Precursors For Chemical Vapor Deposition Research Articles

Targeting Manganese Amidinates and ß-Ketoiminates Complexes as Precursors for Mn-Based Thin Film Vapor Deposition.

With a focus on Mn based organometallic compounds with suitable physico-chemical properties to serve as precursors for chemical vapor deposition (CVD) and atomic layer deposition (ALD) of Mn-containing materials, systematic synthetic approaches with ligand variation, detailed characterization, and theoretical input from density functional theory (DFT) studies are presented. A series of new homoleptic all-nitrogen and mixed oxygen/nitrogen-coordinated Mn(II) complexes bearing the acetamidinate, formamidinate, guanidinate and ß-ketoiminate ligands have been successfully synthesized for the first time. The specific choice of these ligand classes with changes in structure and coordination sphere and side chain variations result in significant structural differences whereby mononuclear and dinuclear complexes are formed. This was supported by density functional theory (DFT) studies. The compounds were thoroughly characterized by single crystal X-ray diffraction, magnetic measurements, mass spectrometry and elemental analysis. To evaluate their suitability as precursors for deposition of Mn-based materials, the thermal properties were investigated in detail. Mn(II) complexes possessing the most promising thermal properties, namely Bis(N,N´-ditertbutylformamidinato)manganese(II) (IV) and Bis(4-(isopropylamino)pent-3-en-2-onato)manganese(II) (ßIII) were used in reactivity studies with DFT to explore their interaction with oxidizing co-reactants such as oxygen and water which will guide future CVD and ALD process development.

Volatile N,N′-dialkyl-β-dialdiminate complexes of magnesium and zinc as possible chemical vapor deposition precursors

A series of volatile magnesium(II) and zinc(II) bis(β-dialdiminato) complexes (of stoichiometry M[RN(CH)3NR]2 where R = methyl, ethyl, isopropyl, or tert-butyl) have been prepared and investigated as potential precursors for the chemical vapor deposition of thin films. Several of the compounds have been characterized crystallographically; the metal centers adopt pseudo-tetrahedral geometries with the two ligands forming six-membered rings with the metal center. All eight compounds sublime cleanly both in vacuum and under 1 atm of N2, and the most volatile compounds (those having N-methyl substituents) have vapor pressures of 1 Torr at 88 (Mg) and 90 °C (Zn). In general, metal complexes of N,N′-dialkyl-β-dialdiminate ligands are more volatile than their corresponding N,N′-dialkyl-β-diketiminate and N,N-dialkylamidinate analogues.

Lightweight, freestanding hybrids of graphene and hexagonal boron nitride foams

Lightweight boron carbon nitride foams which are a hybrid of graphene and hexagonal boron nitride (hBN), are produced using the nickel template method and remain freestanding after the etching of nickel without the stabilization of a polymer during etching. Chemical vapor deposition (CVD) precursors with varying carbon content were utilized, but only a 10% range of carbon atomic percentage variation is observed in the resulting boron carbon nitride foams due to the high carbon solubility of nickel. However, the cooling rate during the CVD process has a much more significant effect on the carbon content. Moreover, a 6.5-fold increase in resistivity is observed for our foams compared to a graphene foam with an overall trend of decreasing resistance with increasing carbon content. Furthermore, when the foam is infiltrated with epoxy to form a composite at 0.3% volumetric percentage concentration, there is a 27% increase in the thermal conductivity over hBN foam composites. These foams are suitable to use as a substitute for graphene foams when a lower electrical conductivity is desired and could potentially be used as a thermal interface material if a higher pore density nickel template is utilized.

