Recent Advances in Growth of Large‐Sized 2D Single Crystals on Cu Substrates

Large‐scale and high‐quality 2D materials have been an emerging and promising choice for use in modern chemistry and physics owing to their fascinating property profile. The past few years have witnessed inspiringly progressing development in controlled fabrication of large‐sized and single‐crystal 2D materials. Among those production methods, chemical vapor deposition (CVD) has drawn the most attention because of its fine control over size and quality of 2D materials by modulating the growth conditions. Meanwhile, Cu has been widely accepted as the most popular catalyst due to its significant merit in growing monolayer 2D materials in the CVD process. Herein, very recent advances in preparing large‐sized 2D single crystals on Cu substrates by CVD are presented. First, the unique features of Cu will be given in terms of ultralow precursor solubility and feasible surface engineering. Then, scaled growth of graphene and hexagonal boron nitride (h‐BN) crystals on Cu substrates is demonstrated, wherein different kinds of Cu surfaces have been employed. Furthermore, the growth mechanism for the growth of 2D single crystals is exhibited, offering a guideline to elucidate the in‐depth growth dynamics and kinetics. Finally, relevant issues for industrial‐scale mass production of 2D single crystals are discussed and a promising future is expected.     

2D Intrinsic Ferromagnetic MnP Single Crystals

2D intrinsic ferromagnetic materials are highly anticipated in spintronic devices due to their coveted 2D limited magnetism. However, 2D non‐layered intrinsic ferromagnets have received sporadic attention, which is largely attributed to the fact that their synthesis is still a great challenge. Significantly, manganese phosphide (MnP) is a promising non‐layered intrinsic ferromagnet with excellent properties. Herein, high‐quality 2D MnP single crystals formed over liquid metal tin (Sn) is demonstrated through a facile chemical vapor deposition technique. The introduction of liquid metal Sn provides a fertile ground for the growth of 2D MnP single crystals. Interestingly, 2D MnP single crystals maintain their intrinsic ferromagnetism and exhibit a Curie temperature above room temperature. The research enriches the diversity of 2D intrinsic ferromagnetic materials, opening up opportunities for further exploration of their unique properties and rich applications.     

Epitaxial Growth of Ternary Topological Insulator Bi2Te2Se 2D Crystals on Mica

Nanostructures of ternary topological insulator (TI) Bi₂Te₂Se are, in principle, advantageous to the manifestation of topologically nontrivial surface states, due to significantly enhanced surface‐to‐volume ratio compared with its bulk crystals counterparts. Herein, the synthesis of 2D Bi₂Te₂Se crystals on mica via the van der Waals epitaxy method is explored and systematically the growth behaviors during the synthesis process are investigated. Accordingly, 2D Bi₂Te₂Se crystals with domain size up to 50 µm large and thickness down to 2 nm are obtained. A pronounced weak antilocalization effect is clearly observed in the 2D Bi₂Te₂Se crystals at 2 K. The method for epitaxial growth of 2D ternary Bi₂Te₂Se crystals may inspire materials engineering toward enhanced manifestation of the subtle surface states of TIs and thereby facilitate their potential applications in next‐generation spintronics.     

氧化碲大单晶的加压提拉生长

本文叙述了加压单晶炉的结构,重点介绍了传动机构及利用压力下的模拟体等径控制系统实现 TeO_2大单晶生长的直径自动控制。生长出了等径度和质量良好的以[110]、[100]等为提拉生长方向的 TeO_2大单晶,晶体直径为φ35～85mm,等径长度35～100mm,晶体的最大重量达1.4kg。本文还讨论了影响等径生长优质 TeO_2晶体的某些因素。经多次实验证明,我们设计研制的加压单晶炉是一种既经济又有实用价值的装置。     

A “Phase Separation” Molecular Design Strategy Towards Large‐Area 2D Molecular Crystals

