Large-area Single Crystals Research Articles

Mechanism of Thermodynamically Rationalized Selective Growth of a Two-Dimensional Ternary Ferromagnet on Insulating Substrates.

Two-dimensional (2D) semiconducting ferromagnet Fe3GeTe2 holds great promise for advanced spintronic applications because of its gate-tunable ferromagnetic ordering at room temperature, whereas the controllable growth of large-area single crystals remains very challenging due to its ternary nature and variable stoichiometry inducing many competitive phases. Here, we theoretically probe the mechanism of selective growth of monolayer Fe3GeTe2 on various epitaxial substrates. Thermodynamic analysis shows that the corresponding phase-pure chemical potential windows for the selective growth of Fe3GeTe2 can be reasonably attained in ternary phase space on insulating and chemically inert c-plane sapphire and Ga2O3(0001) substrates by properly modulating the interfacial interaction and employing suitable feedstocks to avoid competitive growth of possible impurity phases with different stoichiometry ratios. It is also revealed that both the weak edge-substrate interaction and interlayer coupling of Fe3GeTe2 together lead to a surface-dominated nucleation behavior and, thereby, energetically favor lateral growth of the monolayer rather than vertical growth of the multilayer. Importantly, straight protocols for the experimentally selective growth of phase-pure ternary Fe3GeTe2 are also provided by establishing the relationship between the feedstock chemical potential and growth parameters on a thermochemical basis. Our insightful study can also be reasonably extended to guide future experimental design for the selective growth of other multicomponent 2D materials.

Integration of Large-Area Halide Perovskite Single Crystals and Substrates via Chemical Welding Using an Ionic Liquid for Applications in X-ray Detection.

The large carrier lifetime mobility product and strong stopping power for high-energy X-rays make halide perovskites an attractive candidate for next-generation X-ray detectors. In particular, high-energy X-rays in the range of several tens of keV require halide perovskite absorber layers with thicknesses exceeding a few millimeters. To avoid carrier scattering caused by grain boundaries at such thicknesses, the utilization of single crystals is desirable. Large-area single crystals are predominantly grown in a freestanding form, and integration onto a substrate is necessary for the fabrication of commercial devices. However, an effective method for integrating large single crystals onto a substrate has not yet been developed. In this study, a large-area (20 cm2) MAPbBr3 single crystal is bonded to an indium tin oxide (ITO) substrate using an ionic liquid, showing strong adhesion strength of 164 kPa. X-ray detectors based on ITO/MAPbBr3 single crystal bonded by methylammonium acetate achieved excellent sensitivity of 91,200 μC Gyair-1 cm-2, the highest among substrate-integrated halide perovskite single crystal X-ray detectors.

Structural transformation of C+ implanted diamond and lift-off process

Lift-off is a promising method to prepare thin, high-finish, and freestanding large-area single crystal and polycrystalline diamonds. However, accurate control of the damage layer characteristic to achieve both stress release and lift-off process is difficult. In this work, high-energy C + was implanted in single crystal diamond and polycrystalline diamond to create subsurface damage. The defect behavior and structural transformation of the ion implantation and annealing process were investigated. The homoepitaxial growth was subsequently carried out and the epitaxial layer was lifted off from the substrate by selectively etching the damaged layer. The results show that the cap layer and the substrate (below the damage layer) keep the sp 3 carbon structure before and after annealing, which is confirmed by the atomic-scale electron energy loss spectroscopy (EELS). The high-resolution transmission electron microscopy (HRTEM) images show that after annealing at 1000 °C for 1 h, the damaged layer was transformed from amorphous carbon to a mixture of graphite and amorphous carbon, providing the damaged layer that could be removed by electrochemical solution. Meanwhile, the distorted diamond area was changed to a sharp interface, which ensures the low roughness of the substrate surface after the lift-off process. After etching for 30 h, a freestanding polycrystalline diamond film with a thickness of 100 μm and a surface roughness of 1.68 nm was obtained. The roughness of the lift-off substrate surface is 1.10 nm, indicating the epitaxial growth can be repeated directly without polishing. • The defect behavior and structural transformation of the high-energy C + implanted diamonds before and after annealing process were investigated. • The stress state of the diamonds before and after ion implantation and after lift-off process were evaluated. • A freestanding polycrystalline diamond film with a thickness of 100 μm and a surface roughness of 1.68 nm was successful obtained.