Guiding Principles for the Design of a Chemical Vapor Deposition Process for Highly Crystalline Transition Metal Dichalcogenides

2D transition metal dichalcogenides (TMDs) for advanced logic transistor technologies are deposited by various modifications of the chemical vapor deposition (CVD) method using a wide variety of precursors. Being a major electrical performance limiter, the TMD crystal grain size strongly differs between the various CVD precursor chemistries from nano‐ to millimeter‐sized crystals. However, it remains unclear how the CVD precursor chemistry affects the nucleation density and resulting TMD crystal grain size. This work postulates guiding principles to design a CVD process for highly crystalline TMD deposition using a quantitative analytical model benchmarked against the literature. The TMD nucleation density reduces favorably under low supersaturation conditions where the metal precursor sorption on the starting surface is reversible and the corresponding metal precursor desorption rate exceeds the overall deposition rate. Such reversible precursor adsorption guarantees efficient long‐range gas‐phase lateral diffusion of precursor species in addition to short‐range surface diffusion, which vitally increases crystal grain size. The proposed model explains the large spread in experimentally observed TMD nucleation densities and crystal grain sizes for state‐of‐the‐art CVD chemistries. Ultimately, it empowers the reader to interpret and modulate precursor adsorption and diffusion reactions through designing CVD precursor chemistries.

The investigation of initial decomposition paths of methyltrichlorosilane on (0001) and (000[formula omitted]) surfaces of 4H-SiC: A DFT study

Methyltrichlorosilane (CH3SiCl3, MTS), a favored precursor for chemical vapor deposition (CVD) process of silicon carbide (SiC) epitaxial layer fabrication in a wide variety of temperatures, has been investigated prevalently. In this work, the investigation focused on the initial decomposition paths of MTS with active surface sites on 4H-SiC surfaces. The surfaces employed in this study include both (0001) face and (0001¯) face, which represent Si face and C face, respectively. The decomposition pathways of MTS decomposed with the active surface sites of 4H-SiC surfaces were researched theoretically with employment of transition state theory (TST). The barriers of Gibbs free energies and the estimated reaction rate constants were acquired to discuss the decomposition reactivity of MTS with the active sites on 4H-SiC surfaces. This work shows that MTS has tendency to decompose on both (0001) face and (0001¯) face of 4H-SiC, the H and Cl atoms can be abstracted by active surface sites on (0001) face and (0001¯) face, and impingement of MTS to active surface sites on (0001) and (0001¯) surfaces can yield C-containing and Si-containing surface species.

Area-selective atomic layer deposition on 2D monolayer lateral superlattices

The advanced patterning process is the basis of integration technology to realize the development of next-generation high-speed, low-power consumption devices. Recently, area-selective atomic layer deposition (AS-ALD), which allows the direct deposition of target materials on the desired area using a deposition barrier, has emerged as an alternative patterning process. However, the AS-ALD process remains challenging to use for the improvement of patterning resolution and selectivity. In this study, we report a superlattice-based AS-ALD (SAS-ALD) process using a two-dimensional (2D) MoS2-MoSe2 lateral superlattice as a pre-defining template. We achieved a minimum half pitch size of a sub-10 nm scale for the resulting AS-ALD on the 2D superlattice template by controlling the duration time of chemical vapor deposition (CVD) precursors. SAS-ALD introduces a mechanism that enables selectivity through the adsorption and diffusion processes of ALD precursors, distinctly different from conventional AS-ALD method. This technique facilitates selective deposition even on small pattern sizes and is compatible with the use of highly reactive precursors like trimethyl aluminum. Moreover, it allows for the selective deposition of a variety of materials, including Al2O3, HfO2, Ru, Te, and Sb2Se3.

Early events in the mechanism of single-source chemical vapor deposition of zirconium and hafnium diboride: a computational investigation.

Chemical vapor deposition (CVD) of group 4 metal-diboride ceramics from a single source is a versatile technique that finds many applications from hypersonic flight to microelectronics. Though the kinetics of CVD have been studied extensively-allowing significant process improvements-a mechanistic understanding of the process has yet to be attained. Computations suggest two plausible reaction pathways-one higher-energy and the second lower-that correlate well with experimental results reported in the literature, explaining phenomena such as high-temperature deposition resulting in films overstoichiometric in boron. These insights offer a new perspective that may be instrumental in the rational design of new precursors for single-source CVD.

Synthesis, Characterization, and Single-Crystal X-ray Structures of Refractory Metal Compounds as Precursors for the Single-Source Chemical Vapor Deposition of Metal Nitrides.

