Wurtzite Aluminum Nitride Research Articles

Investigation of Piezoelectric Properties of Wurtzite AlN Films under In-Plane Strain: A First-Principles Study

This research article presents a comprehensive first-principles study on the piezoelectric properties of Wurtzite Aluminum Nitride (AlN) films under in-plane strain conditions. By calculating the piezoelectric tensor coefficients (e33, e31, and e15), we investigate the variation patterns of these constants with respect to in-plane strain. Our results indicate significant changes in the piezoelectric constants within the range of in-plane strain considered, exhibiting a linear trend despite opposite trends for e33 compared to e31 and e15. This study highlights the extreme sensitivity of AlN films’ piezoelectric performance to in-plane strain, suggesting its potential as an effective means for tuning and optimizing the piezoelectric properties of AlN-based devices.

Orbital hybridization and defective states of vacancy defects in AlN

Intrinsic atomic defects pose a great effect in wide-bandgap semiconductors owing to the high tendency of forming in-gap defective states. Utilizing density-functional theory, the atomic vacancy defects of Al and N vacancies in hexagonal wurtzite aluminum nitride (AlN) are investigated. We find that the most energetically favorable form of vacancies is predicted to be negatively trivalent charged Al vacancy (VAl−3) in n-type AlN and positively monovalent charged N vacancy (VN+1) in p-type AlN, respectively. N vacancy generally has a low formation energy and could be either an acceptor or a donor: Under p-type conduction, it is a deep donor with a positively monovalent charge of +1, acting as a compensating center for holes; Under n-type conduction, it is a deep acceptor carrying charge of −3, acting as a compensating center for electrons. For the Al vacancy, it tends to be a shallow acceptor in p-type AlN but a high formation energy or a deep acceptor in n-type AlN with low formation energy, most possibly at a negatively trivalent charged state. Our orbital hybridization analysis shows that these vacancies can be facilely generated which are rooted in the antibonding coupling Al3 s-N2p states in valence band. The above finding is independent of the chemical potential of nitrogen and aluminum and holds true under both nitrogen rich and poor conditions. Our work provides a guide to experimental works by providing the energetics and atomic-scale mechanism of doping nature of atomic vacancies in AlN.

The elasticity and piezoelectricity of AlN containing charged vacancies

Wurtzite aluminum nitride (w-AlN) piezoelectric film plays a key role in modern MEMS actuators and sensors. Density functional theory can be used to predict the elastic and piezoelectric properties of AlN containing various charged vacancies, thereby obtaining methods for improving the piezoelectric properties. The theoretical investigations suggested that the Young’s modulus of defectants are smaller than that of intrinsic AlN, indicating that charged vacancies can effectively improve the elastic properties of AlN. A high piezoelectric coefficient d 33 values were obtained in V Al 3 − , V N 1 + and V N 3 + that may be a cause of the non-symmetrical charges assignation. This work suggests that the elasticity and piezoelectricity of AlN films can be effectively enhancing using the introduction of charged vacancies.

Research on the Stability of Different Polar Surfaces in Aluminum Nitride Single Crystals

Wurtzite aluminum nitride (AlN) crystal has a non-centrosymmetric crystal structure with only a single axis of symmetry. In an AlN crystal, the electronegativity difference between the Al atom and N atom leads to a distortion of electron cloud distribution outside the nucleus and a spontaneous polarization (SP) along the c-axis direction. The N-polar surface along the directions of [000-1] has higher surface energy than the Al-polar surface along the directions of [0001]. Due to the different atomic arrangement, Al atoms on the Al-polar surface bond with O and OH− in the environment to generate Al2O3·xH2O, which prevents the reaction from occurring inside the crystal. After the Al2O3·xH2O dissolve in an alkaline environment, N atoms have three dangling bonds exposed on the surface, which can also protect OH− from destroying the internal Al-N bonds, so the Al-polar surface is more stable than the N-polar surface.

Machine-learned atomic cluster expansion potentials for fast and quantum-accurate thermal simulations of wurtzite AlN

Thermal transport in wurtzite aluminum nitride (w-AlN) significantly affects the performance and reliability of corresponding electronic devices, particularly when lattice strains inevitably impact the thermal properties of w-AlN in practical applications. To accurately model the thermal properties of w-AlN with high efficiency, we develop a machine learning interatomic potential based on the atomic cluster expansion (ACE) framework. The predictive power of the ACE potential against density functional theory (DFT) is demonstrated across a broad range of properties of w-AlN, including ground-state lattice parameters, specific heat capacity, coefficients of thermal expansion, bulk modulus, and harmonic phonon dispersions. Validation of lattice thermal conductivity is further carried out by comparing the ACE-predicted values to the DFT calculations and experiments, exhibiting the overall capability of our ACE potential in sufficiently describing anharmonic phonon interactions. As a practical application, we perform a lattice dynamics analysis using the potential to unravel the effects of biaxial strains on thermal conductivity and phonon properties of w-AlN, which is identified as a significant tuning factor for near-junction thermal design of w-AlN-based electronics.

