Dephasing by optical phonons in GaN defect single-photon emitters.

Single-photon defect emitters (SPEs), especially those with magnetically and optically addressable spin states, in technologically mature wide bandgap semiconductors are attractive for realizing integrated platforms for quantum applications. Broadening of the zero phonon line (ZPL) caused by dephasing in solid state SPEs limits the indistinguishability of the emitted photons. Dephasing also limits the use of defect states in quantum information processing, sensing, and metrology. In most defect emitters, such as those in SiC and diamond, interaction with low-energy acoustic phonons determines the temperature dependence of the dephasing rate and the resulting broadening of the ZPL with the temperature obeys a power law. GaN hosts bright and stable single-photon emitters in the 600-700 nm wavelength range with strong ZPLs even at room temperature. In this work, we study the temperature dependence of the ZPL spectra of GaN SPEs integrated with solid immersion lenses with the goal of understanding the relevant dephasing mechanisms. At temperatures below ~ 50 K, the ZPL lineshape is found to be Gaussian and the ZPL linewidth is temperature independent and dominated by spectral diffusion. Above ~ 50 K, the linewidth increases monotonically with the temperature and the lineshape evolves into a Lorentzian. Quite remarkably, the temperature dependence of the linewidth does not follow a power law. We propose a model in which dephasing caused by absorption/emission of optical phonons in an elastic Raman process determines the temperature dependence of the lineshape and the linewidth. Our model explains the temperature dependence of the ZPL linewidth and lineshape in the entire 10-270 K temperature range explored in this work. The ~ 19 meV optical phonon energy extracted by fitting the model to the data matches remarkably well the ~ 18 meV zone center energy of the lowest optical phonon band ([Formula: see text]) in GaN. Our work sheds light on the mechanisms responsible for linewidth broadening in GaN SPEs. Since a low energy optical phonon band ([Formula: see text]) is a feature of most group III-V nitrides with a wurtzite crystal structure, including hBN and AlN, we expect our proposed mechanism to play an important role in defect emitters in these materials as well.

Molecular beam homoepitaxy of N-polar AlN: Enabling role of aluminum-assisted surface cleaning.

N-polar aluminum nitride (AlN) is an important building block for next-generation high-power radio frequency electronics. We report successful homoepitaxial growth of N-polar AlN by molecular beam epitaxy (MBE) on large-area, cost-effective N-polar AlN templates. Direct growth without any in situ surface cleaning leads to films with inverted Al polarity. It is found that Al-assisted cleaning before growth enables the epitaxial film to maintain N-polarity. The grown N-polar AlN epilayer with its smooth, pit-free surface duplicates the structural quality of the substrate, as evidenced by a clean and smooth growth interface with no noticeable extended defects generation. Near band-edge photoluminescence peaks are observed at room temperature on samples with MBE-grown layers but not on the bare AlN templates, implying the suppression of nonradiative recombination centers in the epitaxial N-polar AlN.

Momentum-resolved electronic structure and band offsets in an epitaxial NbN/GaN superconductor/semiconductor heterojunction.

The electronic structure of heterointerfaces is a pivotal factor for their device functionality. We use soft x-ray angle-resolved photoelectron spectroscopy to directly measure the momentum-resolved electronic band structures on both sides of the Schottky heterointerface formed by epitaxial films of the superconducting NbN on semiconducting GaN, and determine their momentum-dependent interfacial band offset as well as the band-bending profile. We find, in particular, that the Fermi states in NbN are well separated in energy and momentum from the states in GaN, excluding any notable electronic cross-talk of the superconducting states in NbN to GaN. We support the experimental findings with first-principles calculations for bulk NbN and GaN. The Schottky barrier height obtained from photoemission is corroborated by electronic transport and optical measurements. The momentum-resolved understanding of electronic properties of interfaces elucidated in our work opens up new frontiers for the quantum materials where interfacial states play a defining role.

An all-epitaxial nitride heterostructure with concurrent quantum Hall effect and superconductivity.

