Numerical modeling of SiH4 discharge for Si thin film deposition for thin film transistor and solar cells

Amorphous and microcrystalline silicon thin films are used in solar cells as a multi-junction photovoltaic device. Plasma enhanced chemical vapor deposition is used and high deposition rate of a few nm/s is required while keeping film quality. SiH₄ is used as a precursor diluted with H₂. Electron impact processes give complex interdependent plasma chemical reactions. Many researchers suggest keeping high H/SiH_x ratio is important. Numerical modeling of this process for capacitively coupled plasma and inductively coupled plasma is done to investigate which process parameters are playing key roles in determining it. A full set of 67 volume reactions and reduced set are used. Under most of conditions, CCP shows 100 times higher H/SiH₃ ratio over ICP case due to its spatially localized two electron temperature distribution. Multi hollow cathode type CCP is also modeled as a 2 × 2 hole array. For Ar, the discharge is well localized at the neck of the hole at a few Torr of gas pressure. H₂ and SiH₄ + H₂ needed higher gas pressure and power density to get a multi hole localized density profile. H/SiH₃ was calculated to be about 1/10.     

Characterisation of ultrasonically sprayed InxSy buffer layers for Cu(In,Ga)Se2 solar cells

In order to replace chemical bath deposited (CBD) CdS buffer layers in Cu(In,Ga)Se₂ (CIGS) solar cells by an alternative material, In_xS_y thin-film buffer layers were prepared by ultrasonic spray pyrolysis at various substrate temperatures. X-ray Diffraction measurements confirmed that the films contained primarily the tetragonal In₂S₃ phase. X-ray Photoelectron Spectroscopy measurements revealed a small concentration of chlorine impurity throughout the In_xS_y layer. By depositing the indium sulphide layer as buffer layer in the CIGS solar cell configuration, a maximum solar cell efficiency of 8.9% was achieved, whilst the reference cell with CdS/CIGS on a similar absorber exhibited 12.7% efficiency. Additionally, light soaking enhanced the efficiency of In_xS_y/CIGS cells primarily by improvements in fill factor and open circuit voltage.     

Development of TiSiN CVD process using TiCl4/SiH4/NH3 chemistry for ULSI anti-oxidation barrier applications

CVD-TiSiN may be promising material for O₂ diffusion-barrier films in ultra-large scale integrated (ULSI) circuit applications, especially for dynamic random-access memory (DRAM) capacitors. We developed a method for introducing Si into TiN, which is a common material used for diffusion-barrier films. TiSiN films were deposited by reacting TiCl₄, SiH₄, and NH₃ in a hot-wall CVD reactor. We measured TiSiN film deposition rates, composition, crystal structure, and resistivity as a function of SiH₄ partial pressure. Adding Si to TiN converts the TiN film structure from columnar grains to columnar-free structure films, thereby effectively removing the diffusion paths for O₂. The resistivity of TiSiN films was increased by adding SiH₄ to the reactant gas. With an increase in SiH₄ partial pressure up to P_SiH4=0.8 Torr, the resistivity gradually increased, but for P_SiH4=1.2 Torr, the phase present in the film was almost SiN and its resistivity jumped up. TiSiN film rapid thermal annealing was performed to evaluate the anti-oxidation performance at the temperature range from 400 to 600 °C in 100 Torr of O₂. For an increase the Si concentration up to 4.4 at.% improved anti-oxidation performance of TiSiN films. Flow modulation chemical vapor deposition (FMCVD) was used to create TiSiN films with low Cl concentration and improved anti-oxidation performance.     

Effect of NH3 plasma treatment on the device performance of ZnO based thin film transistors

We fabricated an enhancement-mode thin film transistor (TFT) using ZnO as an active channel layer deposited by radio frequency (rf) magnetron sputtering. The NH₃ plasma passivation was performed in order to improve the electrical properties of the ZnO TFTs. We observed that the NH₃ plasma treated ZnO TFTs revealed improved device performances, which include the field effect mobility of 34 cm²/Vs, threshold voltage of 14 V, subthreshold swing of 0.44 V/dec, off-current of 10⁻¹¹ A and on to off ratio higher than 10⁵. These results demonstrate that NH₃ plasma treatment could effectively enhance the performance of the ZnO based TFT device.     

