Thin film encapsulation of DSSCs on plastic substrate

Aluminum oxynitride (AlO_xN_y) films were deposited on polyethylene naphthalate (PEN) substrates using a reactive radio frequency (RF) magnetron sputtering system by varying the nitrogen flow rate. Experimental results show that the AlO_xN_y films deposited on PEN substrate exhibit a pebble-like surface morphology. The deposition rate decreases slightly upon increasing the nitrogen flow rate. The surface roughness of the deposited AlO_xN_y films also decreases upon increasing the nitrogen flow rate. The AlO_xN_y film deposited at a nitrogen flow rate of 15 sccm exhibited the lowest water vapor transmission rate of 0.02 g/m²·day. Meanwhile, the passivation of AlO_xN_y films can effectively improve the long-term stability of plastic DSSC. Their power conversion efficiency can sustain 50% of the initial values even after 300 h.     

Cat-CVD SiN passivation films for OLEDs and packaging

A Roll-to-roll type catalytic chemical vapor deposition (Cat-CVD) apparatus was developed for the application to flexible organic light-emitting diode (OLED) displays and packaging. Silicon nitride (SiN_x) films were prepared by this roll-to-roll type apparatus at temperatures below 60 °C. It was found that these SiN_x films are highly moisture resistant, and the water vapor transmission rate (WVTR) on plastic substrates could be lowered to 0.01 g/m² day. Roll-to-roll type Cat-CVD is one of the most promising methods for the preparation of barrier films for OLED displays and packaging.     

Thin film passivation of organic light emitting diodes by inductively coupled plasma chemical vapor deposition

The characteristics of an SiN_x passivation layer grown by a specially designed inductively coupled plasma chemical vapor deposition (ICP-CVD) system with straight antennas for the top-emitting organic light emitting diodes (TOLEDs) are investigated. Using a high-density plasma on the order of ∼ 10¹¹ electrons/cm³ formed by nine straight antennas connected in parallel, a high-density SiN_x passivation layer was deposited on a transparent Mg-Ag cathode at a substrate temperature of 40 °C. Even at a low substrate temperature, single SiN_x passivation layer prepared by ICP-CVD showed a low water vapor transmission rate of 5 × 10^− 2 g/m²/day and a transparency of ∼ 85% respectively. In addition, current-voltage-luminescence results of the TOLED passivated by the SiN_x layer indicated that the electrical and optical properties of the TOLED were not affected by the high-density plasma during the SiN_x deposition process.     

Optimization of n nc-Si:H and a-SiNx:H layers for their application in nc-Si:H TFT

The n-type doped silicon thin films were deposited by plasma enhanced chemical vapor deposition (PECVD) technique at high and low H₂ dilutions. High H₂ dilution resulted in n⁺ nanocrystalline silicon films (n⁺ nc-Si:H) with the lower resistivity (ρ ∼0.7 Ω cm) compared to that of doped amorphous silicon films (∼900 Ω cm) grown at low H₂ dilution. The change of the lateral ρ of n⁺ nc-Si:H films was measured by reducing the film thickness via gradual reactive ion etching. The ρ values rise below a critical film thickness, indicating the presence of the disordered and less conductive incubation layer. The 45 nm thick n⁺ nc-Si:H films were deposited in the nc-Si:H thin film transistor (TFT) at different RF powers, and the optimum RF power for the lowest resistivity (∼92 Ω cm) and incubation layer was determined. On the other hand, several deposition parameters of PECVD grown amorphous silicon nitride (a-SiN_x:H) thin films were changed to optimize low leakage current through the TFT gate dielectric. Increase in NH₃/SiH₄ gas flow ratio was found to improve the insulating property and to change the optical/structural characteristics of a-SiN_x:H film. Having lowest leakage currents, two a-SiN_x:H films with NH₃/SiH₄ ratios of ∼19 and ∼28 were used as a gate dielectric in nc-Si:H TFTs. The TFT deposited with the NH₃/SiH₄∼19 ratio showed higher device performance than the TFT containing a-SiN_x:H with the NH₃/SiH₄∼28 ratio. This was correlated with the N−H/Si−H bond concentration ratio optimized for the TFT application.     

