Resolution Scanning Transmission Electron Microscopy Research Articles

Thermally Induced Irreversible Disorder in Interlayer Stacking of γ-GeSe.

The interlayer stacking shift in van der Waals (vdW) crystals represents an important degree of freedom to control various material properties, including magnetism, ferroelectricity, and electrical properties. On the other hand, the structural phase transitions driven by interlayer sliding in vdW crystals often exhibit thickness-dependent, sample-specific behaviors with significant hysteresis, complicating a clear understanding of their intrinsic nature. Here, the stacking configuration of the recently identified vdW crystal, γ-GeSe, is investigated, and the disordering manipulation of stacking sequence is demonstrated. It is observed that the well-ordered AB' stacking configuration in as-synthesized samples undergoes irreversible disordering upon Joule heating via electrical biasing or thermal treatment, as confirmed by atomic resolution scanning transmission electron microscopy (STEM). Statistical analysis of STEM data reveal the emergence of stacking disorder, with samples subjected to high electrical bias reaching the maximum levels of disorder. The energies of various stacking configurations and energy barriers for interlayer sliding are examined using first-principles calculation and a parameterized model to elucidate the key structural parameters related to stacking shift. The susceptibility of interlayer stacking to disorder through electrical or thermal treatments should be carefully considered to fully comprehend the structural and electrical properties of vdW crystals.

Atomistic oxidation mechanism of Bi0.5Sb1.5Te3 (0001) surface

Surface oxidation can potentially influence transport properties of thermoelectric materials and service performance of thermoelectric devices. Here, the oxidation mechanism of the (0001) surface of a widely used p-type TE material, Bi0.5Sb1.5Te3 (BST), was investigated using spherical aberration corrected scanning transmission electron microscopy (STEM). Combining atomic resolution STEM and density function theory (DFT), it was revealed that oxidation occurs at room temperature in the dry air through O diffusion into the surface quintuple layer, facilitating formation of both cation and anion vacancies, weakening the Bi-Te and Sb-Te bonds, leading to oxidation product Sb2O3, amorphous Te, and Bi-rich Bi2Te3. Formation of a thin O-rich cation-deficient quintuple layer on the surface and the Bi-rich BST region can significantly reduce the interfacial reaction between BST and Ni electrode, as the reaction layer thickness is reduced by 75% after the surface oxidation. This work provides essential structural information on surface oxidation mechanism and its influence on properties and performance of TE materials and devices.

Non-radiative recombination centres in InGaN/GaN nanowires revealed by statistical analysis of cathodoluminescence intensity maps and electron microscopy

The methodology of statistical analysis of cathodoluminescence (CL) intensity mappings on ensembles of several hundreds of InGaN/GaN nanowires (NWs) used to quantify non-radiative recombination centres (NRCs) was validated on InGaN/GaN NWs exhibiting spatially homogeneous cathodoluminescence at the scale of single NWs. Cathodoluminescence intensity variations obeying Poisson's statistics were assigned to the presence of randomly incorporated point defects acting as NRCs. Additionally, another type of NRCs, namely extended defects leading to spatially inhomogeneous cathodoluminescence intensity at the scale of single InGaN/GaN NWs are revealed by high resolution scanning transmission electron microscopy, geometrical phase analysis and two-beam diffraction conditions techniques. Such defects are responsible for deviations from Poisson's statistics, allowing one to achieve a rapid evaluation of the crystallographic and optical properties of several hundreds of NWs in a single cathodoluminescence intensity mapping experiment.

Real-Space Tilting Method for Atomic Resolution STEM Imaging of Nanocrystalline Materials.

Atomic-resolution scanning transmission electron microscopy (STEM) characterization requires precise tilting of the specimen to a high symmetric zone axis, which is usually processed in reciprocal space by following the diffraction patterns. However, for small-sized nanocrystalline materials, their diffraction patterns are often too faint to guide the tilting process. Here, a simple and effective tilting method is developed based on the diffraction contrast change of the shadow image in the Ronchigram. The misorientation angle of the specimen can be calculated and tilted to the zone axis based on the position of the shadow image with lowest intensity. This method requires no prior knowledge of the sample and the maximum misorientation angle that can be corrected is >±6.9° with sub-mrad accuracy. It operates in real space, without recording the diffraction patterns of the specimens, making it particularly effective for nanocrystalline materials. Combined with the scripting to control the microscope, the sample can be automatically tilted to the zone axis under low dose conditions (<0.17 e-Å- 2s-1), facilitating the imaging of beam sensitive materials such as zeolites or metal-organic frameworks. This automated tilting method can significantly contribute to the atomic-scale characterization of the nanocrystalline materials by STEM imaging.

