Field Emission and Electric Discharge of Nanocrystalline Diamond Films

Nanocrystalline diamond (NCD) films were produced by microwave plasma-enhanced chemical vapor deposition (MPECVD) using gas mixtures of Ar, H₂, and CH₄. The structural properties, electron emission, and electric discharge behaviors of the NCD films varied with H₂ flow rates during MPECVD. The turn-on field for electron emission at a pressure of 2.66 × 10⁻⁴ Pa increased from 4.2 V μm⁻¹ for the NCD films that were deposited using a H₂ flow rate of 10 cm³ min⁻¹ to 7 V μm⁻¹ for films deposited at a H₂ flow rate of 20 cm³ min⁻¹. The NCD film with a low turn-on field also induced low breakdown voltages in N₂. The grain size and roughness of the NCD films may influence both the electron emission and the electric discharge behaviors of the NCD cathodes.     

基片预处理工艺对CVD金刚石成核行为的影响

本文采用微波等离子体辅助化学气相沉积工艺,对不同预处理的(100)单晶硅基片上金刚石的成核行为进行了初步研究,并利用定量金相及扫描电子显微镜分析了金刚石的成核速率及晶体特征。由此提出了用0.1μm超细金刚石粉对基片的研磨工艺。该工艺可有效提高金刚石成核率,从而有助于获得晶粒细小均匀,表面粗糙度低的金刚石薄膜。采用C60涂复并结合研磨工艺,使成核率获得了进一步提高。     

The Substrate Effects on Kinetics and Mechanism of Solid-Phase Crystallization of Amorphous Silicon Thin Films

The substrate effects on solid-phase crystallization of amorphous silicon (a-Si) films deposited by low-pressure chemical vapor deposition (LPCVD) using Si₂H₆ gas have been extensively investigated. The a-Si films were prepared on various substrates, such as thermally oxidized Si wafer (SiO₂/Si), quartz and LPCVD-oxide, and annealed at 600 °C in an N₂ ambient for crystallization. The crystallization behavior was found to be strongly dependent on the substrate even though all the silicon films were deposited in amorphous phase. It was first observed that crystallization in a-Si films deposited on the SiO₂/Si starts from the interface between the a-Si and the substrate, so called interface-induced crystallization, while random nucleation process dominates on the other substrates. The different kinetics and mechanism of solid-phase crystallization is attributed to the structural disorderness of a-Si films, which is strongly affected by the surface roughness of the substrates.     

Metalorganic chemical vapor deposition of silver thin films for future interconnects by direct liquid injection system

Deposition of Ag films by direct liquid injection-metal organic chemical vapor deposition (DLI-MOCVD) was chosen because this preparation method allows precise control of precursor flow and prevents early decomposition of the precursor as compared to the bubbler-delivery. Silver(I)-2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedionato-triethylphosphine [Ag(fod)(PEt₃)] as the precursor for Ag CVD was studied, which is liquid at 30 °C. Ag films were grown on different substrates of SiO₂/Si and TiN/Si. Argon and nitrogen/hydrogen carrier gas was used in a cold wall reactor at a pressure of 50–500 Pa with deposition temperature ranging between 220 °C and 350 °C. Ag films deposited on a TiN/Si diffusion barrier layer have favorable properties over films deposited on SiO₂/Si substrate. At lower temperature (220 °C), film growth is essentially reaction-limited on SiO₂ substrate. Significant dependence of the surface morphology on the deposition conditions exists in our experiments. According to XPS analysis pure Ag films are deposited by DLI-MOCVD at 250 °C by using argon as carrier gas.     

Electrical properties of carbon nitride thin films: Role of morphology and hydrogen content

The influence of hydrogen content and ambient humidity on the electrical properties of carbon nitride (CN_x) films deposited by reactive magnetron sputtering from a graphite target in Ar discharges mixed with N₂ and H₂ at a substrate temperature of 350°C have been investigated. Carbon films deposited in pure Ar exhibit a dark resistivity at room temperature of ∼4 × 10⁻² Ωcm, while the resistivity is one order of magnitude lower for CN_0.25 films deposited in pure N₂, due to their denser morphology. The increasing H₂ fraction in the discharge gas leads to an increased resistivity for all gas mixtures. This is most pronounced for the nitrogen-free films deposited in an Ar/H₂ mixture, where the resistivity increases by over four orders of magnitude. This can be related to a decreased electron mobility as H inhibits the formation of double bonds. After exposure to air, the resistivity increases with time through two different diffusion regimes. The measured electrical properties of the films are related to the apparent film microstructure, bonding nature, and ambient humidity.     