Theory of electronic structure and effective masses of ultra-wide bandgap wurtzite aluminum nitride

I develop a theory of electronic structure for wurtzite(W)-Aluminium Nitride, based on the three uppermost valence bands and the lowest conduction band at the Γ-point. As distinguished from the Chuang-Chang approach [9], where the Hamiltonian is diagonalised considering all the bands, through an matrix, I follow a different procedure. In my approach, initially I follow a two-band approximation for the matrix, where the Hamiltonian is diagonalised by treating the conduction band and each of the valence bands separately. Thus, I diagonalise three different matrices, for obtaining the dispersions of the valence bands. The conduction band energy is obtained from the first diagonalization, involving band edge states. Effect of other two valence bands on a given valence band is considered through second order perturbation theory. Details of this procedure are outlined in Appendix A. It gives analytic expressions for the dispersion of the bands. I compare the results obtained for W-AlN with recent calculations and note satisfactory agreements. I also calculate the effective masses of holes in the valence bands both at the Γ-point and also as functions of the wavevector. My results agree fairly well with a recent calculation [3]. The hole effective masses for all the bands show large anisotropy. The effective mass of the electron in the conduction band does not show appreciable anisotropy.

Piezoelectric response enhancement of w-AlN by Hf (or Zr) and Sc co-alloying: A first principles study

In this report, rigorous calculations based on density functional theory have been performed to study the piezoelectric and elastic properties of wurtzite aluminum nitride (w-AlN) with single- and co-alloying by Hf (or Zr) and Sc. It is found that the (HfSc)0.375Al0.625N and (ZrSc)0.375Al0.625N with stable wurtzite phase, exhibit a piezoelectric coefficient d33 as large as 49.18 pC/N and 47.00 pC/N, respectively. However, the piezoelectric voltage constant g33 and electromechanical coupling constant k233 of HfAlN, ZrAlN, HfScAlN, and ZrScAlN are smaller than that of the ScAlN counterpart, which is due to the large dielectric constant ε33 of Hf (or Zr) alloying samples. Furthermore, the internal parameter u and the bond angle α were calculated to elucidate the brittle-to-ductile transformation in alloying w-AlN crystal structure. Electronic structure calculations show that the bandgap decreases almost linearly concerning the increase of alloying concentration, and the Hf (or Zr) alloying compounds become n-type semiconductors due to the existing high-charge states.

Structural and electrical correlation in aluminum nitride thin films grown by plasma enhanced atomic layer deposition as interface insulating layers on silicon carbide (4H-SiC)

(0001) oriented aluminum nitride (AlN) thin films have been grown by plasma enhanced atomic layer deposition (PE-ALD) on silicon carbide (4H-SiC) substrates. During different PE-ALD processes, the ammonia (NH3) plasma pulsing time has been varied and its effect on the microstructure and on the orientation degree of the AlN layers has been monitored. Structural characterization by Transmission Electron Microscopy (TEM) showed that the crystalline structure of the deposited films was strongly dependent on the NH3-plasma pulsing, so that different polymorphic structures were observed. In particular, both processes resulted in wurtzite AlN structure for few nanometers at the interface with the 4H-SiC substrate, while upon increasing thickness a poly-crystalline wurtzite phase was obtained by short-pulse NH3-plasma, whereas longer plasma exposure resulted in a mixture of wurtzite and zincblende defective phases. Phase formation mechanism were discussed and electrical nanoscopic characterization by conductive atomic force microscopy showed a clear correlation between the different AlN crystalline phases and the insulating properties.

The evolution of preferred orientation and morphology of AlN films under various sputtering parameters

Wurtzite aluminum nitride (AlN) films with (100) and (002) preferred orientations are obtained on Si (100) wafers by radio frequency magnetron sputtering. The effects of target to substrate distance (TSD), RF power, deposition pressure and substrate temperature on crystal orientation and morphology of AlN films are analyzed. It is demonstrated that the TSD is the key factor affecting the preferred orientation of AlN films. The preferred orientation transforms from (002) to (100) with the increase of TSD. Further increase of substrate temperature and RF power causes the coexistence of (002) and (100) orientation. The evolution of orientation is explained by the change in kinetic energy of sputtered particles. The correlation between the crystal orientation and the surface morphology is investigated.