Growth of Very Large MoS2 Single Crystals Using Out-Diffusion Transport and Their Use in Field Effect Transistors

Monolayer molybdenum disulfide (MoS2) is an attractive 2D material with a wide range of potential applications in the field of electronics and optoelectronics. To obtain the best performance, it is very necessary to grow large area single crystals of MoS2 (single domain) to avoid the effects of grain boundaries, but is exceptionally challenging to do this. Here, we report a novel method which we call out-diffusion vapor transport to grow large area single crystal monolayer MoS2 using an otherwise conventional chemical vapor deposition system. In this method, microchannels were created on the boat to significantly limit the region where MoOx vapor can react with S vapor to form crystals. This growth method resulted in triangular monolayer MoS2 single crystals up to ∼640 μm on a side grown on an oxidized silicon substrate, the largest crystals reported to date. Most of these crystals were multilayer at the center. This common feature has been identified in the literature as partially reduced transition metal oxide nucleates a second layer. We also achieved fully monolayer MoS2 single crystals up to ∼450 μm on a side, the largest demonstrated without the MoOx. Fabricated field effect transistors (FET) using MoS2 monolayer crystal as the active layer demonstrate a conventional n-type behavior, room-temperature mobility up to 45.5 cm2 V−1 s−1 and a maximum ON-Current (ION)/OFF-current (IOFF) ratio of 1.8 × 107. Raman and Photoluminescence results indicate that the as-grown large area monolayer crystals have high crystalline quality and uniformity with minimal defects, a finding that is consistent with the high electron mobility. This research work provides a superior technique to grow large-area high-quality single-crystal monolayer MoS2 without resorting to exotic equipment or techniques.

High mobility large area single crystal III–V thin film templates directly grown on amorphous SiO2 on silicon

In this Letter, we report the direct growth of single crystal III–V thin film mesas on amorphous SiO2 on Si using templated liquid phase growth. Unlike previous works, where crystal sizes demonstrated have been less than ∼10 μm, here, we show that by tuning the crystal growth conditions, crystals with dimensions greater than 100 μm and of high electron mobility can be directly grown on oxides. Specifically, InAs-on-oxide with mobilities reaching 5100 cm2/V s at 100 K, and ∼3200 cm2/V s at room temperature has been demonstrated. The excellent electronic performance is due to the single crystallinity of the grown material and creates new avenues for the monolithic direct integration of high-performance materials on non-epitaxial substrates, including silicon, and amorphous substrates, such as glasses and metals.

(Invited) 2D Materials: Crystal Growth for Future Device Structures

The isolation of graphene, now over decade ago, has given rise to the revitalization of an old full set of materials, two-dimensional materials (2DM), which have exceptional electrical, chemical and physical properties. Some of the materials under investigation in addition to graphene are hexagonal boron nitride (h-BN), semiconducting, metallic, and superconducting transition metal dichalcogenides (TMD) with a general chemical formula, MX2 where M is for example equal to Mo, W, Ta, Nb, Zr, Ti, and X = S, Se and Te, and others. While graphene is a material with many exceptional properties and h-BN is an excellent 2D insulator, TMD materials provide what neither graphene nor h-BN can, bandgap engineering that, in principle, can be used to create new devices that cannot be fabricated with h-BN and graphene alone. There is hope that 2DM can be integrated to fabricate numerous device types for many applications ranging from inkjet-printed circuits, photonic applications, flexible electronics, and high-performance electronics. However, to fully realize the benefits of these materials, the community will have to work together to define new device structures, device integration schemes, and materials growth processes to help the semiconductor industry make progress toward meeting the original goals of the International Technology Roadmap for Semiconductors (ITRS). A number of deposition/growth techniques have been used to prepare large area graphene, such as growth on SiC through the evaporation of Si at high temperatures, precipitation of carbon from metals, and catalytic chemical vapor deposition on Cu and Pt. Direct growth of good quality graphene on dielectrics/semiconductors other than SiC with reasonable properties has also been reported recently on Ge. Due to its insulating nature and compatibility with graphene and TMDs, the preparation of large area h-BN is also being developed on both metals and dielectrics. Transition metal dichalcogenides, however, present altogether different opportunities and difficulties in the preparation of low defect density large area single crystals. Vapor transport, chemical vapor deposition (CVD), and molecular beam epitaxy (MBE) are being developed to produce these materials for initial studies of materials physics and device fabrication. In addition, there is some effort in performing simulations to guide growth for both CVD and MBE growers. Therefore, there is an opportunity here to have the crystal growers and the modeling community collaborate to develop high quality materials and processes. A number of devices structures are currently under evaluation to take advantage of the basic properties of graphene, bi-layer graphene, h-BN and TMDs. Some of the devices are based on tunneling phenomena while others are based on excitonic phenomena. In this presentation I will present the state of the art results of graphene, h-BN, and a few TMD materials and their prospects for future electronic device applications.