核化密度对硅上生长异质外延金刚石膜的影响

本文利用扫描电子显微镜及Raman谱等研究了Si（100）上异质外延金刚石膜的生长．金刚石膜是由微波等离子体CVD法制备的。实验结果表明核化密度对Si（100）上异质外延金刚石膜生长有重要的影响．过低或过高的核化密度都不可能形成异质外延金刚石膜。     

Plasma-assisted chemical vapor deposited silicon oxynitride as an alternative material for gate dielectric in MOS devices

Silicon oxynitride films have been deposited on Si substrates at 200 °C by a remote-plasma-assisted process in a RF-plasma CVD reactor using Si(OC₂H₅)₄ (TEOS) as a precursor and nitrogen as gas ambient. During deposition the Si substrates were biased with negative voltages of −120 and −600 V or were under no DC bias and the influence of this voltage on the film properties has been considered. Film parameters, such as density, chemical bonds, refractive index, composition, oxide and interface charge densities of the deposited dielectric films have been estimated by analysis of the results from the infrared (IR) spectroscopy, spectral ellipsometry (SE) and capacitance-voltage (C-V) measurements. The IR and SE results have proven the films are oxynitrides of silicon with predominantly oxide network. The analysis of the capacitance-voltage characteristics has shown that the dielectric charge densities increase with increasing DC bias but they remain considerably low in comparison to that for a standard SiO₂/Si structure before any annealing steps.     

PLD方法在CVD金刚石膜上生长ZnO薄膜及其特性研究

采用脉冲激光沉积(PLD)技术,在(110)和(100)织构金刚石膜上成功制备出高度c-轴取向的ZnO薄膜,然后在纯氮气氛条件下对ZnO薄膜进行退火处理.作为比较,也在(100)Si上生长的ZnO薄膜进行了相同的处理.通过测量X射线衍射(XRD)谱和光致发光(PL)谱,研究了不同衬底性质和退火对薄膜结构和发光特性的影响.实验结果表明,在(100)织构金刚石上的ZnO膜具有最好的结晶质量,其半高宽只有0.2°.退火之后近紫外发光峰明显减弱的同时,绿色发光峰得到增强.这里归结为氮气退火后氧空位的增加,这点从退火后的XPS谱中可以得到进一步的确认.     

Electrical property dependence on thickness and morphology of nanocrystalline diamond thin films

In this study, we investigate the influence of nanocrystalline diamond (NCD) thin film morphology and thickness on their electrical properties. NCD films are grown on p-type Si substrates with varied thicknesses from 250 to 788 nm. Electrical contacts are formed from combination of Ti/Au metal layers (100 nm thick each). The I-V and breakdown field measurements are used to analyze the electrical properties of metal/NCD/Si sandwich structure. In addition, NCD films are analyzed by scanning electron microscopy and Raman spectroscopy for better interpretation of the I-V measurements.     

Formation of thin-film HfO<Subscript>2</Subscript>/Si(100) structures by high-frequency magnetron sputtering

The results of X-ray structural investigations and current-voltage measurements of the HfO₂/Si(100) structures are presented. The HfO₂ films of 50 nm thickness were deposited in a Si substrate by high-frequency magnetron sputtering in argon plasma and subjected to rapid thermal annealing at 500, 700, and/or 800°C in the Ar or O₂ ambient. It is shown that the HfO₂ films become polycrystalline after annealing. The presence of various crystalline phases in them and the form of the I–V characteristics of the Al/HfO₂/Si(100) test structures strongly depend on the growth conditions and the gas ambient during the rapid thermal annealing. It is established that the HfO₂ films deposited at a high-frequency bias at a substrate of −7 V during the growth and then passed through rapid thermal treatment in the O₂ ambient at 700°C have the highest breakdown voltages.     