The chemical vapor deposition of refractory metal nitrides requires volatile precursors and has previously been achieved by using metal complexes containing a variety of imide ligands. Recently, the 1,4-di-tert-butyl-1,3-diazabutadiene (DAD) adduct of bis(tert-butylimide)dichloridemolybdenum(VI) was shown to be an excellent precursor for the single-source CVD of Mo2N thin films. Leveraging the success of this work, we prepared chromium and tungsten compounds with the same framework. Additionally, the framework has been modified slightly to allow the isolation of mono(tert-butylimide)trichloride complexes of vanadium, niobium, tantalum, and molybdenum(V) to extend the search for new vapor-phase precursors. These compounds were all fully characterized using the standard methods of multinuclear magnetic resonance spectroscopy, combustion analysis, and single-crystal X-ray diffraction. Their thermal properties were determined by using thermogravimetric analysis and differential scanning colorimetry to assess their utility as vapor-phase precursors. Finally, preliminary deposition studies were carried out to investigate their potential as single-source CVD precursors.

Toward an understanding of the mechanism of mixed-salt-mediated CVD growth of MoSe2

The use of liquid precursors in chemical vapor deposition (CVD) techniques is advantageous for growing large-area, uniform two-dimensional (2D) transition-metal dichalcogenides (TMDs) compared to conventional methods using solid precursors. While various liquid precursors have been explored, recent studies highlight the use of mixed-salt precursors for growing uniform and wafer-scale TMDs. In this study, we propose a growth mechanism and present our findings on the epitaxial growth of MoSe2 domains as a function of annealing/growth time and H2 flow rate using Na2MoO4 and Na2SeO3 mixed-salt precursors. We confirm that the increase in the annealing time enhances the distribution of spin-coated precursors, leading to a rise in flake number density. On the other hand, prolonged growth time results in better-aligned MoSe2 flakes along the c-sapphire substrate step-edges. A significant finding is the dynamic diffusion of dendritic structures within large domains over the growth period, owing to the constant dissolution and recrystallization in the presence of residual liquid alloys. An increase in the H2 flow during CVD growth yields small, triangular domains aligned with the step edges, a result of the efficient reduction of precursor alloys and subsequent selenization. Our results provide an insight on achieving uniform and aligned morphology in CVD growth of 2D TMDs using liquid-phase precursors, a crucial step toward large-area fabrication.

In Pursuit of Next Generation N-Heterocyclic Carbene-Stabilized Copper and Silver Precursors for Metalorganic Chemical Vapor Deposition and Atomic Layer Deposition Processes

Volatile, reactive, and thermally stable organometallic copper and silver complexes are of significant interest as precursors for the metalorganic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) of ultra-thin metallic films. Well-established CuI and AgI precursors are commonly stabilized by halogens, phosphorous, silicon, and oxygen, potentially leading to the incorporation of these elements as impurities in the thin films. These precursors are typically stabilized by a neutral and anionic ligand. Recent advancements were established by the stabilization of these complexes using N-heterocyclic carbenes (NHCs) as neutral ligands. To further enhance the reactivity, in this study the anionic ligand is sequentially changed from β-diketonates to β-ketoiminates and β-diketiminates, yielding two new CuI and two new AgI NHC-stabilized complexes in the general form of [M(NHC) (R)] (M = Cu, Ag; R = β-ketoiminate, β-diketiminate). The synthesized complexes were comparatively analyzed in solid, dissolved, and gaseous states. Furthermore, the thermal properties were investigated to assess their potential application in MOCVD or ALD. Among the newly synthesized complexes, the β-diketiminate-based [Cu(tBuNHC) (NacNacMe)] was identified to be the most suitable candidate as a precursor for Cu thin film deposition. The resulting halogen-, oxygen-, and silicon-free CuI and AgI precursors for MOCVD and ALD applications are established for the first time and set a new baseline for coinage metal precursors.