Hot-wire chemical vapor deposition of WO3−x thin films of various oxygen contents

We present the synthesis of tungsten oxide (WO_3−x) thin films consisting of layers of varying oxygen content. Configurations of layered thin films comprised of W, W/WO_3−x, WO₃/W and WO₃/W/WO_3−x are obtained in a single continuous hot-wire chemical vapor deposition process using only ambient air and hydrogen. The air oxidizes resistively heated tungsten filaments and produces the tungsten oxide species, which deposit on a substrate and are subsequently reduced by the hydrogen. The reduction of tungsten oxides to oxides of lower oxygen content (suboxides) depends on the local water vapor pressure and temperature. In this work, the substrate temperature is either below 250 °C or is kept at 750 °C. A number of films are synthesized using a combined air/hydrogen flow at various total process pressures. Rutherford backscattering spectrometry is employed to measure the number of tungsten and oxygen atoms deposited, revealing the average atomic compositions and the oxygen profiles of the films. High-resolution scanning electron microscopy is performed to measure the physical thicknesses and display the internal morphologies of the films. The chemical structure and crystallinity are investigated with Raman spectroscopy and X-ray diffraction, respectively.     

Supermagnetron plasma CVD of highly effective a-CNx:H electron-transport and hole-blocking films suited to Au/a-CNx:H/p-Si photovoltaic cells

Hydrogenated carbon nitride (a-CN_x:H) films (0-500 nm) were deposited on p-Si wafers to make Au/a-CN_x:H/p-Si photovoltaic cells using i-C₄H₁₀/N₂ supermagnetron plasma chemical vapor deposition. At a lower electrode RF power (LORF) of 50 W and an upper electrode RF power (UPRF) of 50-800 W, hard a-CN_x:H films with optical band gaps of 0.7-1.0 eV were formed. At a film thickness of 25 nm (UPRF of 500 W), the open circuit voltage and short circuit current density were 247 mV and 2.62 mA/cm², respectively. The highest energy conversion efficiency was 0.29%. The appearance of the photovoltaic phenomenon was found to be due to the electron-transport and hole-blocking effect of thin a-CN_x:H film.     

Developments in hot-filament metal oxide deposition (HFMOD)

Hot-filament metal oxide deposition (HFMOD) is a variant of conventional hot-filament chemical vapor deposition (HFCVD) recently developed in our laboratory and successfully used to obtain high-quality, uniform films of MO_x, WO_x and VO_x. The method employs the controlled oxidation of a filament of a transition metal heated to 1000 °C or more in a rarefied oxygen atmosphere (typically, of about 1 Pa). Metal oxide vapor formed on the surface of the filament is transported a few centimetres to deposit on a suitable substrate. Key system parameters include the choice of filament material and diameter, the applied current and the partial pressures of oxygen in the chamber. Relatively high film deposition rates, such as 31 nm min^− 1 for MoO_x, are obtained. The film stoichiometry depends on the exact deposition conditions. MoO_x films, for example, present a mixture of MoO₂ and MoO₃ phases, as revealed by XPS. As determined by Li⁺ intercalation using an electrochemical cell, these films also show a colouration efficiency of 19.5 cm² C^− 1 at a wavelength of 700 nm. MO_x and WO_x films are promising in applications involving electrochromism and characteristics of their colouring/bleaching cycles are presented. The chemical composition and structure of VO_x films examined using IRRAS (infrared reflection-absorption spectroscopy), RBS (Rutherford backscattering spectrometry) and XPS (X-ray photoelectron spectrometry) are also presented.     

Plastic substrate with gas barrier layer and transparent conductive oxide thin film for flexible displays

A novel plastic substrate for flexible displays was developed. The substrate consisted of a polycarbonate (PC) base film coated with a gas barrier layer and a transparent conductive thin film. PC with ultra-low intrinsic birefringence and high temperature dimensional stability was developed for the base film. The retardation of the PC base film was less than 1 nm at a wavelength of 550 nm (film thickness, 120 µm). Even at 180 °C, the elastic modulus was 2 GPa, and thermal shrinkage was less than 0.01%. The surface roughness of the PC base film was less than 0.5 nm. A silicon oxide (SiO_x) gas barrier layer was deposited on the PC base film by a roll-to-roll DC magnetron reactive sputtering method. The water vapor transmission rate of the SiO_x film was less than 0.05 g/m²/day at 40 °C and 100% relative humidity (RH), and the permeation of oxygen was less than 0.5 cc/m² day atm at 40 °C and 90% RH. As the transparent conductive thin film, amorphous indium zinc oxide was deposited on the SiO_x by sputtering. The transmittance was 87% and the resistivity was 3.5 × 10^− 4 ohm cm.     