Atomic resolution scanning transmission electron microscopy at liquid helium temperatures for quantum materials

Fundamental quantum phenomena in condensed matter, ranging from correlated electron systems to quantum information processors, manifest their emergent characteristics and behaviors predominantly at low temperatures. This necessitates the use of liquid helium (LHe) cooling for experimental observation. Atomic resolution scanning transmission electron microscopy combined with LHe cooling (cryo-STEM) provides a powerful characterization technique to probe local atomic structural modulations and their coupling with charge, spin and orbital degrees-of-freedom in quantum materials. However, achieving atomic resolution in cryo-STEM is exceptionally challenging, primarily due to sample drifts arising from temperature changes and noises associated with LHe bubbling, turbulent gas flow, etc. In this work, we demonstrate atomic resolution cryo-STEM imaging at LHe temperatures using a commercial side-entry LHe cooling holder. Firstly, we examine STEM imaging performance as a function of He gas flow rate, identifying two primary noise sources: He-gas pulsing and He-gas bubbling. Secondly, we propose two strategies to achieve low noise conditions for atomic resolution STEM imaging: either by temporarily suppressing He gas flow rate using the needle valve or by acquiring images during the natural warming process. Lastly, we show the applications of image acquisition methods and image processing techniques in investigating structural phase transitions in Cr2Ge2Te6, CuIr2S4, and CrCl3. Our findings represent an advance in the field of atomic resolution electron microscopy imaging for quantum materials and devices at LHe temperatures, which can be applied to other commercial side-entry LHe cooling TEM holders.

Analysis of Defect Structures during the Early-Stages of PVT Growth of 4H-SiC Crystals

To better understand the effects of various growth parameters during the early-stages of PVT growth of 4H-SiC on resulting defect structures, multiple short duration growths have been carried out under varying conditions of seed quality, nucleation rate, thermal gradients, and N incorporation. Besides the replication of TSDs/TMDs and TEDs as well as the deflection of TSDs/TMDs into Frank dislocations, synchrotron monochromatic beam x-ray topography (SMBXT) studies also reveal the formation of stacking faults bounded by Frank dislocations. Using ray tracing simulations to characterize the Frank dislocations, three types of stacking faults are revealed: Type 1 stacking fault resulting from 2D nucleation of 6H polytype on terraces; Type 2 stacking fault resulting from macrostep overgrowth of the surface growth spiral steps of TSDs/TMDs which separate into c/2 or c/4 increments; Type 3 stacking fault resulting from vicinal step overgrowth of surface growth spiral steps of TSDs/TMDs which separate into c/4 and 3c/4 increments. Analysis of atomic resolution scanning transmission electron microscopy (STEM) images reveals the mechanism of the Type 3 fault.

Influence of Domain Size and Support Composition on the Reducibility of SiO2 and TiO2 Supported Tungsten Oxide Clusters.

Supported tungsten oxides are widely used in a variety of catalytic reactions. Depending on the support, the cluster size, oxidation state, reducibility and speciation of the tungsten oxides can widely differ. When promoted with a platinum group metal, the resulting spillover of hydrogen may facilitate the reduction of supported tungsten oxide species, depending on the support. High resolution scanning transmission electron microscopy imaging showed nanometer scale WO x clusters were synthesized on SiO2 whereas highly dispersed species were formed on TiO2. Results from H2-temperature-programmed reduction showed the presence of Pd lowered the initial reduction temperature of SiO2-supported WO x species but interestingly did not affect that of TiO2-supported WO x . X-ray photoelectron and absorption spectroscopies showed the W atoms in SiO2-supported WO x species reduce from a +6 oxidation state to primarily +5 after thermal treatment in 5% H2, while the fraction of W in the +5 oxidation state was relatively unaffected by reduction treatment of TiO2-supported WO x . The unusual behavior of TiO2-supported WO x was explained by quantum chemical calculations that reveal the lack of change in the oxidation state of W is attributed to charge delocalization on the surface atoms of the titania support, which does not occur on silica. Moreover, modeling results at <600 K in the presence of H2 suggest the formation of Brønsted acid sites, and the absence of Lewis acid sites, on larger aggregates of WO x on silica and all cluster sizes on titania. These results provide experimental and theoretical insights into the nature of supported tungsten oxide clusters under conditions relevant to various catalytic reactions.