Oriented Growth of Ultrathin Single Crystals of 2D Ruddlesden-Popper Hybrid Lead Iodide Perovskites for High-Performance Photodetectors.

Compared with their 3D counterparts, layered 2D Ruddlesden-Popper perovskites (2D RPPs) with the formula of (A')2A n-1Pb nX3 n+1 exhibit improved photo and moisture stability. To develop flexible single-crystalline electronics and wearable devices, cost-effective growth of large-area single crystals of 2D RPPs with large lateral size, ultrathin thickness, parallel orientation, and well-defined and controlled n values are highly desirable, but it remains still a challenge. Here, we modified the space-confined aqueous solution growth method to fabricate single-crystalline films of (BA)2(MA) n-1Pb nX3 n+1 and n = 1, 2, 3, respectively, with the lateral size reaching millimeter and thickness about 400-1000 nm. Moreover, the quantum well layers are found to be parallel to the substrate, well suitable for lateral transport requirement. We successfully integrated ultrathin single crystals of (BA)2(MA) n-1Pb nX3 n+1 ( n = 1-3) into a metal-semiconductor-metal two-terminal photodetector. The photoresponsive wavelength range was extended from 525 nm for n = 1 and 590 nm for n = 2 to 630 nm for n = 3 as a result of the reduced exciton band gap. The device of n = 2 single crystals shows the highest responsivity of 2.96 A/W and a detectivity of 1013 jones, while the device of n = 3 shows the lowest dark current 10-14 A, and therefore, its on/off ratio reaches 2862 at the bias voltage of 1 V.

Optical properties of single crystal silver thin films on mica for high performance plasmonic devices

We systematically investigate the optical properties of silver films to clear up the inconsistency in the published values of the dielectric function of silver. The silver films were deposited on mica by using a facing target sputtering system, which yielded a large area single crystal of silver suitable for the fabrication of high-finesse plasmonic devices and metamaterials. We confirmed that wide variations in the optical properties of silver were associated with the overall quality of the silver films including crystal structure, thickness, and surface roughness. The quality factor of the surface plasmon polaritons calculated for the obtained single crystal is 5 × 103, which is about five times higher than that for polycrystalline films.

Assembling semiconducting molecules by covalent attachment to a lamellar crystalline polymer substrate.

We have investigated the potential of polymers containing precisely spaced side-branches for thin film applications, particularly in the context of organic electronics. Upon crystallization, the side-branches were excluded from the crystalline core of a lamellar crystal. Thus, the surfaces of these crystals were covered by side-branches. By using carboxyl groups as side-branches, which allow for chemical reactions, we could functionalize the crystal with semiconducting molecules. Here, we compare properties of crystals differing in size: small nanocrystals and large single crystals. By assembling nanocrystals on a Langmuir trough, large areas could be covered by monolayers consisting of randomly arranged nanocrystals. Alternatively, we used a method based on local supersaturation to grow large area single crystals of the precisely side-branched polymer from solution. Attachment of the semiconducting molecules to the lamellar surface of large single crystals was possible, however, only after an appropriate annealing procedure. As a function of the duration of the grafting process, the morphology of the resulting layer of semiconducting molecules changed from patchy to compact.