Creating seamless heterostructures that exhibit the quantum Hall effect and superconductivity is highly desirable for future electronics based on topological quantum computing. However, the two topologically robust electronic phases are typically incompatible owing to conflicting magnetic field requirements. Combined advances in the epitaxial growth of a nitride superconductor with a high critical temperature and a subsequent nitride semiconductor heterostructure of metal polarity enable the observation of clean integer quantum Hall effect in the polarization-induced two-dimensional (2D) electron gas of the high-electron mobility transistor. Through individual magnetotransport measurements of the spatially separated GaN 2D electron gas and superconducting NbN layers, we find a small window of magnetic fields and temperatures in which the epitaxial layers retain their respective quantum Hall and superconducting properties. Its analysis indicates that in epitaxial nitride superconductor/semiconductor heterostructures, this window can be significantly expanded, creating an industrially viable platform for robust quantum devices that exploit topologically protected transport.

Engineering the Berreman mode in mid-infrared polar materials.

We demonstrate coupling to and control over the broadening and dispersion of a mid-infrared leaky mode, known as the Berreman mode, in samples with different dielectric environments. We fabricate subwavelength films of AlN, a mid-infrared epsilon-near-zero material that supports the Berreman mode, on materials with a weakly negative permittivity, strongly negative permittivity, and positive permittivity. Additionally, we incorporate ultra-thin AlN layers into a GaN/AlN heterostructure, engineering the dielectric environment above and below the AlN. In each of the samples, coupling to the Berreman mode is observed in angle-dependent reflection measurements at wavelengths near the longitudinal optical phonon energy. The measured dispersion of the Berreman mode agrees well with numerical modes. Differences in the dispersion and broadening for the different materials is quantified, including a 13 cm-1 red-shift in the energy of the Berreman mode for the heterostructure sample.

Enhanced injection efficiency and light output in bottom tunnel-junction light-emitting diodes.

Recently, the use of bottom-TJ geometry in LEDs, which achieves N-polar-like alignment of polarization fields in conventional metal-polar orientations, has enabled enhancements in LED performance due to improved injection efficiency. Here, we elucidate the root causes behind the enhanced injection efficiency by employing mature laser diode structures with optimized heterojunction GaN/In0.17Ga0.83N/GaN TJs and UID GaN spacers to separate the optical mode from the heavily doped absorbing p-cladding regions. In such laser structures, polarization offsets at the electron blocking layer, spacer, and quantum barrier interfaces play discernable roles in carrier transport. By comparing a top-TJ structure to a bottom-TJ structure, and correlating features in the electroluminescence, capacitance-voltage, and current-voltage characteristics to unique signatures of the N- and Ga-polar polarization heterointerfaces in energy band diagram simulations, we identify that improved hole injection at low currents, and improved electron blocking at high currents, leads to higher injection efficiency and higher output power for the bottom-TJ device throughout 5 orders of current density (0.015-1000 A/cm2). Moreover, even with the addition of a UID GaN spacer, differential resistances are state-of-the-art, below 7 × 10-4 Ωcm2. These results highlight the virtues of the bottom-TJ geometry for use in high-efficiency laser diodes.

A polarization-induced 2D hole gas in undoped gallium nitride quantum wells.

A high-conductivity two-dimensional (2D) hole gas, analogous to the ubiquitous 2D electron gas, is desirable in nitride semiconductors for wide-bandgap p-channel transistors. We report the observation of a polarization-induced high-density 2D hole gas in epitaxially grown gallium nitride on aluminium nitride and show that such hole gases can form without acceptor dopants. The measured high 2D hole gas densities of about 5 × 1013 per square centimeters remain unchanged down to cryogenic temperatures and allow some of the lowest p-type sheet resistances among all wide-bandgap semiconductors. The observed results provide a probe for studying the valence band structure and transport properties of wide-bandgap nitride interfaces.

Band Structure Engineering of Layered WSe2 via One-Step Chemical Functionalization.

Chemical functionalization is demonstrated to enhance the p-type electrical performance of two-dimensional (2D) layered tungsten diselenide (WSe2) field-effect transistors (FETs) using a one-step dipping process in an aqueous solution of ammonium sulfide [(NH4)2S(aq)]. Molecularly resolved scanning tunneling microscopy and spectroscopy reveal that molecular adsorption on a monolayer WSe2 surface induces a reduction of the electronic band gap from 2.1 to 1.1 eV and a Fermi level shift toward the WSe2 valence band edge (VBE), consistent with an increase in the density of positive charge carriers. The mechanism of electronic transformation of WSe2 by (NH4)2S(aq) chemical treatment is elucidated using density functional theory calculations which reveal that molecular "SH" adsorption on the WSe2 surface introduces additional in-gap states near the VBE, thereby, inducing a Fermi level shift toward the VBE along with a reduction in the electronic band gap. As a result of the (NH4)2S(aq) chemical treatment, the p-branch ON-currents (ION) of back-gated few-layer ambipolar WSe2 FETs are enhanced by about 2 orders of magnitude, and a ∼6× increase in the hole field-effect mobility is observed, the latter primarily resulting from the p-doping-induced narrowing of the Schottky barrier width leading to an enhanced hole injection at the WSe2/contact metal interface. This (NH4)2S(aq) chemical functionalization technique can serve as a model method to control the electronic band structure and enhance the performance of devices based on 2D layered transition-metal dichalcogenides.