Role of density gradients in the growth dynamics of 2-dimensional MoS2 using liquid phase molybdenum precursor in chemical vapor deposition

The key objective of this work was the comparison of MoS2 2-dimensional monolayer flakes grown by Chemical Vapour Deposition with different density gradients in the liquid precursors solution. Structures grown using solutions with iodixanol or glycerol were characterized by Optical Microscopy, Atomic Force Microscopy, Raman spectroscopy and Photoluminescence. Furthermore, electrical properties of structures were studied by characterizing backgated Field-Effect Transistors fabricated on individual flakes.The fundamental outcome of this study is that there are relevant differences between the structures grown with the two different liquid solutions: MoS2 structures grown with glycerol present a large variability in the lateral size of the sharp-corner triangular structure with a good crystalline quality while the employment of iodixanol (the most used substance) causes a poorer crystalline quality, demonstrated by the presence of nanometric pores, with a more homogeneous sizing of the triangular structures.The poor crystalline quality of the iodixanol samples results in reduced light emission efficiency and lower mobility.

Triethylamine borane thermal decomposition for BN low pressure chemical vapour deposition

Triethylamine borane (TEAB) complex was studied as a potential precursor for the thermal low pressure chemical vapour deposition (LPCVD) of pure crystalline sp2-hybridised BN. In particular, its thermal decomposition with or without ammonia was characterised from thermodynamic and experimental points of view in the temperature ranges 400–2000 °C and 300–1300 °C, respectively. NH3 plays a role in the gas phase equilibrium by providing a nitriding source that promotes HCN formation at high temperatures. NH3 is also a source of hydrogen for light hydrocarbons formation as it decomposes. It is thus possible to promote gaseous carbon species formation at high temperatures and limit carbon introduction into coatings by adding ammonia. A turbostratic BN coating could be obtained by CVD from a TEAB/NH3/N2 mixture and conditions chosen thanks to the gas phase decomposition study.

Molybdenum(III) Amidinate: Synthesis, Characterization, and Vapor Phase Growth of Mo-Based Materials.

The synthesis, characterization, and thermogravimetric analysis of tris(N,N'-di-isopropylacetamidinate)molybdenum(III), Mo(iPr-AMD)3, are reported. Mo(iPr-AMD)3 is a rare example of a homoleptic mononuclear complex of molybdenum(III) and fills a longstanding gap in the literature of transition metal(III) trisamidinate complexes. Thermogravimetric analysis (TGA) reveals excellent volatilization at elevated temperatures, pointing to potential applications as a vapor phase precursor for higher temperature atomic layer deposition (ALD), or chemical vapor deposition (CVD) growth of Mo-based materials. The measured TGA temperature window was 200-314 °C for samples in the 3-20 mg range. To validate the utility of Mo(iPr-AMD)3, we demonstrate aerosol-assisted CVD growth of MoO3 from benzonitrile solutions of Mo(iPr-AMD)3 at 500 °C using compressed air as the carrier gas. The resulting films are characterized by X-ray photoelectron spectroscopy, X-ray diffraction, and Raman spectroscopy. We further demonstrate the potential for ALD growth at 200 °C with a Mo(iPr-AMD)3/Ar purge/300 W O2 plasma/Ar purge sequence, yielding ultrathin films which retain a nitride/oxynitride component. Our results highlight the broad scope utility and potential of Mo(iPr-AMD)3 as a stable, high-temperature precursor for both CVD and ALD processes.

Comparative study of thermal behavior of a series beta-diketonate precursors for chemical vapor deposition of lithium-containing films

Five volatile lithium beta-diketonates: Li(tmhd) (1), Li(pta) (2), LiL (3), LiLF (4), Li(tmha) (5) (tmhd = 2,2,6,6-tetramethyl-heptane-3,5-dionate, pta = 1,1,1-trifluoro-5,5-dimethyl-hexane-2,4-dionate, L = 2-methoxy-2,6,6-trimethyl-heptane-3,5-dionate, LF = 1,1,1-trifluoro-5-methoxy-5-methyl-hexane-2,4-dionate, tmha = 2,2,6,6-tetramethyl-heptane-3-imino-5-onate) and lithium alkoxide Li(OtBu) (6) were examined by combination of several complementary methods to study their thermal behavior in solid and gas phase and to check their suitability as precursors for chemical vapor deposition of Li-containing films. The best storage stability was observed for 3 and 4. Thermal gravimetric analysis and vacuum sublimation test were used to compare stability of the complexes under vaporization. In situ mass spectrometry was used to study the gas phase composition and the surface decomposition chemistry. Diketonate complexes 1, 3-5 passed into the gas phase as tetranuclear particles. Upon further heating, they split into binuclear species. The binuclear species thermolysis is responsible for the film deposition. The vapor thermal stability in oxygen increases in the row 3 > 1>5 > 2>4 > 6. CVD films obtained at 500 °C in the presence of oxygen using 1, 3 and 5 consisted of Li2CO3. LiF films can be obtained using 2, while 4 allow one to obtain the Li metal films in the oxygen presence on both Si and Pt/Si substrates.