2D molecular crystals (2DMCs) have attracted considerable attention because of their unique optoelectronic properties and potential applications. Taking advantage of the solution processability of organic semiconductors, solution self‐assembly is considered an effective way to grow large‐area 2DMCs. However, this route is largely blocked because a precise molecular design towards 2DMCs is missing and little is known about the relationship between 2D solution self‐assembly and molecular structure. A “phase separation” molecular design strategy towards 2DMCs is proposed and layer‐by‐layer growth of millimeter‐sized monolayer or few‐layer 2DMCs is realized. High‐performance organic phototransistors are constructed based on the 2DMCs with unprecedented photosensitivity (2.58 × 10⁷), high responsivity (1.91 × 10⁴ A W^?1), and high detectivity (4.93 × 10¹⁵ Jones). This “phase separation” molecular design strategy provides a guide for the design and synthesis of novel organic semiconductors that self‐assemble into large‐area 2DMCs for advanced organic (opto)electronics.     

锗单晶材料的生长与应用

锗单晶材料由于独特的性能而被广泛应用于微电子技术、红外技术、核探测、太阳电池等多个领域.简要介绍了直拉生长的工艺及特点,无位错直拉锗单晶的生长与现状,以及锗单晶材料在不同领域的应用和发展.     

Free‐Standing 2D Hexagonal Aluminum Nitride Dielectric Crystals for High‐Performance Organic Field‐Effect Transistors

The existence of defects and traps in a transistor plays an adverse role on efficient charge transport. In response to this challenge, extensive research has been conducted on semiconductor crystalline materials in the past decades. However, the development of dielectric crystals for transistors is still in its infancy due to the lack of appropriate dielectric crystalline materials and, most importantly, the crystal morphology required by the gate dielectric layer, which is also crucial for the construction of high‐performance transistor as it can greatly improve the interfacial quality of carrier transport path. Here, a new type of dielectric crystal of hexagonal aluminum nitride (AlN) with the desired 2D morphology of combing thin thickness with large lateral dimension is synthesized. Such a suitable morphology in combination with the outstanding dielectric properties of AlN makes it promising as a gate dielectric for transistors. Furthermore, ultrathin 2,6‐diphenylanthracene molecular crystals with only a few molecular layers can be prepared on AlN crystal via van der Waals epitaxy. As a result, this all‐crystalline system incorporating dielectric and semiconductor crystals greatly enhances the overall performance of a transistor, indicating the importance of minimizing defects and preparing high‐quality semiconductor/dielectric interface in a transistor configuration.     

大尺寸6H-SiC半导体单晶材料的生长

报道了生长SiC单晶的PVT法生长工艺,研究了晶体生长温度、温度梯度、生长室压力、杂质等因素对晶体生长和晶体质量的影响,确定出合理的工艺条件,生长出φ45mmSiC单晶.X射线衍射表明,生长的单晶为6H多型结构,通过腐蚀法得到晶体中微管道密度约为10³cm^-2,位错密度约为10⁴～10⁵cm^-2.测试了SiC单晶的半导体特性,结果表明:晶体为n型,电阻率约300Ω·cm,迁移率90cm2V^-1S^-1,载流子浓度在10¹⁴cm^-3量级.     

Graphene Single Crystals: Size and Morphology Engineering

Recently developed chemical vapor deposition (CVD) is considered as an effective way to large‐area and high‐quality graphene preparation due to its ultra‐low cost, high controllability, and high scalability. However, CVD‐grown graphene film is polycrystalline, and composed of numerous grains separated by grain boundaries, which are detrimental to graphene‐based electronics. Intensive investigations have been inspired on the controlled growth of graphene single crystals with the absence of intrinsic defects. As the two most concerned parameters, the size and morphology serve critical roles in affecting properties and understanding the growth mechanism of graphene crystals. Therefore, a precise tuning of the size and morphology will be of great significance in scale‐up graphene production and wide applications. Here, recent advances in the synthesis of graphene single crystals on both metals and dielectric substrates by the CVD method are discussed. The review mainly covers the size and morphology engineering of graphene single crystals. Furthermore, recent progress in the growth mechanism and device applications of graphene single crystals are presented. Finally, the opportunities and challenges are discussed.     