Chemical bonding states and local structures of the oriented hexagonal BCN films synthesized by microwave plasma CVD

In order to synthesize oriented hexagonal boron carbonitride (h-BCN) films, borane-triethylamine complex (C₆H₁₈BN) was used as a single-source precursor. The films were deposited on Si (1 0 0) substrate by microwave plasma-enhanced chemical-vapor deposition using CH₄+H₂ as the carrier gas. The deposition was performed at different microwave powers of 200–500 W at working pressure of 5.0 Torr. The microhardness, estimated by nano-indentation test, of the films was found to be around 4 GPa. Fourier transform infrared spectroscopy (FT-IR) confirmed the formation of hexagonal BCN phase in a short-range order. The chemical composition and the local structures of films were studied by X-ray photoelectron spectroscopy (XPS) and the near-edge X-ray absorption fine structure (NEXAFS) spectroscopic measurements. XPS revealed that B, C and N atoms in the deposited films are in various chemical environments such as B–N, B–C, C–N and B–C–N atomic hybrid configuration. The NEXAFS measurement suggested that the B atoms are bonded not only to the N atoms but also to the C atoms to form various local structures of sp² B–C–N hybrid configurations. The polarization dependence of NEXAFS suggested that the local structures of the sp² BCN layers have different atomic orientations to the substrate.     

Optical dispersion analysis within the IR range of thermally grown and TEOS deposited SiO2 films

SiO₂ thin films, with thickness ranging between approximately 13 and 95 nm, have been thermally grown at 950°C in dry oxygen and chemically vapor deposited at low pressures (0.3 Torr) by decomposition of tetraethylorthosilicate (TEOS) at 710°C, on Si (100) substrates. Dispersion analysis was performed on Fourier transform infrared (FTIR) transmission spectra of these films within the range 900–1400 cm⁻¹. It was found that the spectra were best described within this range, by four Lorentz oscillators located near 1060, 1089, 1165 and 1220 cm⁻¹ almost independent of film thickness. The polarization of the oscillators (proportional to their strength) was found to increase slightly, and their widths to decrease, with film thickness. From the study of the FTIR spectra obtained at room temperature, it was suggested that at this temperature, a considerable number of Si–O–Si angles in these SiO₂ films are distributed in a way expected at higher temperatures and that the distribution of the Si–O–Si angles depends on the thermal history of the film and the method of growth.     

Anomalous Effect of Hydrogen Dilution on the Crystallinity of ICPCVD-Grown Silicon Thin Films at Very Low Temperature

The structural properties of Si thin films deposited by inductively coupled plasma chemical vapor deposition at 150°C and at different dilution ratios of H₂ to SiH₄ + H₂ were studied. The crystallinity and grain sizes of Si films decreased with increasing H dilution ratios and the onset of the transition from polycrystalline Si (poly-Si) to amorphous Si (a-Si) was observed at a 98% H dilution ratio. This is an anomalous effect compared with the effect of H dilution on the morphology of Si films grown by conventional plasma- enhanced chemical vapor deposition processes. At a 99% H dilution ratio, the morphology completely changed to the amorphous state. The influence of radiofrequency (RF) power on crystallinity was also studied and the quality of poly-Si was improved by increasing the RF power.     

The formation of ß SiC on Si

ß-SiC was formed on Si substrates in an horizontal, rf powered reactor. The reaction of Si with CH₄} was either directly at temperatures of 1200-1350?C or by a two step reaction in which CH₄} was first cracked at 900?C and then the deposited C reacted with Si at temperatures of 1200-1350?C. Important features of the study were the minimization of contam-inants from susceptor and substrate support materials, removal of native oxides and a novel susceptor design. A rectangular, TaC coated Ta susceptor was used in conjunction with sapphire supports. Preheated He was used as a carrier gas. Growth characteristics and film structure are presented as a function of CH₄} concentration and substrate temperature.     

Characterizations of high resistivity TiNxOy thin films for applications in thin film resistors

We report about developing high resistivity thin film resistors using titanium oxy-nitride. Titanium nitride films of different thicknesses ranging from 50 to 300 nm were deposited on SiO₂/Si substrates using the reactive magnetron sputtering method. After deposition, these films were annealed in the air ambient. The structural and electrical properties of the films were examined as a function of annealing temperature. The samples with various thicknesses show TiN(1 1 1) phase. The sheet resistance increases from 150 up to 420 Ω/□ when the film thickness decreases from 300 to 50 nm. Temperature coefficience of resistance (TCR) of the films significantly decreased with decreasing the film thickness. The TCR of 50-nm thick film is quite low, about 49 ppm/K.     