Dopant site occupancies and iron valence states in SrZnxFe18−xO27 W-type hexaferrites using site-selective X-ray/electron spectroscopy

Zn-doped W-type Sr hexaferrite (SrZnxFe18−xO27; SrZnx-WHF) is an anticipated rare-earth-free hard magnetic material with strong magnetocrystalline anisotropy and saturation magnetization. To examine the origin of its high magnetic performance, the site distribution of Zn over seven crystallographically inequivalent Fe sites and the site-dependent valence states of Fe were investigated using site-selective elemental/chemical analysis techniques. The dominant occupation of Zn2+ at the 4etet(S) and 4ftet(S) tetrahedral sites was determined quantitatively using high-angular-resolution electron-channeling X-ray spectroscopy and statistical data analysis. The combined application of high-angular-resolution electron channeling electron spectroscopy and atomic-column resolution scanning transmission electron microscopy–electron energy-loss spectroscopy helped unambiguously clarify that most of the Fe2+ ions existed at the 6goct(S-S) octahedral site. Density functional theory calculations have shown that Zn doping leads to a redistribution of the charges toward Fe ions at this site. This redistribution preserves the local charge balance and amplifies the total number of parallel spins. Hence, the enhanced magnetocrystalline anisotropy and saturation magnetization in SrZnx-WHF can be inferred to originate from the charge redistribution at the 6goct(S-S) site, which is influenced by the presence of nonmagnetic Zn.

Tuning Van Der Waals Heterostructure of WS2/SrTiO3 Via in Situ Transmission Electron Microscopy

Monolayer two-dimensional (2D) materials have been widely researched and discussed in recent years, while multi-layers have received comparatively less attention. Nowadays, combining different materials to create heterostructures has become mainstream. In semiconductor industry, heterostructure can form devices such as lasers, light-emitting diodes, fast transistors and so on. Heterostructures can create well electronic properties by combining two different materials together. Therefore, heterostructures become a great tool to manipulate the electronic structures. In traditional heterostructures, the interfaces between two different materials are formed by covalent bonds, hence it requires similar lattice constants and structures. On the other hand, novel van der Waal heterostructures (vdW-heterostructure), formed by 2D materials, do not require the same strict similarity as traditional ones. VdW-heterostructures, which create 3D structures through van der Waals forces, provide a new perspective. In this study, we created a vdW-heterostructures by stacking tungsten disulfide (WS2) with single-crystal strontium titanate, SrTiO3 (STO), shown in Figure 1a,b. The crystalline atomic-layer WS2 and STO were synthesized by chemical vapor deposition (CVD) and pulsed laser deposition (PLD), respectively. They are analyzed by high-resolution transmission electron microscope (HRTEM) shown in Figure 1c-h. Once the vdW-heterostructures are formed, we conducted in situ heating by TEM. Through the advanced in situ technique, we observed the change of the twisted stacking angle by heating the vdW-heterostructure. Ultimately, the lattices will shift and rotate, minimizing the free energy, so that the vdW-heterostructure will be aligned and formed epitaxially. In addition, we utilized atomic resolution scanning transmission electron microscope (STEM) to identify the stacking images and the moiré pattern of the vdW-heterostructure. During the rotation, we can observed different moiré patterns by various twisted stacking angles. These different moiré patterns can produce different electrical properties, which can be applied to advanced semiconductor devices. Keywords: high-resolution TEM/STEM, in situ heating, 2D materials, van der Waal heterostructures, moiré pattern Figure 1. The vdW-heterostructure of STO/WS2. a) The diagram showing that the formation process of WS2/STO vdW-heterostructures which have different twisted stacking angles. b) The low-magnification SEM image showing that the single crystal STO thin film is transferred onto the TEM heating chips. The circles in the middle are the observation windows for transmission electrons. c-e) HRTEM images. f-g) Diffraction patterns of HRTEM. c,f) Single crystal STO thin film with d-spacing (1−10) = 0.284 nm. d,g) Monolayer single crystal WS2 with d-spacing (−110) = 0.274 nm. e,h) WS2(red)/STO(yellow) vdW-heterostructure with stacking angle 3.6°. Figure 1