Luminescence properties of Eu ions doped in Y2−xGdxO3 thin films grown by pulsed laser deposition method

Luminescence properties of Y_2−xGd_xO₃:Eu³⁺ (x = 0 to 2.0) thin films are investigated by site-selective laser excitation spectroscopy. The films were grown by pulsed laser deposition method on SiO₂ (100) substrates. Cubic phase Y₂O₃ and Gd₂O₃ and monoclinic phase Gd₂O₃ are identified in the excitation spectrum of the ⁷F₀ → ⁵D₀ transition of Eu³⁺. The emission spectra of the ⁵D₀ → ⁷F_J (J = 1 and 2) transition from individual Eu³⁺ centers were obtained by tuning the laser to resonance with each excitation line. The excitation line at around 580.60 nm corresponds to the line from Eu³⁺ with C₂ site symmetry of cubic phase. New lines at 578.65 and 582.02 nm for the C_S sites of Gd₂O₃ with monoclinic phase are observed by the incorporation of Gd in Y₂O₃ lattice. Energy transfer occurs between Eu³⁺ ions at the C_S sites and from Eu³⁺ ions at the C_S sites to those at the C₂ site in Y_2−xGd_xO₃.     

Surface etching effects of amorphous C:H and CNx:H films formed by supermagnetron plasma for field emission use

Supermagnetron plasma was used to deposit amorphous hydrogenated carbon (a-C:H) and hydrogenated carbon nitride (a-CN_x:H) films for field-emission devices using i-C₄H₁₀/(H₂ or N₂). It was also used to improve the field-emission characteristics by surface etching using N₂/H₂ plasma. The best emission threshold electric field (E_TH) was 13 and 12 V/μm for devices using as-deposited a-C:H and as-deposited a-CN_x:H films, respectively, while they were remarkably improved to 11 and 8 V/μm by surface etching using N₂/H₂ (120/40 sccm) gas, though surface roughness was slightly increased by the surface etching. The hardness of as-deposited films was higher than 22 GPa.     

Enhanced G4 emission in NaLaF4: Pr, Yb and charge transfer in NaLaF4: Ce, Yb studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF₄: 1%Pr³⁺, 5%Yb³⁺ and NaLaF₄: 1%Ce³⁺, 5%Yb³⁺ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr³⁺(³P₀ → ¹G₄), Yb³⁺(²F_7/2 → ²F_5/2) energy transfer step takes place, significant Pr³⁺¹G₄ emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr³⁺ and Yb³⁺ can be given. In the case of NaLaF₄: Ce³⁺, Yb³⁺ it is concluded that the observed Yb³⁺ emission upon Ce³⁺ 5d excitation is the result of a charge transfer process instead of down-conversion.     

Electrical properties of AlNx/Al/Mo composite film prepared for use in thin-film transistors

In the present study, AlN_x/Al/Mo composite films with various thicknesses of AlN_x and Al layers were prepared to replace commercial AlNd/Mo composite film as the gate metal of the two metal layers (namely the gate metal and the source-drain metal) in thin-film transistor (TFT) specimens. The prerequisite for the TFT device is that no hillock is formed. The electrical properties of the AlN_x/Al/Mo TFT device rival those of the AlNd/Mo TFT device. One of eight kinds of AlN_x/Al/Mo composite films (0.05 µm/0.2 µm/0.07 µm) without hillocks was compared with the AlNd/Mo (0.25 µm/0.07 µm) composite film. The line width after development and strip inspections, the I_g (gate leakage current)-V_g (gate voltage) curve, the coating film resistance to electricity, the contact resistance between the indium tin oxide (ITO) film and the metal film, the I_d-V_g curve, and the critical dimension loss (CD loss) were compared. The experimental results indicate that the metal line widths for these two composite films are similar. The coating film resistance, the contact resistance between the ITO film and the metal film, and the I_d-V_g curve for the AlN_x/Al/Mo TFT device were similar to those for the AlNd/Mo TFT device. The CD loss shown in the AlN_x/Al/Mo TFT device was lower than that for the AlNd/Mo TFT device.     

Multilayer amorphous hydrogenated carbon (a-C:H) and SiOx doped a-C:H films for optical applications

In this study SiO_x doped amorphous hydrogenated carbon (a-C:H) films were formed from hexamethyldisiloxane (with hydrogen transport gas) by closed drift ion beam deposition applying variable ion beam energy (300-800 eV). The band gap dependence on the deposition energy was determined and used in production of SiO_x doped a-C:H and a-C:H (formed from acetylene gas) multilayer (two and four layers) stack. Optical properties of the multilayer structures as well as individual layers were analysed in the UV-VIS-NIR range (200-1000 nm). It was shown that employing double or four layer systems, the reflectivity of the multilayer structure-crystalline silicon can be tuned to almost 0% at specific wavelength range (550-950 nm), important in solar cell applications.     