Vibrational spectroscopy characterization of low-dielectric constant SiOC:H films prepared by PECVD technique

Low-dielectric constant SiOC:H films were prepared by plasma enhanced chemical vapour deposition (PECVD) from trimethyl-silane (H–Si–(CH₃)₃) and ozone (O₃) gas mixture. The samples were preliminarily annealed at 400 °C in N₂ atmosphere and then in N₂+He plasma. Afterwards, they were treated in vacuum at some fixed temperatures in the range between 400 and 900 °C. Structural investigations of the annealed films were carried out by means of vibrational spectroscopy techniques. FT-IR spectrum of a preliminarily treated sample shows absorption bands due to stretching modes of structural groups like Si–CH₃ at 1270 cm⁻¹, Si–O–Si at 1034 cm⁻¹ and C–H_x in the region between 2800 and 3000 cm⁻¹. No significant spectral change was observed in the absorption spectra of samples annealed up to 600 °C, indicating that the preliminarily treated film retains a substantial structural stability up to this temperature. Above 600 °C, absorption spectra show a strong quenching of H-related peaks while the band due to Si–O–Si anti-symmetric stretching mode shifts towards higher energy, approaching the value observed for thermally grown SiO₂. Raman spectra of samples treated at temperatures T500 °C exhibit both D and G bands typical of sp²-hybridised carbon, due to the formation of C–C bonds within the film which is accompanying the release of hydrogen. The intensity of D and G bands becomes more pronounced in samples annealed at higher temperatures, thus suggesting a progressive precipitation of carbon within the oxide matrix.     

Optical and electrical characterization of hafnium oxide deposited by liquid injection atomic layer deposition

Optical and electrical properties of a set of high-k dielectric HfO₂ films, deposited by liquid injection atomic layer deposition (LI-ALD) and post deposition annealed (PDA) in nitrogen (N₂) ambient at various temperatures (400–600 °C), were investigated. The films were prepared using the cyclopentadienyl of hafnium precursor [Cp₂Hf(CH₃)₂] with water deposited at 340 °C. The spectroscopic ellipsometric (SE) results show that the characteristics of the dielectric functions of these films are strongly affected by annealing temperatures. I–V results show that N₂-based PDA enhances the average energy depth of the shallow trapping defects from Poole–Frenkel conduction fitting. This also correlated with the measured increase in MOS capacitance–voltage hysteresis.     

Conduction type and defect levels of β-FeSi2 films grown by MBE with different Si/Fe ratios

[1 0 0]-oriented β-FeSi₂ films were grown on Si(0 0 1) substrates by molecular beam epitaxy (MBE) with a deposited Si to Fe atomic ratio (Si/Fe ratio) varied from 1.6 to 2.8. It was found that the conduction type of the β-FeSi₂ films changed from p- to n-type between the deposited Si/Fe=2.4 and 2.8. Rutherford Back Scattering (RBS) measurements revealed that the real Si/Fe ratio of β-FeSi₂ is 2.0–2.1 for all the samples after 900°C annealing for 14 h, showing that stoichiometry of the grown films is almost satisfied even though the deposited Si/Fe ratio was away from stoichiometry.     

Atomic-layer-deposited tantalum silicate as a gate dielectric for III-V MOS devices

TaSiO_x thin films with Si/(Ta + Si) mole fractions between 0 and 0.6 have been deposited using atomic-layer deposition on Si and InGaAs at 250 °C. Interface defects on InGaAs were on the order of 10¹² cm⁻² eV⁻¹, which is comparable to state-of-the-art Al₂O₃ deposited by atomic-layer deposition using Al(CH₃)₃ and H₂O while the dielectric permittivity of TaSiO_x is considerably higher.     

Optical properties of Zn1−xMgxO nanorods using catalysis-driven molecular beam epitaxy

We report on the optical properties of (Zn,Mg)O nanorods grown by catalyst-driven molecular beam epitaxy. The process is site-specific, as single crystal (Zn,Mg)O nanorod growth is realized via nucleation on Ag films or islands that are deposited on a SiO₂-terminated Si substrate surface. Growth occurs within a flux of Zn, Mg, and O₂/O₃ mixture at substrate temperatures of 400–500 °C. With the addition of Mg, the nanorod morphology becomes more uniform relative to the pure ZnO nanomaterials synthesized under similar conditions. The (Zn,Mg)O nanorods are cylindrical, exhibiting diameters of 15–40 nm and lengths in excess of 1 μm. The (Zn,Mg)O nanorods exhibit a strong photoluminescence response, showing a slight shift to shorter wavelengths due to Mg incorporation.