Salt-Assisted Low-Temperature Growth of 2D Bi2O2Se with Controlled Thickness for Electronics

Bi₂O₂Se is the most promising 2D material due to its semiconducting feature and high mobility, making it propitious channel material for high-performance electronics that demands highly crystalline Bi₂O₂Se at low-growth temperature. Here, a low-temperature salt-assisted chemical vapor deposition approach for growing single-domain Bi₂O₂Se on a millimeter scale with thicknesses of multilayer to monolayer is presented. Because of the advantage of thickness-dependent growth, systematical scrutiny of layer-dependent Raman spectroscopy of Bi₂O₂Se from monolayer to bulk is investigated, revealing a redshift of the A_1g mode at 162.4 cm⁻¹. Moreover, the long-term environmental stability of ≈2.4 nm thick Bi₂O₂Se is confirmed after exposing the sample for 1.5 years to air. The backgated field effect transistor (FET) based on a few-layered Bi₂O₂Se flake represents decent carrier mobility (≈287 cm² V⁻¹s⁻¹) and an ON/OFF ratio of up to 10⁷. This report indicates a technique to grow large-domain thickness controlled Bi₂O₂Se single crystals for electronics.     

Electronic-Grade High-Quality Perovskite Single Crystals by a Steady Self-Supply Solution Growth for High-Performance X-ray Detectors

High-quality perovskite single crystals with large size are highly desirable for the fundamental research and high energy detection application. Here, a simple and convenient solution method, featuring continuous-mass transport process (CMTP) by a steady self-supply way, is shown to keep the growth of semiconductor single crystals continuously stable at a constant growth rate until an expected crystal size is achieved. A significantly reduced full width at half-maximum (36 arcsec) of the (400) plane from the X-ray rocking curve indicates a low angular dislocation of 6.8 × 10⁶ cm⁻² and hence a higher crystalline quality for the CH₃NH₃PbI₃(MAPbI₃) single crystals grown by CMTP as compared to the conventional inverse temperature crystallization (ITC) method. Furthermore, the CMTP-based single crystals have lower trap density, reduced by nearly 200% to 4.5 × 10⁹ cm⁻³, higher mobility increased by 187% to 150.2 cm² V⁻¹ s⁻¹, and higher mobility–lifetime product increased by around 450% to 1.6 × 10⁻³ cm² V⁻¹, as compared with the ITC-grown reference sample. The high performance of the CMTP-based MAPbI₃ X-ray detector is comparable to that of a traditional high-quality CdZnTe device, indicating the CMTP method as being a cost-efficient strategy for high-quality electronic-grade semiconductor single crystals.     

N‐Type 2D Organic Single Crystals for High‐Performance Organic Field‐Effect Transistors and Near‐Infrared Phototransistors

Organic field‐effect transistors and near‐infrared (NIR) organic phototransistors (OPTs) have attracted world's attention in many fields in the past decades. In general, the sensitivity, distinguishing the signal from noise, is the key parameter to evaluate the performance of NIR OPTs, which is decided by responsivity and dark current. 2D single crystal films of organic semiconductors (2DCOS) are promising functional materials due to their long‐range order in spite of only few molecular layers. Herein, for the first time, air‐stable 2DCOS of n‐type organic semiconductors (a furan‐thiophene quinoidal compound, TFT‐CN) with strong absorbance around 830 nm, by the facile drop‐casting method on the surface of water are successfully prepared. Almost millimeter‐sized TFT‐CN 2DCOS are obtained and their thickness is below 5 nm. A competitive field‐effect electron mobility (1.36 cm² V^?1 s^?1) and high on/off ratio (up to 10⁸) are obtained in air. Impressively, the ultrasensitive NIR phototransistors operating at the off‐state exhibit a very low dark current of ≈0.3 pA and an ultrahigh detectivity (D*) exceeding 6 × 10¹⁴ Jones because the devices can operate in full depletion at the off‐state, superior to the majority of the reported organic‐based NIR phototransistors.     