Selective Chemical Response of Transition Metal Dichalcogenides and Metal Dichalcogenides in Ambient Conditions.

To fabricate practical devices based on semiconducting two-dimensional (2D) materials, the source, channel, and drain materials are exposed to ambient air. However, the response of layered 2D materials to air has not been fully elucidated at the molecular level. In the present report, the effects of air exposure on transition metal dichalcogenides (TMD) and metal dichalcogenides (MD) are studied using ultrahigh-vacuum scanning tunneling microscopy (STM). The effects of a 1-day ambient air exposure on MBE-grown WSe2, chemical vapor deposition (CVD)-grown MoS2, and MBE SnSe2 are compared. Both MBE-grown WSe2 and CVD-grown MoS2 display a selective air exposure response at the step edges, consistent with oxidation on WSe2 and adsorption of hydrocarbon on MoS2, while the terraces and domain/grain boundaries of both TMDs are nearly inert to ambient air. Conversely, MBE-grown SnSe2, an MD, is not stable in ambient air. After exposure in ambient air for 1 day, the entire surface of SnSe2 is decomposed to SnOx and SeOx, as seen with X-ray photoelectron spectroscopy. Since the oxidation enthalpy of all three materials is similar, the data is consistent with greater oxidation of SnSe2 being driven by the weak bonding of SnSe2.

Atomic Layer Deposition of Al2O3 on WSe2 Functionalized by Titanyl Phthalocyanine.

To deposit an ultrathin dielectric onto WSe2, monolayer titanyl phthalocyanine (TiOPc) is deposited by molecular beam epitaxy as a seed layer for atomic layer deposition (ALD) of Al2O3 on WSe2. TiOPc molecules are arranged in a flat monolayer with 4-fold symmetry as measured by scanning tunneling microscopy. ALD pulses of trimethyl aluminum and H2O nucleate on the TiOPc, resulting in a uniform deposition of Al2O3, as confirmed by atomic force microscopy and cross-sectional transmission electron microscopy. The field-effect transistors (FETs) formed using this process have a leakage current of 0.046 pA/µm(2) at 1 V gate bias with 3.0 nm equivalent oxide thickness, which is a lower leakage current than prior reports. The n-branch of the FET yielded a subthreshold swing of 80 mV/decade.

Covalent bonding modulated graphene-metal interfacial thermal transport.

We report the covalent bonding enabled modulation of the interfacial thermal conductance between graphene and metals Cu, Al, and Pt by controlling the oxidation of graphene. By combining comprehensive X-ray photoelectron spectroscopy (XPS) analysis and time-domain thermoreflectance measurements, we quantify the effect of graphene oxidation on interfacial thermal conductance. It was found that thermal conductance increases with the degree of graphene oxidation until a peak value is obtained at an oxygen/carbon atom percentage of ∼7.7%. The maximum enhancement in thermal conductance was measured to be 55%, 38%, and 49% for interfaces between oxidized graphene and Cu, Al, and Pt, respectively. In situ XPS measurements show that oxygen covalently binds to Cu and graphene simultaneously, forming a highly efficient bridge to enhance the thermal transport. Our molecular dynamics simulations verify that strong interfacial covalent bonds are the key to the thermal conductance enhancement. This work provides valuable insights into the mechanism of functionalization-induced thermal conductance enhancement and design guidelines for graphene-based devices.

Layered transition metal dichalcogenides: promising near-lattice-matched substrates for GaN growth.