Characterization of prismatic slip in PVT-grown AlN crystals

The most frequently observed deformation mechanism in wurtzite aluminum nitride (AlN) grown by the physical vapor transport (PVT) method is basal plane slip. However, prismatic slip also takes place in such crystals. In this study, prismatic slip is observed in a 50 mm commercial AlN substrate wafer, leading to a sixfold symmetric BPD pattern in the wafer. Prismatic dislocations cross slip on to basal plane and multiply there, increasing the dislocation density of the wafer. A radial thermal model is established to explore the origin of the unevenly distributed dislocations. The unevenly distributed resolved shear stress across the whole radial area of the boule during PVT growth caused by radial thermal gradients offers driving force for the activation of the three sets of prismatic slip systems, producing nonuniform dislocation distribution in the boule and thus the wafer. Both experimental observations and theoretical calculations of the critical resolved shear stress (CRSS) correlate well with the model results, revealing that controlling radial thermal gradients is critical for lowering dislocation density and enhancing the crystal quality using PVT growth method.

High thermal conductivity and ultrahigh thermal boundary conductance of homoepitaxial AlN thin films

Wurtzite aluminum nitride (AlN) has attracted increasing attention for high-power and high-temperature operations due to its high piezoelectricity, ultrawide-bandgap, and large thermal conductivity k. The k of epitaxially grown AlN on foreign substrates has been investigated; however, no thermal studies have been conducted on homoepitaxially grown AlN. In this study, the thickness dependent k and thermal boundary conductance G of homoepitaxial AlN thin films were systematically studied using the optical pump–probe method of frequency-domain thermoreflectance. Our results show that k increases with the thickness and k values are among the highest reported for film thicknesses of 200 nm, 500 nm, and 1 μm, with values of 71.95, 152.04, and 195.71 W/(mK), respectively. Our first-principles calculations show good agreement with our measured data. Remarkably, the G between the epilayer and the substrate reported high values of 328, 477, 1180, and 2590 MW/(m2K) for sample thicknesses of 200 nm, 500 nm, 1 μm, and 3 μm, respectively. The high k and ultrahigh G of homoepitaxially grown AlN are very promising for efficient heat dissipation, which helps in device design and has advanced applications in micro-electromechanical systems, ultraviolet photonics, and high-power electronics.

Recent Advances in Fabricating Wurtzite AlN Film on (0001)-Plane Sapphire Substrate

Ultrawide bandgap (UWBG) semiconductor materials, with bandgaps far wider than the 3.4 eV of GaN, have attracted great attention recently. As a typical representative, wurtzite aluminum nitride (AlN) material has many advantages including high electron mobility, high breakdown voltage, high piezoelectric coefficient, high thermal conductivity, high hardness, high corrosion resistance, high chemical and thermal stability, high bulk acoustic wave velocity, prominent second-order optical nonlinearity, as well as excellent UV transparency. Therefore, it has wide application prospects in next-generation power electronic devices, energy-harvesting devices, acoustic devices, optical frequency comb, light-emitting diodes, photodetectors, and laser diodes. Due to the lack of low-cost, large-size, and high-ultraviolet-transparency native AlN substrate, however, heteroepitaxial AlN film grown on sapphire substrate is usually adopted to fabricate various devices. To realize high-performance AlN-based devices, we must first know how to obtain high-crystalline-quality and controllable AlN/sapphire templates. This review systematically summarizes the recent advances in fabricating wurtzite AlN film on (0001)-plane sapphire substrate. First, we discuss the control principles of AlN polarity, which greatly affects the surface morphology and crystalline quality of AlN, as well as the electronic and optoelectronic properties of AlN-based devices. Then, we introduce how to control threading dislocations and strain. The physical thoughts of some inspirational growth techniques are discussed in detail, and the threading dislocation density (TDD) values of AlN/sapphire grown by various growth techniques are compiled. We also introduce how to achieve high thermal conductivities in AlN films, which are comparable with those in bulk AlN. Finally, we summarize the future challenge of AlN films acting as templates and semiconductors. Due to the fast development of growth techniques and equipment, as well as the superior material properties, AlN will have wider industrial applications in the future.

Glide Mobility of a-Type Edge Dislocations in Aluminum Nitride by Molecular Dynamics Simulation.