Electro-deposition of Y2O3:Eu thin film phosphor and its luminescent properties

Y₂O₃:Eu³⁺ red-emitting thin film phosphor was prepared by a two-step process: the cathodical deposition of thin film of yttrium hydroxide and europium hydroxide followed by an annealing process to achieve Eu³⁺ doped Y₂O₃ film. It is found that the atomic content of Eu³⁺ can be well controlled by simply adjusting the volume ratio of Y(NO₃)₃ to Eu(NO₃)₃ solutions. Dependence of the photoluminescence intensity on the atomic content of Eu³⁺ in Y₂O₃ was also studied. The best photoluminescence performance of Y₂O₃:Eu³⁺ thin film phosphor was achieved as atomic content of Eu³⁺ equal to 1.85 at.%.     

Tuning the luminescence color and enhancement of afterglow properties of Sr(4−x−y)CaxBayAl14O25:Eu,Dy phosphor by adjusting the composition

Color point tuning is an important challenge for improving the practical applications of various displays, especially there are very limited white color single hosts that emits in the white spectrum. In this paper, the possibility of color tuning by substituting part of host lattice cation (Sr²⁺ ions) by Ca²⁺ or Ba²⁺ ions in an efficient strontium aluminate phosphor, Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺, is reported and found to be very promising for displays. A detail study by replacing part of Sr²⁺ with Ca²⁺ or Ba²⁺ has been investigated. X-ray diffraction study showed that crystal structure of Sr₄Al₁₄O₂₅ is preserved up to 20 mol of Ca²⁺ ion exchange while it is limited to 10 mol of Ba²⁺ ions exchange. Substantial shift in the emission band and color were observed by substitution of Sr²⁺ by Ca²⁺ or Ba²⁺ ions. A bluish-white emission and afterglow was observed at higher Ca²⁺ ions substitution. Further, partial Ca²⁺ substitutions (up to 0.8 mol) resulted in enhanced afterglow of Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺ phosphor. However, Ba²⁺ substitution decreased the fluorescence as well afterglow of the Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺ phosphor significantly. The enhanced phosphorescence by partial Ca²⁺ substitution is explained on the basis of increased density of shallow traps associated with higher solubility of Dy³⁺ ions in to the host lattice due to equivalent size of Ca²⁺ and Dy³⁺ ions. Thus, Ca²⁺ substitution in the Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺ phosphor is a promising method for tuning the emission color and improving the afterglow intensity of the phosphor.     

Facile fabrication of La(OH)3 nanorod arrays and their application in wastewater treatment

Hexagonal and vertically aligned La(OH)₃ nanorod arrays have been fabricated in a large scale via a simple electrochemical method without any hard templates and surfactants. By the aid of potential-time curve, a possible formation process of the La(OH)₃ nanorod arrays is proposed, and the gas bubbles functioning as a dynamic template might be responsible for the growth of ordered La(OH)₃ nanorods. The total absorption capacities of the as-prepared products for Congo red is about 73.5 mg g^− 1, which shows an environmental engineering application in removing organic dye from water. In short, this synthetic method shows prominent advantages such as its low-cost, easy preparation, good adherence and suitability for preparing other nanoarrays.     

Structure, magnetic and electrical transport properties of (Fe3O4)100 − xPtx composite films

Structure, magnetic and electrical transport properties of the polycrystalline (Fe₃O₄)_100 − xPt_x composite films fabricated using DC reactive magnetron sputtering at ambient temperature were investigated systematically. It is found that the films are composed of inverse-spinel-structured polycrystalline Fe₃O₄ and Pt. Pt addition proves the growth of Fe₃O₄ grains with the (111) orientation. All the films are ferromagnetic at room temperature. The dominant magnetic reversal mechanism turns from domain wall motion to Stoner-Wohlfarth rotation with the increasing x. The electrical transport mechanism also changes with the increasing x because Pt addition decreases the height of the tunneling barrier at the Fe₃O₄ grain boundaries, and makes the magnetoresistance of the films decrease.     

Development of TiSiN CVD process using TiCl4/SiH4/NH3 chemistry for ULSI anti-oxidation barrier applications