Experimental and Computational Research on the Effect of Flow Distribution on the Growth of Boron Nitride Nanotubes by Chemical Vapor Deposition

The chemical vapor deposition (CVD) method offers a controlled and scalable approach for the large-scale production of boron nitride nanotubes (BNNTs). However, current research on BNNTs has been primarily focused on identifying precursors that can facilitate the efficient preparation of pure BNNTs. The collection of BNNTs remains a significant challenge due to the complex nature of the CVD reaction, which is influenced by the variable location of the floating aggregation of BNNTs generated from the gas phase reaction. To address this issue, we utilized B/MgO/Fe2O3, a well-established CVD precursor, to grow BNNTs in a horizontal furnace. Through experimental and computational fluid dynamics simulation analysis, we identified the impact of vortex generation and low flow rate on the floating height of BNNTs. Using the insights gained from these investigations, we designed a more efficient growth setup, laying the foundation for achieving larger-scale BNNT production in the future.

Novel Volatile Heteroleptic Barium Complexes Using Tetradentate Ligand and β-Diketonato Ligand.

Novel barium heteroleptic complexes were synthesized through the substitution of the bis(trimethylsilyl)amide of Ba(btsa)2·2DME with aminoalkoxide and β-diketonate ligands. Compounds [Ba(ddemap)(tmhd)]2 (1) and [Ba(ddemmp)(tmhd)]2 (2) were obtained and analyzed through Fourier transform infrared spectroscopy, nuclear magnetic resonance, thermogravimetric analysis, and elemental analysis (ddemapH = 1-(dimethylamino)-5-((2-(dimethylamino)ethyl) (methyl)amino)pentan-3-ol and ddemmpH = 1-(dimethylamino)-5-((2-(dimethylamino)ethyl) (methyl)amino)-3-methylpentan-3-ol). In single-crystal X-ray crystallography, complex 1 exhibited a dimeric structure with μ2-O bonds of the ddemap ligand. All complexes exhibited high volatility and could be sublimed under reduced pressure (0.5 Torr) at 160 °C, indicating that these complexes are promising candidates as atomic layer deposition or chemical vapor deposition precursors for the growth of barium-containing thin films.

1,4-Bis(trimethylsilyl)piperazine—Thermal Properties and Application as CVD Precursor

We report an investigation into 1,4-Bis-N,N-(trimethylsilyl)piperazine (BTMSP) as a novel precursor for the synthesis of silicon carbonitride films by chemical vapor deposition (CVD). The thermal stability, temperature dependence of vapor pressure and thermodynamic constants of the evaporation process of BTMSP were determined by static tensimetry with a glass membrane zero manometer. The transformation of the compound in low-power (25 W) plasma conditions was investigated by optical emission spectroscopy. It was shown that BTMSP undergoes destruction, accompanied by H and CH elimination and CN formation. SiCN(H) films were deposited in a hot-wall plasma-enhanced CVD reactor. The optical properties of the films were studied by spectral ellipsometry (refractive index: 1.5–2.2; absorption coefficient: 0–0.12) and UV–Vis spectroscopy (transmittance: up to 95%; optical bandgap: 1.6–4.9 eV). Information on the aging behavior of the films is also provided. The transformation of the films occurred through water adsorption and the formation of Si–O bonds with the degradation of Si–H, N–H and Si–CHx–Si bonds.