Silicon oxide diffusion barrier coatings on polypropylene

In this study the influence of process conditions for the plasma-enhanced chemical vapor deposition of SiO_x diffusion barrier coatings on polypropylene (PP) is investigated and compared to results obtained on polyethylene terephthalate (PET). It was observed that the thermal load during deposition is much more crucial in the case of PP. If the thermal load is not the limiting factor, the composite parameter (CP) energy input per mass of precursor showed to be valuable to describe plasma conditions at constant oxygen to monomer ratio. Low oxygen transmission rates (OTRs) of 5.1 ± 3.6 and 0.3 ± 0.1 cm³/m²day/atm were achieved on PP and PET foil, respectively, for an optimal CP of 4.1 × 10⁵ J/g. Fourier transform infrared (FTIR) spectroscopy revealed that low carbon and silanol content is necessary for good barrier performance. Low RF power, necessary to reduce thermal load on PP, can be compensated by increasing the oxygen to monomer ratio.For favorable plasma conditions, the dependence of the OTR on the coating thickness follows a similar trend for both substrate materials with a critical thickness of approximately 12 nm. The residual permeation can be correlated to the defect density at each stage of film growth by means of a simple correlation. Further support for permeation through defects is found by the activated rate theory, since the apparent activation energy of oxygen permeation is below typical values of amorphous glasses and remains unchanged due to the deposition of SiO_x on both substrates.     

Co-sputtered oxide thin film encapsulated organic electronic devices with prolonged lifetime

Effective top-side thin film encapsulation for organic light-emitting devices (OLEDs) was achieved by deposition of a multi-layer water diffusion barrier stack to protect the device against moisture permeation. The barrier stack was formed by alternative depositions of co-oxide and fluorocarbon (CF_x) films. The co-oxide layer was fabricated by magnetron co-sputtering of silicon dioxide (SiO₂) and aluminum oxide (Al₂O₃). While the CF_x layer was formed by plasma enhanced chemical vapor deposition. The water vapor transmission rate of the optimized diffusion barrier stack can be down to 10^− 6 g/m²/day. The OLEDs encapsulated with the multilayer stack have been shown to have operation lifetime of over 18,000 h which is nearly the same as devices with conventional glass-cover encapsulation.     

Characteristics of SiOxNy films deposited by inductively coupled plasma enhanced chemical vapor deposition using HMDS/NH3/O2/Ar for water vapor diffusion barrier

SiO_xN_y thin films were deposited by inductively coupled plasma enhanced chemical vapor deposition (ICP-PECVD) using hexamethyldisilazane (HMDS, 99.9%)/NH₃/O₂/Ar at a low temperature, and examined for use as a water vapor diffusion barrier. The film characteristics were investigated as a function of the O₂:NH₃ ratio. An increase in the O₂:NH₃ ratio decreased the level of impurities such as -CH_x, N-H in the film through a reaction with oxygen. Thereby, a more transparent and harder film was obtained. In addition, an increase in the O₂:NH₃ ratio decreased the nitrogen content in the film resulting in a more SiO₂-like SiO_xN_y film. Using SiO_xN_y fabricated with an O₂:NH₃ ratio of 1:1, a multilayer thin film consisting of multiple layers of SiO_xN_y/parylene layers was formed on a polyethersulfone (PES, 200 μm) substrate, and its water vapor transmittance rate (WVTR) was investigated. A WVTR < 0.005 g/(m² day) applicable to organic thin film transistors or organic light emitting diodes was obtained using a multilayer composed of SiO_xN_y (260 nm)/parylene (< 1.2 μm) on the PES.     

Effect of oxygen pressure of SiOx buffer layer on the electrical properties of GZO film deposited on PET substrate

The present work was made to investigate the effect of oxygen pressure of SiO_x layer on the electrical properties of Ga-doped ZnO (GZO) films deposited on poly-ethylene telephthalate (PET) substrate by utilizing the pulsed-laser deposition at ambient temperature. For this purpose, the SiO_x buffer layers were deposited at various oxygen pressures ranging from 13.3 to 46.7 Pa. With increasing oxygen pressure during the deposition of SiO_x layer as a buffer, the electrical resistivity of GZO/SiO_x/PET films gradually decreased from 7.6 × 10^− 3 to 6.8 × 10^− 4 Ω·cm, due to the enhanced mobility of GZO films. It was mainly due to the grain size of GZO films related to the roughened surface of the SiO_x buffer layers. In addition, the average optical transmittance of GZO/SiO_x/PET films in a visible regime was estimated to be ~ 90% comparable to that of GZO deposited onto a glass substrate.     

