of linear polarization P=I(‖)−I(⊥)I(‖)+I(⊥) is around 80%, where I(∥)(I(⊥)) is the intensity of PL with parallel (perpendicular) polarization with respect to the excitation polarization. In contrast, the linear polarization is much weaker in monolayer samples (4% under the same experimental conditions, as shown in Fig. 5B). As presented in Fig. 5C, the polarization of A exciton is independent of crystal orientation and exactly follows the polarization of excitations. The degree of the linear polarization in bilayer WS₂ slightly decreases with the increased temperature and drops from 80% at 10 K to 50% at room temperature (Fig. 5D). This is the paradigm of the robust valley coherency in bilayer WS₂.Open in a separate windowFig. 5.Linearly polarized excitations on monolayer and bilayer WS₂. (A) Linear-polarization-resolved luminescence spectra of bilayer WS₂ under near-resonant linearly polarized excitation (2.088 eV) at 10 K. Red (black) presents the spectrum with parallel (cross) polarization with respect to the linear polarization of excitation source. A linear polarization of 80% is observed for exciton A, and the indirect gap transition (I) is unpolarized. (B) Linear-polarization-resolved luminescence spectra of monolayer WS₂ under near-resonant linearly polarized excitation (2.088 eV) at 10 K. Red (black) denotes the spectrum with the parallel (cross) polarization with respect to the linear polarization of excitation source. The linear polarization for exciton A in monolayer WS₂ is much weaker, with a maximum value of 4%. (C) Polar plot for intensity of the exciton A in bilayer WS₂ (black) as a function of the detection angle at 10 K. Red curve is a fit-following cos²(θ). (D) The degree of linear polarization of exciton A in bilayer WS₂ (black) as a function of temperature. The curve (red) is a fit following a Boltzmann distribution where the intervalley scattering by phonons is assumed. (E) Electric doping dependence of the linear polarization of exciton A in bilayer WS₂ at 10 K.The linear polarization of both exciton and trion in bilayer, contrasting to the circular polarization, which is insensitive to the electric field in the range, shows a weak electric gating dependence as shown in Fig. 5E. The PL linear polarization, presenting valley coherence, decreases as the Fermi level shifts to the conduction band. It does not directly affect intervalley scattering within individual layers and makes negligible change in circular dichroism. Nevertheless, the electric field between the layers induces a layer polarization and slightly shifts the band alignments between the layers by different amounts in conduction and valence bands (13, 25), although the shift is indistinguishable in the present PL spectra due to the broad spectral width. The layer polarization and the shift of band alignments may induce a relative phase difference between two layers and therefore affect the PL linear polarization via interference. Further study is needed to fully understand the mechanism.In summary, we demonstrated anomalously robust valley polarization and valley polarization coherence in bilayer WS₂. The valley polarization and valley coherence in bilayer WS₂ are the direct consequences of giant spin–orbit coupling and spin valley coupling in WS₂. The depolarization and decoherence processes are greatly suppressed in bilayer, although the mechanism is ambiguous. The robust valley polarization and valley coherence make bilayer WS₂ an intriguing platform for spin and valley physics.