Most III-nitride semiconductors are grown on non-lattice-matched substrates like sapphire or silicon due to the extreme difficulty of obtaining a native GaN substrate. We show that several layered transition-metal dichalcogenides are closely lattice-matched to GaN and report the growth of GaN on a range of such layered materials. We report detailed studies of the growth of GaN on mechanically-exfoliated flakes WS2 and MoS2 by metalorganic vapour phase epitaxy. Structural and optical characterization show that strain-free, single-crystal islands of GaN are obtained on the underlying chalcogenide flakes. We obtain strong near-band-edge emission from these layers, and analyse their temperature-dependent photoluminescence properties. We also report a proof-of-concept demonstration of large-area growth of GaN on CVD MoS2. Our results show that the transition-metal dichalcogenides can serve as novel near-lattice-matched substrates for nitride growth.

Scanning Tunneling Microscopy and Spectroscopy of Air Exposure Effects on Molecular Beam Epitaxy Grown WSe2 Monolayers and Bilayers.

The effect of air exposure on 2H-WSe2/HOPG is determined via scanning tunneling microscopy (STM). WSe2 was grown by molecular beam epitaxy on highly oriented pyrolytic graphite (HOPG), and afterward, a Se adlayer was deposited in situ on WSe2/HOPG to prevent unintentional oxidation during transferring from the growth chamber to the STM chamber. After annealing at 773 K to remove the Se adlayer, STM images show that WSe2 layers nucleate at both step edges and terraces of the HOPG. Exposure to air for 1 week and 9 weeks caused air-induced adsorbates to be deposited on the WSe2 surface; however, the band gap of the terraces remained unaffected and nearly identical to those on decapped WSe2. The air-induced adsorbates can be removed by annealing at 523 K. In contrast to WSe2 terraces, air exposure caused the edges of the WSe2 to oxidize and form protrusions, resulting in a larger band gap in the scanning tunneling spectra compared to the terraces of air-exposed WSe2 monolayers. The preferential oxidation at the WSe2 edges compared to the terraces is likely the result of dangling edge bonds. In the absence of air exposure, the dangling edge bonds had a smaller band gap compared to the terraces and a shift of about 0.73 eV in the Fermi level toward the valence band. However, after air exposure, the band gap of the oxidized WSe2 edges became about 1.08 eV larger than that of the WSe2 terraces, resulting in the electronic passivation of the WSe2.

Esaki Diodes in van der Waals Heterojunctions with Broken-Gap Energy Band Alignment.

van der Waals (vdW) heterojunctions composed of two-dimensional (2D) layered materials are emerging as a solid-state materials family that exhibits novel physics phenomena that can power a range of electronic and photonic applications. Here, we present the first demonstration of an important building block in vdW solids: room temperature Esaki tunnel diodes. The Esaki diodes were realized in vdW heterostructures made of black phosphorus (BP) and tin diselenide (SnSe2), two layered semiconductors that possess a broken-gap energy band offset. The presence of a thin insulating barrier between BP and SnSe2 enabled the observation of a prominent negative differential resistance (NDR) region in the forward-bias current-voltage characteristics, with a peak to valley ratio of 1.8 at 300 K and 2.8 at 80 K. A weak temperature dependence of the NDR indicates electron tunneling being the dominant transport mechanism, and a theoretical model shows excellent agreement with the experimental results. Furthermore, the broken-gap band alignment is confirmed by the junction photoresponse, and the phosphorus double planes in a single layer of BP are resolved in transmission electron microscopy (TEM) for the first time. Our results represent a significant advance in the fundamental understanding of vdW heterojunctions and broaden the potential applications of 2D layered materials.

Exceptional charge transport properties of graphene on germanium.

The excellent charge transport properties of graphene suggest a wide range of application in analog electronics. While most practical devices will require that graphene be bonded to a substrate, such bonding generally degrades these transport properties. In contrast, when graphene is transferred to Ge(001) its conductivity is extremely high and the charge carrier mobility derived from the relevant transport measurements is, under some circumstances, higher than that of freestanding, edge-supported graphene. We measure a mobility of ∼ 5 × 10(5) cm(2) V(-1) s(-1) at 20 K, and ∼ 10(3) cm(2) V(-1) s(-1) at 300 K. These values are close to the theoretical limit for doped graphene. Carrier densities in the graphene are as high as 10(14) cm(-2) at 300 K.

Thermal conductivity of monolayer molybdenum disulfide obtained from temperature-dependent Raman spectroscopy.