Deposition and characterization of ultra-high barrier coatings for flexible electronic applications

A barrier structure consisting of SiO_x and SiN_x films was deposited on the polymer substrate at 80 °C via plasma-enhanced chemical vapor deposition (PECVD). However, the low radius of curvature (R_c) of the barrier-coated substrate may cause the inconvenience of the following fabrication processes. By depositing a 150 nm-SiN_x film, the R_c of the barrier-coated polycarbonate (PC) substrate can increase from 80 to 115 mm without inducing any cracks in the barrier structure. Furthermore, the thermal stress of the barrier structure can be adjusted via extending the PECVD process duration in the chamber and replacing PC by the polyethersulone (PES) substrate. The R_c can increase to ∼356 mm by depositing the 150 nm-SiN_x film on the other side of the PES substrate. Finally, the calcium test result of the barrier films/PES/SiN_x sample was calculated to be around 3.05 × 10⁻⁶ g/m²/day, representing that the barrier structure did not fail after modification.     

Effects of argon and oxygen flow rate on water vapor barrier properties of silicon oxide coatings deposited on polyethylene terephthalate by plasma enhanced chemical vapor deposition

Plasma polymer coatings were deposited from hexamethyldisiloxane on polyethylene terephthalate (PET) substrates while varying the operating conditions, such as the Ar and O₂ flow rates, at a fixed radio frequency power of 300 W. The water vapor transmission rate (WVTR) of the untreated PET was 54.56 g/m²/day and was decreased after depositing the silicon oxide (SiO_x) coatings. The minimum WVTR, 0.47 g/m²/day, was observed at Ar and O₂ flow rates of 4 and 20 sccm, respectively, with a coating thickness of 415.44 nm. The intensity of the peaks for the Si-O-Si bending at 800-820 cm^− 1 and Si-O-Si stretching at 1000-1150 cm^− 1 varied depending on the Ar and O₂ flow rates. The contact angle of the SiO_x coated PET increased as the Ar flow rate was increased from 2 to 8 sccm at a fixed O₂ flow rate of 20 sccm. It decreased gradually as the oxygen flow rate increased from 12 to 28 sccm at a fixed Ar carrier gas flow rate. The examination by atomic force microscopy revealed a correlation of the SiO_x morphology and the water vapor barrier performance with the Ar and O₂ flow rates. The roughness of the deposited coatings increased when either the O₂ or Ar flow rate was increased.     

The effect of substrate temperature on the physical properties of tantalum oxide thin films grown by reactive radio-frequency sputtering

Thin films of TaO_x were deposited on Si(1 0 0) by radio-frequency magnetron sputtering at substrate temperatures of 25, 100, 200, 300, 400, and 500 °C. The properties of TaO_x thin films deposited with different oxygen-to-argon gas ratios and substrate temperatures were evaluated. The results show that the films with lowest leakage current density were obtained at ambient temperature with an oxygen mixture ratio (OMR) of 60% and the oxygen-to-tantalum ratio has a minimum with increasing deposition substrate temperature. From the current–voltage (I–V) characteristics of the TaO_x thin films as a function of deposition substrate temperature, we found that the leakage current density in the TaO_x thin films increases with increasing deposition substrate temperature. The higher leakage current density in the TaO_x films is correlated to the oxygen deficiency in TaO_x films and crystallization at higher deposition temperature.     

Wide optical bandgap p-type μc-Si:Ox:H prepared by Cat-CVD and comparisons to p-type μc-Si:H

Oxygen-impurity boron-doped hydrogenated microcrystalline silicon (p-μc-Si:O_x:H) films have been deposited using catalytic chemical vapor deposition (Cat-CVD). Pure silane (SiH₄), hydrogen (H₂), oxygen (O₂), and diluted diborane (B₂H₆) gases were used. The tungsten catalyst temperature (T_fil) was varied from 1900 to 2100 °C and films were deposited on glass substrates at temperatures of 100 to 300 °C. Different catalyst-to-substrate distances were employed and single- or double-coiled filaments were used. In addition to p-μc-Si:O_x:H deposition, we have also deposited conventional p-type microcrystalline silicon (p-μc-Si:H) in order to compare their electrical and optical properties to p-μc-Si:O_x:H.     