CVD-TiSiN may be promising material for O₂ diffusion-barrier films in ultra-large scale integrated (ULSI) circuit applications, especially for dynamic random-access memory (DRAM) capacitors. We developed a method for introducing Si into TiN, which is a common material used for diffusion-barrier films. TiSiN films were deposited by reacting TiCl₄, SiH₄, and NH₃ in a hot-wall CVD reactor. We measured TiSiN film deposition rates, composition, crystal structure, and resistivity as a function of SiH₄ partial pressure. Adding Si to TiN converts the TiN film structure from columnar grains to columnar-free structure films, thereby effectively removing the diffusion paths for O₂. The resistivity of TiSiN films was increased by adding SiH₄ to the reactant gas. With an increase in SiH₄ partial pressure up to P_siH4 = 0.8 Torr, the resistivity gradually increased, but for P_siH4 = 1.2 Torr, the phase present in the film was almost SiN and its resistivity jumped up. TiSiN film rapid thermal annealing was performed to evaluate the anti-oxidation performance at the temperature range from 400 to 600 °C in 100 Torr of O₂. For an increase the Si concentration up to 4.4 at.% improved anti-oxidation performance of TiSiN films. Flow modulation chemical vapor deposition (FMCVD) was used to create TiSiN films with low Cl concentration and improved anti-oxidation performance.     

Depth redistribution of components of SiOx layers prepared by magnetron sputtering in the process of their decomposition

The process of thermal decomposition of SiO_x layers prepared by magnetron co-sputtering of Si and SiO₂ on Si and quartz substrates is studied by Auger and secondary ion mass spectroscopies. It is found that high temperature annealing of the layers causes a Si-depleted region near the layer/substrate interface. It is shown that the formation of this region does not depend on the type of substrate but depends on the content of excess Si and is observed at high content of excess Si. When the excess Si content decreases, the Si-depleted region at first smears and then disappears. The mechanism of SiO_x decomposition and possible reasons for the appearance of the Si-depleted region are discussed.     

Photoluminescence characteristics of Li-doped CaTiO3:Pr thin films grown on Si (100) substrate by PLD

The effects of Li-doped CaTiO₃:Pr³⁺ thin films have been investigated by varying the lithium ion concentrations from 0 to 5 wt.%. The films have been deposited on Si (100) substrate using a pulsed laser deposition technique. Structural properties of these films have been studied by the measurement of their XRD, SEM, and AFM. The variation of Li⁺ concentration influences the crystallinity and surface morphology of the CaTiO₃:Pr³⁺ thin films. As Li⁺ content increases from 0 to 1 wt.%, the crystallinity and intensity of emission increases. The dominant emission is from ¹D₂ → ³H₄ transition at 613 nm. The ¹D₂ emission quenching has also been observed in highly doped sample and is related to the cross-relaxation process between Pr³⁺ ions.     

Synthesis and characterization of Ca3Co4O9 thin films prepared by sol-gel spin-coating technique on Al2O3(001)

Ca₃Co₄O₉ thin films are deposited on Al₂O₃(001) substrates using a sol-gel spin-coating process. X-ray diffraction shows that the film exhibits a single phase of Ca₃Co₄O₉ with the (00l) planes parallel to the film surface. The temperature dependence of magnetic susceptibility showed as expected the existence of two magnetic transitions similar to those observed in bulk samples: a ferrimagnetic and a spin-state transition around 19 and 375 K, respectively. At 5 K the magnetization curves along the c-axis of the Al₂O₃(001) show that the remanent magnetization and coercive field are close to those obtained for films grown by pulsed laser deposition, which evidences the interest to use such an easy technique to grow complex thin films oxides.     

Photoluminescence properties of Y2O3:Tb and YBO3:Tb green phosphors synthesized by hydrothermal method

In this work, two Tb³⁺ activated green phosphors: Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺ were prepared by hydrothermal method. Photoluminescence properties of both phosphors were studied in details. Both phosphors exhibit similar luminescent characteristics symbolized by the dominant green emission at 545 nm. Concentration quenching occurs at the Tb³⁺ concentration of 1.60 atomic% and 2.57 atomic% for Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺, respectively. Luminescence decay properties were characterized to better understand the mechanism of concentration quenching. Based on the calculation, the concentration quenching in both phosphors was caused by the dipole–dipole interaction between Tb³⁺ ions.     

Polarized spectral properties of Tm:K5Bi(MoO4)4 crystal

Trivalent thulium-doped K₅Bi(MoO₄)₄ single crystals were grown by the Czochralski method. Its polarized absorption and fluorescence spectra and fluorescence decay curves were recorded at room temperature. On the basis of the Judd-Ofelt theory, the spectral parameters of the Tm³⁺:K₅Bi(MoO₄)₄ crystal were calculated. The cross relaxations between Tm³⁺ ions were analyzed. The emission cross sections of the ³F₄ → ³H₆ transition were obtained by the Fuchtbauer-Ladenburg formula and then the gain cross sections around 1.9 μm were calculated. The peak emission cross section and width of emission band around 1.9 μm are comparable to those for Tm³⁺:YAG and the tunable range is about 280 nm for the potential ∼1.9 μm laser operation via the ³F₄ → ³H₆ transition.