Classical molecular dynamics simulations are performed to investigate the motion of a-type edge dislocations in wurtzite aluminum nitride (AlN). The nucleation and propagation of kinks are observed via the dislocation extraction algorithm. Our simulation results show that the nucleation energy of the kink pair in AlN is 1.2 eV and that the migration energy is 2.8 eV. The Peierls stress of the 1/3⟨112̅0⟩{101̅0} edge dislocation at 0 K is 15.9 GPa. The viscous motion of dislocations occurs when τ > τp, and the dislocation velocity is inversely proportional to the temperature and directly proportional to the applied stress. Below room temperature, the value of the critical resolved shear stress (CRSS) on the prismatic plane is the lowest, which suggests that the dislocation mobility on the prismatic plane is the easiest. The CRSS on the pyramidal plane is always the highest at all temperatures, which suggests that pyramidal slip is the hardest among these three slip systems.

Demonstration of ferroelectricity in ScGaN thin film using sputtering method

It is recently found that wurtzite aluminum nitride exhibits ferroelectricity by alloying with scandium. Because its remanent polarization (Pr) is large, ScxAl1−xN has attracted much attention. Gallium nitride with similar structure and properties is also expected to show ferroelectricity. Herein, ScxGa1−xN was prepared on a silicon substrate at 673 K using the sputtering method, and its ferroelectricity was investigated. Sc0.41Ga0.59N exhibited ferroelectricity before dielectric breakdown. Pr of this film, as evaluated via positive-up-negative-down (PUND) measurement, was around 120 μC/cm2, which can reduce the influence of the leakage current. This was comparable to the value of ScxAl1−xN with the same internal parameter u, which is approximately estimated from the lattice constants. Moreover, in the PUND measurement, the measurement temperature dependence of Ec was observed, which was 4.3 MV/cm at 300 K and reduced to 3.2 MV/cm at 473 K.

Mapping the Structure of Oxygen-Doped Wurtzite Aluminum Nitride Coatings from Ab Initio Random Structure Search and Experiments.

Machine learning is changing how we design and interpret experiments in materials science. In this work, we show how unsupervised learning, combined with ab initio random structure searching, improves our understanding of structural metastability in multicomponent alloys. We focus on the case of Al-O-N alloys where the formation of aluminum vacancies in wurtzite AlN upon the incorporation of substitutional oxygen can be seen as a general mechanism of solids where crystal symmetry is reduced to stabilize defects. The ideal AlN wurtzite crystal structure occupation cannot be matched due to the presence of an aliovalent hetero-element into the structure. The traditional interpretation of the c-lattice shrinkage in sputter-deposited Al-O-N films from X-ray diffraction (XRD) experiments suggests the existence of a solubility limit at 8 at % oxygen content. Here, we show that such naive interpretation is misleading. We support XRD data with accurate ab initio modeling and dimensionality reduction on advanced structural descriptors to map structure-property relationships. No signs of a possible solubility limit are found. Instead, the presence of a wide range of non-equilibrium oxygen-rich defective structures emerging at increasing oxygen contents suggests that the formation of grain boundaries is the most plausible mechanism responsible for the lattice shrinkage measured in Al-O-N sputtered films. We further confirm our hypothesis using positron annihilation lifetime spectroscopy.

Enhancing the piezoelectric modulus of wurtzite AlN by ion beam strain engineering

The piezoelectric modulus of wurtzite aluminum nitride (AlN) is a critical material parameter for electrical components, ultimately contributing to the energy efficiency and achievable bandwidth of modern communication devices. Here, we demonstrate that the introduction of metallic point-defects (Ti, Zr, Hf) improves the piezoelectric modulus of as-received, unstrained, epitaxially grown AlN. The metals are incorporated by ion implantation with an acceleration energy of 30 keV to a fluence of 1015 at cm−2, which causes an elongation along the wurtzite c-axis. The stored internal strain energy increases the piezoelectric polarization of the thin AlN layer. This can equivalently be described by an enhancement of the piezoelectric modulus d33. The incorporation of 0.1 at. % Ti enhances the piezoelectric modulus by ∼30%; significantly exceeding gains obtained by alloying with the same amount of Sc.

First-Principles Study of Electronic Structure and Optical Properties of La-Doped AlN

As a wide-bandgap semiconductor material with small dielectric constant and good thermal stability, aluminium nitride (AlN) can theoretically emit light in the deep ultraviolet wavelength region, so it is important in expanding the response of AlN in the visible region. In order to study the influences of La doping on the photoelectric properties of wurtzite AlN crystal, the first-principle plane-wave pseudopotential method and generalized gradient approximation were used to study the lattice constants, electronic structure and optical properties of undoped and La-doped AlN. The calculation results indicate that the intrinsic AlN is a direct-bandgap semiconductor material which both conduction band bottom and valence band top being at the G point, but La-doped AlN forms an indirect-bandgap semiconductor in which the conduction band bottom is at the G point and the valence band top is at the F point. The peak of the density of states is reduced near Fermi energy, and the electronic localization features are significantly diminished. The La doping makes the forbidden band width of AlN narrow, which reduces the photon energy needed for the electron transition, and shows a red shift phenomenon, which expands the influence on visible light. Therefore, this provides a theoretical basis for the study of the photoelectric properties of rare-earth-metal La-doped AlN.