Unveiling the structural origin of the high carrier mobility of a molecular monolayer on boron nitride

Very recently, it was demonstrated that the carrier mobility of a molecular monolayer dioctylbenzothienobenzothiophene (C8-BTBT) on boron nitride can reach 10 cm2/Vs, the highest among the previously reported monolayer molecular field-effect transistors. Here we show that the high-quality single crystal of the C8-BTBT monolayer may be the key origin of the record-high carrier mobility. We discover that the C8-BTBT molecules prefer layer-by-layer growth on both hexagonal boron nitride and graphene. The flatness of these substrates substantially decreases the C8-BTBT nucleation density and enables repeatable growth of large-area single crystal of the C8-BTBT monolayer. Our experimental result indicates that only out-of-plane roughness greater than 0.6 nm of the substrates could induce disturbance in the crystal growth and consequently affect the charge transport. This information would be important in guiding the growth of high-quality epitaxy molecular film.

Two-dimensional quasi-freestanding molecular crystals for high-performance organic field-effect transistors.

Two-dimensional atomic crystals are extensively studied in recent years due to their exciting physics and device applications. However, a molecular counterpart, with scalable processability and competitive device performance, is still challenging. Here, we demonstrate that high-quality few-layer dioctylbenzothienobenzothiophene molecular crystals can be grown on graphene or boron nitride substrate via van der Waals epitaxy, with precisely controlled thickness down to monolayer, large-area single crystal, low process temperature and patterning capability. The crystalline layers are atomically smooth and effectively decoupled from the substrate due to weak van der Waals interactions, affording a pristine interface for high-performance organic transistors. As a result, monolayer dioctylbenzothienobenzothiophene molecular crystal field-effect transistors on boron nitride show record-high carrier mobility up to 10 cm(2) V(-1) s(-1) and aggressively scaled saturation voltage ~1 V. Our work unveils an exciting new class of two-dimensional molecular materials for electronic and optoelectronic applications.

Large-area high-quality single crystal diamond

Abstract

Large area single crystal (0001) oriented MoS2

Layered metal dichalcogenide materials are a family of semiconductors with a wide range of energy band gaps and properties, the potential for exciting physics and technology applications. However, obtaining high crystal quality thin films over a large area remains a challenge. Here we show that chemical vapor deposition (CVD) can be used to achieve large area single crystal Molybdenum Disulfide (MoS2) thin films. Growth temperature and choice of substrate were found to critically impact the quality of film grown, and high temperature growth on (0001) oriented sapphire yielded highly oriented single crystal MoS2 films. Films grown under optimal conditions were found to be of high structural quality from high-resolution X-ray diffraction, transmission electron microscopy, and Raman measurements, approaching the quality of reference geological MoS2. Photoluminescence and electrical measurements confirmed the growth of optically active MoS2 with a low background carrier concentration, and high mobility. The CVD method reported here for the growth of high quality MoS2 thin films paves the way towards growth of a variety of layered 2D chalcogenide semiconductors and their heterostructures.

Template-Assisted Growth of Nominally Cubic (100)-Oriented Three-Dimensional Crack-Free Photonic Crystals

Three-dimensional (3D) photonic crystals (PhCs) are now beginning to acquire functionality via the use of dopants and heterostructures. However, the self-organized fabrication of large-area single crystals that are free of cracks and stacking faults has remained a challenge. We demonstrate a technology for the fabrication of (100)-oriented thin film 3D opal PhCs that exhibit no cracks over areas having no intrinsic size limit via a modified template-assisted colloidal self-assembly approach onto a patterned substrate. This technology potentially makes available large area regions of single photonic crystal, which can be used for optoelectronic devices.

Flux-Assisted Self-Assembly of Monodisperse Colloids

We have developed a novel method to grow ordered layers of monodisperse colloids on a flat substrate. The evaporation of the colloidal suspension in the presence of the inclined substrate is strengthened by an external gas flux directed on the meniscus. The meniscus oscillations caused by the gas flux have an evident effect on the ordering of the spheres on the substrate. Thick films (more than 150 layers in a single-step deposition) of large area single crystals (∼1 cm 2 ) can be obtained in a very short time (∼1 cm/h maximum growth rate) and from very diluted suspensions (up to 0.022% volume fraction).