Phase Engineering of 2D Tin Sulfides

Tin sulfides can exist in a variety of phases and polytypes due to the different oxidation states of Sn. A subset of these phases and polytypes take the form of layered 2D structures that give rise to a wide host of electronic and optical properties. Hence, achieving control over the phase, polytype, and thickness of tin sulfides is necessary to utilize this wide range of properties exhibited by the compound. This study reports on phase‐selective growth of both hexagonal tin (IV) sulfide SnS₂ and orthorhombic tin (II) sulfide SnS crystals with diameters of over tens of microns on SiO₂ substrates through atmospheric pressure vapor‐phase method in a conventional horizontal quartz tube furnace with SnO₂ and S powders as the source materials. Detailed characterization of each phase of tin sulfide crystals is performed using various microscopy and spectroscopy methods, and the results are corroborated by ab initio density functional theory calculations.     

Room-Temperature Synthesis of 2D Janus Crystals and their Heterostructures

Janus crystals represent an exciting class of 2D materials with different atomic species on their upper and lower facets. Theories have predicted that this symmetry breaking induces an electric field and leads to a wealth of novel properties, such as large Rashba spin–orbit coupling and formation of strongly correlated electronic states. Monolayer MoSSe Janus crystals have been synthesized by two methods, via controlled sulfurization of monolayer MoSe₂ and via plasma stripping followed thermal annealing of MoS₂. However, the high processing temperatures prevent growth of other Janus materials and their heterostructures. Here, a room-temperature technique for the synthesis of a variety of Janus monolayers with high structural and optical quality is reported. This process involves low-energy reactive radical precursors, which enables selective removal and replacement of the uppermost chalcogen layer, thus transforming classical transition metal dichalcogenides into a Janus structure. The resulting materials show clear mixed character for their excitonic transitions, and more importantly, the presented room-temperature method enables the demonstration of first vertical and lateral heterojunctions of 2D Janus TMDs. The results present significant and pioneering advances in the synthesis of new classes of 2D materials, and pave the way for the creation of heterostructures from 2D Janus layers.     

大尺寸ZnTe单晶生长技术的研究进展

介绍了以光电应用为背景的大尺寸ZnTe单晶生长技术的研究进展,综述了大尺寸ZnTe单晶不同生长技术的特点及其对单晶性能的影响,重点分析了为解决ZnTe生长过程中存在的蒸汽压过高的问题,通过控制提高Te的比例,实现低温低压生长,对比了不同生长方法的生长机理差异及其对单晶尺寸、缺陷和性能的影响,为寻求解决大尺寸单晶生长面临的问题提供了参考。     

Growth of larger and more perfect single crystals of KClO4 in silica gel

As part of a continuing effort on crystal growth in gels, this paper describes the growth of large transparent single crystals of KClO₄ by the improved design. The effect of various anionic and cationic components on nucleation, growth and quality of these crystals has been studied. It has been found that a combination of KNO₃ and HClO₄ as the reactants resulted in the best crystals in terms of crystal size, quality and inter-crystalline separation. The effect of various impurities on nucleation, growth and quality of these crystals has been studied. It has been found that the impurities which enhance the solubility of KClO₄ have a positive effect on the size and quality of the crystals. A new etchant, consisting of concentrated HCl and H₂SO₄ in the volume ratio 2:3 has been found to reveal as-grown as well as freshly introduced dislocations.     

Kinetics of Graphene and 2D Materials Growth

During the last 10 years, remarkable achievements on the chemical vapor deposition (CVD) growth of 2D materials have been made, but the understanding of the underlying mechanisms is still relatively limited. Here, the current progress on the understanding of the growth kinetics of 2D materials, especially for their CVD synthesis, is reviewed. In order to present a complete picture of 2D materials' growth kinetics, the following factors are discussed: i) two types of growth modes, namely attachment‐limited growth and diffusion‐limited growth; ii) the etching of 2D materials, which offers an additional degree of freedom for growth control; iii) a number of experimental factors in graphene CVD synthesis, such as structure of the substrate, pressure of hydrogen or oxygen, temperature, etc., which are found to have profound effects on the growth kinetics; iv) double‐layer and few‐layer 2D materials' growth, which has distinct features different from the growth of single‐layer 2D materials; and v) the growth of polycrystalline 2D materials by the coalescence of a few single crystalline domains. Finally, the current challenges and opportunities in future 2D materials' synthesis are summarized.