Aluminum Nitride Thin Films Grown by Sol-Gel Spin Coating Technique

In this study, aluminum nitride (AlN) thin films were grown on p-type silicon (100) substrate by sol-gel spin coating method. Two types of ethanol-based precursors were prepared, namely, precursors with and without the aid of diethanolamine (DEA). The objective of this work is to investigate the effects of the DEA on the surface morphology, structural and optical properties of the deposited thin films. The coating films were undergone nitridation process under ammonia ambient at 1100 °C for 60 min. The surface morphology and structural properties of the deposited AlN thin films were investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). XRD results revealed that both samples have AlN (100) preferred orientation. In addition, the crystallinity of sample without the aid of DEA is higher compared to the sample prepared with DEA. While, the AFM results showed that both samples have uniform and smooth surface. The optical properties of AlN thin films was investigated by Raman spectroscopy. For sample without DEA, Raman results showed the present of wurtzite AlN characteristics phonon modes of E2(high) and A1(LO) at 660 cm-1 and 892 cm-1, respectively. Whereas only E2(high) is observed for sample with the aid of DEA. Finally, all the results revealed that the present of DEA has a strong influence on the properties of deposited AlN thin films and film prepared without DEA have better quality.

Influence of trimethylaluminum predoses on the growth morphology, film-substrate interface, and microstructure of MOCVD-grown AlN on (1 1 1)Si

Aluminum nitride (AlN) was deposited on (111) silicon by metalorganic chemical vapor deposition after varied trimethylaluminum “predoses”. Growth morphologies, film-substrate interfaces, and film microstructures were examined using scanning electron microscopy, atomic force microscopy, X-ray diffraction, and transmission electron microscopy. In samples grown with predoses, lateral growth was observed over faceted “patches” formed during the predose. Three-dimensional growth was observed to seed from small islands on the surface of these patches and eventually overgrow them. The three-dimensional growth mode was similar to that observed when AlN was grown without a predose, resulting in similar morphologies in all films, regardless of predose, after the islands coalesced. The AlN-silicon interface was found to be predominantly amorphous when no predose was used. However, narrow regions were observed over which the film was in atomic registry with the substrate. This indicates AlN nucleates in epitaxy with the substrate and amorphous silicon nitride forms between nucleation sites due to ammonia exposure. Films grown with predoses had structurally abrupt interfaces, suggesting aluminum within the observed patch features inhibits the reaction between ammonia and silicon at the onset of growth. A structure distinct from both wurtzite AlN and diamond cubic silicon was observed at the substrate interface in films grown with a predose, consistent with either zinc blende AlN or a strained Si/Al alloy. A mosaic microstructure was observed in all films, grown with or without predoses, which consisted of sub-boundaries formed by clusters of threading dislocations. Threading dislocations, separated by hundreds of nanometers, were found to be tilted along common directions, providing evidence for a dislocation bending mechanism possibly enhanced by the predose.

Photo-Enhanced Acid Chemical Etching of High-Quality Aluminum Nitride Grown by Metal-Organic Chemical Vapor Deposition

Photo-enhanced chemical (PEC) etch of wurtzite aluminum nitride (AlN) was investigated to overcome its low etch rate. Epitaxial AlN grown on Al2O3 substrate by metal-organic chemical vapor deposition method was immersed in phosphoric acid at different temperatures under 185 nm deep-UV excitation. An inverted pyramid structure with {10-1-1} faces initially appeared, after chemical etching, evolving into hexagonal columns with {1-100} m-planes. The PEC etch rate of m-plane AlN was six-fold higher than that of non-PEC one because the reaction was enhanced by the electron-hole pairs photo-generated by 185 nm wavelength. The decrease of the activation energy from 68.5 kJ/mol (non-PEC etch) to 48.1 kJ/mol (PEC etch) was extracted, implying a reaction-limited etching process. The PEC etch mechanism of wurtzite AlN in phosphoric acid was proposed, including the initiation and growth of the etch pit and the agglomeration of the hexagonal columns. Our results propose a facile method to control the surface morphology of AlN-based electronic and optoelectronic devices.