Field and Structure Imaging by Magnetic-field-free Atomic Resolution Scanning Transmission Electron Microscopy

Field and Structure Imaging by Magnetic-field-free Atomic Resolution Scanning Transmission Electron Microscopy

Clarification of the spontaneous polarization direction in crystals with wurtzite structure

The wurtzite structure is one of the most frequently found crystal structures in modern semiconductors and its inherent spontaneous polarization is a defining materials property. Despite this significance, confusion has been rampant in the literature with respect to the orientation of the spontaneous polarization inside the unit cell of the wurtzite structure, especially for the technologically very relevant III-N compounds (AlN, GaN, and InN). In particular, the spontaneous polarization has been reported to either point up or down for the same unit cell orientation, depending on the literature source—with important implications for, e.g., the carrier type and density expected at interfaces of heterostructures involving materials with the wurtzite structure. This perspective aims to resolve this ambiguity by reviewing available reports on the direction of the energetically preferred polarization direction in the presence of external electric fields as well as atomically resolved scanning transmission electron microscopy images. While we use ferroelectric wurtzite Al1−xScxN as a key example, our conclusions are generalizable to other compounds with the same crystal structure. We demonstrate that a metal-polar unit cell must be associated with an upward polarization vector—which is contrary to long-standing conventional wisdom.

Large-Scale Direct Growth of Monolayer MoS2 on Patterned Graphene for van der Waals Ultrafast Photoactive Circuits.

Two-dimensional (2D) van der Waals heterostructures combine the distinct properties of individual 2D materials, resulting in metamaterials, ideal for emergent electronic, optoelectronic, and spintronic phenomena. A significant challenge in harnessing these properties for future hybrid circuits is their large-scale realization and integration into graphene interconnects. In this work, we demonstrate the direct growth of molybdenum disulfide (MoS2) crystals on patterned graphene channels. By enhancing control over vapor transport through a confined space chemical vapor deposition growth technique, we achieve the preferential deposition of monolayer MoS2 crystals on monolayer graphene. Atomic resolution scanning transmission electron microscopy reveals the high structural integrity of the heterostructures. Through in-depth spectroscopic characterization, we unveil charge transfer in Graphene/MoS2, with MoS2 introducing p-type doping to graphene, as confirmed by our electrical measurements. Photoconductivity characterization shows that photoactive regions can be locally created in graphene channels covered by MoS2 layers. Time-resolved ultrafast transient absorption (TA) spectroscopy reveals accelerated charge decay kinetics in Graphene/MoS2 heterostructures compared to standalone MoS2 and upconversion for below band gap excitation conditions. Our proof-of-concept results pave the way for the direct growth of van der Waals heterostructure circuits with significant implications for ultrafast photoactive nanoelectronics and optospintronic applications.

Atomic resolution transmission electron microscopy visualisation of channel occupancy in beryl in different crystallographic directions

The causes of colour in beryl have been a research topic for decades. For some varieties, such as emerald (green, coloured by Cr3+ and/or V3+), the main cause of colour is substitutions by metal atoms within the framework. However, the causes for the yellow and blue colours in heliodor, golden beryl and aquamarine are still debated. It is generally agreed that Fe ions are responsible for the colour, but there are differing conclusions about the valence states of these ions, the occupied positions and the colour-inducing processes involved. The colour of aquamarine is commonly attributed to intervalence charge transfer (IVCT) between Fe3+ and Fe2+. Various combinations of sites have been proposed to host the Fe ions engaging in this IVCT. Here we present a new approach to address the topic of colour generation: atomic resolution scanning transmission electron microscopy (STEM). For the first time, atomic resolution images of a beryl (natural aquamarine) are presented in the three crystallographic directions [0001], [1-210] and [1-100]. Ions are clearly resolved in the channels. From the ratio of channel occupation and the correlation of the atoms per formula unit (apfu) calculations we conclude that Fe resides in the framework, not in the channels. The projections in the [1-210] direction directly show that the cavity channel site 2a is occupied, most likely by Cs, in agreement with recent results in the literature.