Deposition of WNxCy thin films for diffusion barrier application using the dimethylhydrazido (2) tungsten complex (CH3CN)Cl4W(NNMe2)

Tungsten nitride carbide (WN_xC_y) thin films were deposited by chemical vapor deposition using the dimethylhydrazido (2⁻) tungsten complex (CH₃CN)Cl₄W(NNMe₂) (1) in benzonitrile with H₂ as a co-reactant in the temperature range 300 to 700 °C. Films were characterized using X-ray diffraction (XRD), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy and four-point probe to determine film crystallinity, composition, atomic bonding, and electrical resistivity, respectively. The lowest temperature at which growth was observed from 1 was 300 °C. For deposition between 300 and 650 °C, AES measurements indicated the presence of W, C, N, and O in the deposited film. The films deposited below 550 °C were amorphous, while those deposited at and above 550 °C were nano-crystalline (average grain size < 70 Å). The films exhibited their lowest resistivity of 840 µΩ-cm for deposition at 300 °C. WN_xC_y films were tested for diffusion barrier quality by sputter coating the film with Cu, annealing the Cu/WN_xC_y/Si stack in vacuum, and performing AES depth profile and XRD measurement to detect evidence of copper diffusion. Films deposited at 350 and 400 °C (50 and 60 nm thickness, respectively) were able to prevent bulk Cu transport after vacuum annealing at 500 °C for 30 min.     

Deposition of device quality silicon nitride with ultra high deposition rate (> 7 nm/s) using hot-wire CVD

The application of hot-wire (HW) CVD deposited silicon nitride (SiN_x) as passivating anti-reflection coating on multicrystalline silicon (mc-Si) solar cells is investigated. The highest efficiency reached is 15.7% for SiN_x layers with an N/Si ratio of 1.20 and a high mass density of 2.9 g/cm³. These cell efficiencies are comparable to the reference cells with optimized plasma enhanced (PE) CVD SiN_x even though a very high deposition rate of 3 nm/s is used. Layer characterization showed that the N/Si ratio in the layers determines the structure of the deposited films. And since the volume concentration of Si-atoms in the deposited films is found to be independent of the N/Si ratio the structure of the films is determined by the quantity of incorporated nitrogen. It is found that the process pressure greatly enhances the efficiency of the ammonia decomposition, presumably caused by the higher partial pressure of atomic hydrogen. With this knowledge we increased the deposition rate to a very high 7 nm/s for device quality SiN_x films, much faster than commercial deposition techniques offer [S. von Aichberger, Photon Int. 3 (2004) 40].     

Deposition and characterization of ultra-high barrier coatings for flexible electronic applications

A barrier structure consisting of SiO_x and SiN_x films was deposited on the polymer substrate at 80 °C via plasma-enhanced chemical vapor deposition (PECVD). However, the low radius of curvature (R_c) of the barrier-coated substrate may cause the inconvenience of the following fabrication processes. By depositing a 150 nm-SiN_x film, the R_c of the barrier-coated polycarbonate (PC) substrate can increase from 80 to 115 mm without inducing any cracks in the barrier structure. Furthermore, the thermal stress of the barrier structure can be adjusted via extending the PECVD process duration in the chamber and replacing PC by the polyethersulone (PES) substrate. The R_c can increase to ∼356 mm by depositing the 150 nm-SiN_x film on the other side of the PES substrate. Finally, the calcium test result of the barrier films/PES/SiN_x sample was calculated to be around 3.05 × 10⁻⁶ g/m²/day, representing that the barrier structure did not fail after modification.     

Effects of oxygen addition on electrochromic properties in low temperature plasma-enhanced chemical vapor deposition-synthesized MoOxCy thin films for flexible electrochromic devices

Electrochromic organomolybdenum oxide (MoO_xC_y) films are deposited onto 60 Ω/□ flexible polyethylene terephthalate/indium tin oxide substrates by low temperature plasma-enhanced chemical vapor deposition (PECVD) using a precursor of molybdenum carbonyl vapor, which is carried by argon gas, mixed with oxygen gas and synthesized by radio frequency power at room temperature (23 °C). The MoO_xC_y films with modified surface morphology and compositions of varying oxygen contents are proven to offer noteworthy electrochromic performance. Porous surface of the MoO_xC_y film (398 nm thick) provides Li⁺ ion diffusion coefficient value of 1.7 × 10^− 10 cm²/s for Li⁺ de-intercalation at a potential scan rate of 2 mV/s. High x/y value at high surface composition of oxygen to carbon in the MoO_xC_y film offers light modulation with transmittance variation of up to 63% and coloration efficiency of 36 cm²/C at a wavelength of 800 nm for 200 cycles of Li⁺ intercalation and de-intercalation. PECVD-synthesized MoO_xC_y thin films show promising electrochromic properties for applications in flexible electrochromic devices.