Recent advances in ZnO materials and devices

Wurtzitic ZnO is a wide-bandgap (3.437 eV at 2 K) semiconductor which has many applications, such as piezoelectric transducers, varistors, phosphors, and transparent conducting films. Most of these applications require only polycrystalline material; however, recent successes in producing large-area single crystals have opened up the possibility of producing blue and UV light emitters, and high-temperature, high-power transistors. The main advantages of ZnO as a light emitter are its large exciton binding energy (60 meV), and the existence of well-developed bulk and epitaxial growth processes; for electronic applications, its attractiveness lies in having high breakdown strength and high saturation velocity. Optical UV lasing, at both low and high temperatures, has already been demonstrated, although efficient electrical lasing must await the further development of good, p-type material. ZnO is also much more resistant to radiation damage than are other common semiconductor materials, such as Si, GaAs, CdS, and even GaN; thus, it should be useful for space applications.

Fabrication of large-area face-centered-cubic hard-sphere colloidal crystals by shear alignment

We make hard-sphere colloidal crystals from polymethyl methacrylate spheres suspended in organic solvents at high volume fractions. The samples are crystallized between two glass plates separated by 10-\ensuremath{\mu}m spacer beads. We study the optical scattering from these systems and describe methods for discriminating between the various crystal packings. Crystals formed simply by increasing the volume fraction beyond the liquid-solid phase transition tend to be small and predominantly random close packed. However, we find that by forming these crystals while applying controlled shear to the glass plates, large-area single crystals can be made. These crystals are much more regular and appear to be predominantly twinned face-centred cubic. The creation of single-orientation face-centred cubic crystals appears possible when shear is applied in one direction.

Investigation of the transition range in seeded vapour grown ZnSe crystals

Prerequisite for the growth of large area single crystals are exactly (111)Se orientated seeds. For both used growth methods, seeded physical vapour transport (SPVT) and seeded chemical vapour transport (SCVT), an improved crystal quality can be achieved. In SCVT crystals, optically active deep level (DL) defects dominate mainly due to the self activated (SA)-centre. The transition range width was more than three times that of SPVT material, but in the bulk the concentration of linear defects is lower. Strong exciton luminescence and decreasing DL emission were found in the bulk of SPVT crystals. The decision what method should be used for optimal substrate performance has to be drawn after manufacturing light emitting devices by epitaxial methods.

Beam-Recrystallized Device-Worthy Films of Si on SiO2 via Control of the Grain Boundary Location

ABSTRACTDevice-worthy films of silicon on SiO2 have been produced using laser annealing and antireflection stripes. If no seeding is used, grain boundaries will be localized beneath the stripes; with seeding, large-area single crystals can be grown, of uniform <100> orientation. N-channel transistors show a mobility of 620 cm2/V.s and present leakage currents which can be reduced, however, down to a few pA/um when the substrate (back gate) is negatively biased to − 5 V. Ring oscillators have also been made, which oscillate with a delay per stage of 1 nsec.

Preparation of Large Area Single-Crystal Cuprous Oxide

Large area single crystals of Cu2O were grown by the process of high temperature annealing. Cu2O was prepared in finely polycrystalline form by the complete oxidation of Cu plate in air at temperatures of 1020°C to 1050°C. Subsequent annealing of the polycrystalline plates at higher temperatures allowed secondary recrystallization to occur. Single-crystal grains having surface areas larger than 1 in.2 were grown consistently on Cu2O plates having thicknesses of 0.010 in. to 0.060 in. In some cases, entire polycrystalline plates were transformed into single crystals, and as a result, individual single crystals having surface areas of 3 in.2 and larger were obtained. The annealing temperature and the annealing time were found to depend markedly on the plate thickness. Thick plates required lower temperatures and longer annealing times than the thinner plates. X-ray analysis of the large grains verified that they were single crystals without excess strain, and indicated preferred orientation, with the (211) and (311) planes predominating. Resistance profile measurements at room temperature on quenched samples showed that a variation in resistance exists through the thickness of the plate.