Pt single-atom electrocatalysts at Cu2O nanowires for boosting electrochemical sensing toward glucose

In electrochemical biosensors, rational design and synthesis of high-performance electrochemical glucose sensors based on emerging single-atom catalysts (SACs) are paramount. Herein, a facile approach is proposed for dispersing single-atom doping of cuprous oxide (Cu2O) nanowires with Pt on a copper foam substrate (Pt1/Cu2O@CF) via the electrochemical deposition process. The specific nanostructure of the single-atom catalyst has been elaborately revealed with the aid of atomic resolution scanning transmission electron microscopy (STEM) and X-ray absorption fine structure spectroscopy (XAS). The as-fabricated Pt1/Cu2O@CF biosensor with satisfactory scalability exhibits a low limit of detection (1 μM), ultrahigh sensitivity (31.55 mA mM−1 cm−2), excellent selectivity, and robust reliability toward glucose. The first principles simulations reveal that Pt SAC is beneficial to the adsorption of glucose on the surface and further facilitates the electron transfer for the deprotonation process, resulting in high glucose sensing performance. This work sheds light on the applications of SACs for designing ultrasensitive electrochemical biosensors.

Application of the polyhedral template matching method for characterization of 2D atomic resolution electron microscopy images

High-throughput image segmentation of atomic resolution electron microscopy data poses an ongoing challenge for materials characterization. In this paper, we investigate the application of the polyhedral template matching (PTM) method, a technique widely employed for visualizing three-dimensional (3D) atomistic simulations, to the analysis of two-dimensional (2D) atomic resolution electron microscopy images. This technique is complementary with other atomic resolution data reduction techniques, such as the centrosymmetry parameter, that use the measured atomic peak positions as the starting input. Furthermore, since the template matching process also gives a measure of the local rotation, the method can be used to segment images based on local orientation. We begin by presenting a 2D implementation of the PTM method, suitable for atomic resolution images. We then demonstrate the technique's application to atomic resolution scanning transmission electron microscopy images from close-packed metals, providing examples of the analysis of twins and other grain boundaries in FCC gold and martensite phases in 304 L austenitic stainless steel. Finally, we discuss factors, such as positional errors in the image peak locations, that can affect the accuracy and sensitivity of the structural determinations.

Synthesis and in-depth structure determination of a novel metastable high-pressure CrTe3 phase

This study reports the synthesis and crystal structure determination of a novel CrTe3 phase using various experimental and theoretical methods. The average stoichiometry and local phase separation of this quenched high-pressure phase were characterized by ex situ synchrotron powder X-ray diffraction and total scattering. Several structural models were obtained using simulated annealing, but all suffered from an imperfect Rietveld refinement, especially at higher diffraction angles. Finally, a novel stoichiometrically correct crystal structure model was proposed on the basis of electron diffraction data and refined against powder diffraction data using the Rietveld method. Scanning electron microscopy–energy-dispersive X-ray spectrometry (EDX) measurements verified the targeted 1:3 (Cr:Te) average stoichiometry for the starting compound and for the quenched high-pressure phase within experimental errors. Scanning transmission electron microscopy (STEM)–EDX was used to examine minute variations of the Cr-to-Te ratio at the nanoscale. Precession electron diffraction (PED) experiments were applied for the nanoscale structure analysis of the quenched high-pressure phase. The proposed monoclinic model from PED experiments provided an improved fit to the X-ray patterns, especially after introducing atomic anisotropic displacement parameters and partial occupancy of Cr atoms. Atomic resolution STEM and simulations were conducted to identify variations in the Cr-atom site-occupancy factor. No significant variations were observed experimentally for several zone axes. The magnetic properties of the novel CrTe3 phase were investigated through temperature- and field-dependent magnetization measurements. In order to understand these properties, auxiliary theoretical investigations have been performed by first-principles electronic structure calculations and Monte Carlo simulations. The obtained results allow the observed magnetization behavior to be interpreted as the consequence of competition between the applied magnetic field and the Cr–Cr exchange interactions, leading to a decrease of the magnetization towards T = 0 K typical for antiferromagnetic systems, as well as a field-induced enhanced magnetization around the critical temperature due to the high magnetic susceptibility in this region.

Crystal structures of two new high-pressure oxynitrides with composition SnGe4N4O4, from single-crystal electron diffraction.