Air and O2-Assisted Catalytic VACNT Growth Optimization for Uniformity and Throughput

The development of an optimized air or O2-assisted multi-wall vertically aligned carbon nanotubes (VACNT) process that adjusts the vertical height profile of a standard H2O vapor-assisted VACNT process is reported. The effect of the air or O2 chemical vapor deposition (CVD) precursor flow rate, the catalytic Fe layer thickness, the process growth temperature, and the H2/C2H4 ratio on VACNT length was first investigated to find the optimum growth conditions. Spatial distribution height mapping of VACNT structures on six patterned 4′′ catalyst Si wafers prepared with a 70–90 min long O2-assisted growth step shows an average growth height of 1.8–2.2 mm, with a standard deviation of less than 10%. Characterization techniques included Raman spectroscopy, scanning electron microscopy (SEM), and spatial height mapping analysis for a range of Fluid channel Array Brick (FAB) components with a length of 30 mm, a width range of 2.5–15 mm, a fluid channel diameter range of d = 5–100 mm, and a fluid channel closest gap range of g = 5–50 mm. A significant finding is that the O2-assisted VACNT growth process optimization efforts enable 2 mm parts processing with square edges, flat top surfaces, uniform height tolerances, and maximum catalyst wafer utilization for application in engineering devices.

Theoretical and experimental research on growth and doping mechanisms of diamond films fabricated using liquid carbon source precursors

Fabricating diamond films using liquid carbon source precursors in hot filament chemical vapor deposition (HFCVD) is an emerging technology. Although some experiments have demonstrated the feasibility of depositing doped diamond films using liquid carbon source precursors such as acetone, the theoretical explanation still needs to be elucidated. In this study, the density functional theory (DFT) method was used to analyze the decomposition and adsorption processes of acetone and methane on the surface of a diamond (111) models and to clarify the advantages of liquid carbon source precursors. The decomposition and adsorption reaction processes of trimethyl borate, urea, and ethyl orthosilicate on the surface of diamond (111) model were also analyzed to elucidate the doping mechanisms of B, N, and Si elements. Additionally, undoped diamond films were fabricated using acetone and methane precursors, illustrating that liquid precursors have higher growth rates than gas precursors. B-, N-, and Si-doped diamond films were also fabricated using liquid-doped carbon source precursors. Element detection by TOF-SIMS illustrates that all three elements had been doped into the diamond films and were uniformly distributed. Conversely, no doping elements were detected in N-doped diamond film fabricated with nitrogen and methane precursors.

Tungsten Oxide Mediated Quasi-van der Waals Epitaxy of WS2 on Sapphire.

Conventional epitaxy plays a crucial role in current state-of-the art semiconductor technology, as it provides a path for accurate control at the atomic scale of thin films and nanostructures, to be used as the building blocks in nanoelectronics, optoelectronics, sensors, etc. Four decades ago, the terms "van der Waals" (vdW) and "quasi-vdW (Q-vdW) epitaxy" were coined to explain the oriented growth of vdW layers on 2D and 3D substrates, respectively. The major difference with conventional epitaxy is the weaker interaction between the epi-layer and the epi-substrates. Indeed, research on Q-vdW epitaxial growth of transition metal dichalcogenides (TMDCs) has been intense, with oriented growth of atomically thin semiconductors on sapphire being one of the most studied systems. Nonetheless, there are some striking and not yet understood differences in the literature regarding the orientation registry between the epi-layers and epi-substrate and the interface chemistry. Here we study the growth of WS2 via a sequential exposure of the metal and the chalcogen precursors in a metal-organic chemical vapor deposition (MOCVD) system, introducing a metal-seeding step prior to the growth. The ability to control the delivery of the precursor made it possible to study the formation of a continuous and apparently ordered WO3 mono- or few-layer at the surface of a c-plane sapphire. Such an interfacial layer is shown to strongly influence the subsequent quasi-vdW epitaxial growth of the atomically thin semiconductor layers on sapphire. Hence, here we elucidate an epitaxial growth mechanism and demonstrate the robustness of the metal-seeding approach for the oriented formation of other TMDC layers. This work may enable the rational design of vdW and quasi-vdW epitaxial growth on different material systems.