Atomically thin molybdenum disulfide (MoS2) offers potential for advanced devices and an alternative to graphene due to its unique electronic and optical properties. The temperature-dependent Raman spectra of exfoliated, monolayer MoS2 in the range of 100-320 K are reported and analyzed. The linear temperature coefficients of the in-plane E2g 1 and the out-of-plane A1g modes for both suspended and substrate-supported monolayer MoS2 are measured. These data, when combined with the first-order coefficients from laser power-dependent studies, enable the thermal conductivity to be extracted. The resulting thermal conductivity κ = (34.5(4) W/mK at room temperature agrees well with the first principles lattice dynamics simulations. However, this value is significantly lower than that of graphene. The results from this work provide important input for the design of MoS2-based devices where thermal management is critical.

Terahertz imaging employing graphene modulator arrays.

In this paper we propose and experimentally demonstrate arrays of graphene electro-absorption modulators as electrically reconfigurable patterns for terahertz cameras. The active element of these modulators consists of only single-atom-thick graphene, achieving a modulation of the THz wave reflectance > 50% with a potential modulation depth approaching 100%. Although the prototype presented here only contains 4x4 pixels, it reveals the possibility of developing reliable low-cost video-rate THz imaging systems employing single detector.

Exciton dynamics in suspended monolayer and few-layer MoS2 2D crystals.

Femtosecond transient absorption spectroscopy and microscopy were employed to study exciton dynamics in suspended and Si3N4 substrate-supported monolayer and few-layer MoS2 2D crystals. Exciton dynamics for the monolayer and few-layer structures were found to be remarkably different from those of thick crystals when probed at energies near that of the lowest energy direct exciton (A exciton). The intraband relaxation rate was enhanced by more than 40 fold in the monolayer in comparison to that observed in the thick crystals, which we attributed to defect assisted scattering. Faster electron-hole recombination was found in monolayer and few-layer structures due to quantum confinement effects that lead to an indirect-direct band gap crossover. Nonradiative rather than radiative relaxation pathways dominate the dynamics in the monolayer and few-layer MoS2. Fast trapping of excitons by surface trap states was observed in monolayer and few-layer structures, pointing to the importance of controlling surface properties in atomically thin crystals such as MoS2 along with controlling their dimensions.

Direct measurement of Dirac point energy at the graphene/oxide interface.

We report the direct measurement of the Dirac point, the Fermi level, and the work function of graphene by performing internal photoemission measurements on a graphene/SiO(2)/Si structure with a unique optical-cavity enhanced test structure. A complete electronic band alignment at the graphene/SiO(2)/Si interfaces is accurately established. The observation of enhanced photoemission from a one-atom thick graphene layer was possible by taking advantage of the constructive optical interference in the SiO(2) cavity. The photoemission yield was found to follow the well-known linear density-of-states dispersion in the vicinity of the Dirac point. At the flat band condition, the Fermi level was extracted and found to reside 3.3 eV ± 0.05 eV below the bottom of the SiO(2) conduction band. When combined with the shift of the Fermi level from the Dirac point, we are able to ascertain the position of the Dirac point at 3.6 eV ± 0.05 eV with respect to the bottom of the SiO(2) conduction band edge, yielding a work function of 4.5 eV ± 0.05 eV which is in an excellent agreement with theory. The accurate determination of the work function of graphene is of significant importance to the engineering of graphene-based devices, and the measurement technique we have advanced in this Letter will have significant impact on numerous applications for emerging graphene-like 2-dimensional material systems.

A new class of electrically tunable metamaterial terahertz modulators.

Switchable metamaterials offer unique solutions for efficiently manipulating electromagnetic waves, particularly for terahertz waves, which has been difficult since naturally occurring materials rarely respond to terahertz frequencies controllably. However, few terahertz modulators demonstrated to date exhibit simultaneously low attenuation and high modulation depth. In this letter we propose a new class of electrically-tunable terahertz metamaterial modulators employing metallic frequency-selective-surfaces (FSS) in conjunction with capacitively-tunable layers of electrons, promising near 100% modulation depth and < 15% attenuation. The fundamental departure in our design from the prior art is tuning enabled by self-gated electron layers that is independent from the metallic FSS. Our proposal is applicable to all possible electrically tunable elements including graphene, Si, MoS(2), oxides etc, thus opening up myriad opportunities for realizing high performance switchable metamaterials over an ultra-wide terahertz frequency range.