SnGe4N4O4 was synthesized at high pressure (16 and 20 GPa) and high temperature (1200 and 1500°C) in a large-volume press. Powder X-ray diffraction experiments using synchrotron radiation indicate that the derived samples are mixtures of known and unknown phases. However, the powder X-ray diffraction patterns are not sufficient for structural characterization. Transmission electron microscopy studies reveal crystals of several hundreds of nanometres in size with different chemical composition. Among them, crystals of a previously unknown phase with stoichiometry SnGe4N4O4 were detected and investigated using automated diffraction tomography (ADT), a three-dimensional electron diffraction method. Via ADT, the crystal structure could be determined from single nanocrystals in space group P63mc, exhibiting a nolanite-type structure. This was confirmed by density functional theory calculations and atomic resolution scanning transmission electron microscopy images. In one of the syntheses runs a rhombohedral 6R polytype of SnGe4N4O4 could be found together with the nolanite-type SnGe4N4O4. The structure of this polymorph was solved as well using ADT.

Oxidized structure and Compositional properties of 1144 phase FBS by analytical electron microscopy

The 1144 phase (Ae1A1Fe4As4) shows a strong advantage of engineering fabrication among Fe (Iron)-based superconductor (FBS) family due to the robustness of its superconducting properties with respect to chemical inhomogeneities, granted by its uniform crystalline-layered structure. This regularity is furthermore associated to crystalline defects capable of acting as efficient pinning centers, from which high critical currents can achieved at high fields. Like other FBS phases, its lossless current-carrying capability can be remarkably degraded by distractions at grain boundaries (GBs). GB oxidation is an issue of upmost importance to the realization of the practical FBS application for high field (> 20T) magnet. In this study, we explore oxidized grain boundary and intrinsic grain structural properties of 1144 polycrystalline samples by applying analytical electron microscopy such as atomic resolution scanning transmission electron microscopy and atom probe tomography. These structural properties of samples produced by a mechanochemically assisted synthesis are evaluated following the degradation of superconducting properties due to oxidation. We observe a strong correlation between the contamination at grain boundaries and the decrease of transport properties of the bulk sample, while the crystallin structure seems to be not affected by the oxidation.

Thermomechanical and isothermal fatigue properties of MAR-M247 superalloy

Thermomechanical low-cycle fatigue (TMF) tests were performed on polycrystalline cast nickel-based superalloy MAR-M247 under in-phase (IP) and out-of phase (OP) loading in the temperature range of 500–900 °C. A constant heating and cooling rate of 5 °C.s−1 was selected. Furthermore, isothermal low-cycle fatigue (ILCF) tests with the same cycle period as TMF cycle were carried out at the maximal temperature of TMF cycle (900 °C). All tests ran under strain control and fully reversed cycle on solid cylindrical specimens in laboratory air. High resolution scanning electron microscopy and transmission electron microscopy were utilized to characterize the damage mechanism occurring during TMF and ILCF loading. The cyclic deformation and lifetime behaviour as well as damage mechanisms dependent on loading regime were examined. Results show that the TMF loading has a detrimental effect on the lifetime of MAR-M247. Lifetime reduction is most significant under IP loading. The fracture surfaces are characterized by typical striation fields, where the largest spacing between striations was observed for IP loading with prevailing intercrystalline cracking followed by OP and isothermal ILCF loading with transcrystalline crack propagation. To improve discussion of obtained results, experimental data were compared with damage and life prediction models.

The Influence of Carbon on Polytype and Growth Stability of Epitaxial Hexagonal Boron Nitride Films

AbstractBoron nitride (BN) is a promising 2D material as well as a potential wide‐bandgap semiconductor. Chemical vapor deposition (CVD) is commonly used to deposit single layers or thin films of BN, but the deposition process is insufficiently understood at an atomic scale. the CVD of BN is studied using two boron precursors, the organoboranes, triethylborane, and trimethylborane. Using high resolution (scanning) transmission electron microscopy and electron energy loss spectroscopy, this study shows that hexagonal‐BN (h‐BN) nucleates and grows epitaxially for ≈4 nm before it either polytype transforms to rhombohedral‐BN (r‐BN), turns to less ordered turbostratic‐BN or is terminated by a layer of amorphous carbon. this study proposes that the carbon in the organoboranes deposits on the epitaxially growing h‐BN surface and this either leads to the polytype transition to r‐BN, the transition to less ordered BN growth, or complete surface poisoning with carbon terminating BN growth. These results question the use of organoboranes in CVD of epitaxial BN films, and the polytype stability of h‐BN growing on graphene.