Inverter circuits on glass substrates based on ZnO-nanoparticle thin-film transistors

The integration technique and the properties of inverter circuits on glass substrates using ZnO nanoparticles as semiconductor material are presented. The inverter device consists of a switching and a load metal–insulator–semiconductor field-effect transistor with poly(4-vinylphenol) as the gate dielectric. Although the semiconductor is deposited by spin-coating of a colloidal ZnO dispersion and the process temperature is limited to 200 °C, the inverters show reasonable maximum peak gains at low power consumption. The maximum peak gain was 6 V/V, whereas the maximum static power dissipation density was less than 26 nW/μm². Additionally, the influence of the geometry ratio as well as of the supply voltage on the device performance has been investigated. With regard to the optical characteristics, the proposed technique leads to circuits with an optical transmittance of up to 80%.     

Organic photovoltaics with V2O5 anode and ZnO nanoparticles cathode buffer layers

We report the hybrid inorganic–organic photovoltaics incorporating vanadium pentoxide (V₂O₅) as hole and zinc oxide (ZnO) nanoparticles (NPs) as electron extraction layers. This device demonstrates high open circuit voltage of about 0.89 V with considerably high short-circuit current density of 10.13 mA/cm² along with fill factor of about 61.03%. Combining all these parameters, the power conversion efficiency is 5.53% which is higher compared to that (3.6%) of the cell without ZnO NPs.     

High-efficiency hybrid organic–inorganic light-emitting devices

We report efficient red, orange, green and blue organic–inorganic light emitting devices using light emitting polymers and polyethylenimine ethoxylated (PEIE) interlayer with the respective luminance efficiency of 1.3, 2.7, 10 and 4.1 cd A⁻¹, which is comparable to that of the analogous conventional devices using a low work-function metal cathode. This is enabled by the enhanced electron injection due to the effective reduction of the ZnO work-function by PEIE, as well as hole/exciton-blocking function of PEIE layer. Due to the benign compatibility between PEIE and the neighboring organic layer, the novel phosphorescent organic–inorganic devices using solution-processed small molecule emissive layer show the maximum luminance efficiency of 87.6 cd A⁻¹ and external quantum efficiency of 20.9% at 1000 cd m⁻².     

N-doped ZnO based fast response ultraviolet photoconductive detector

We report a study on the fabrication and characterization of ultraviolet photodetectors based on N-doped ZnO films. Highly oriented N-doped ZnO films with 10 at.% N doping are deposited using spray pyrolysis technique onto glass substrates. The photoconductive UV detector based on N-doped ZnO thin films, having a metal–semiconductor–metal (MSM) configuration are fabricated by using Al as a contact metal. I–V characteristic under dark and UV illumination, spectral and transient response of ZnO and N-doped ZnO photodetector are studied. The photocurrent increases linearly with incident power density by more than two orders of magnitude. The photoresponsivity (580 A/W at 365 nm with 5 V bias, light power density 2 μW/cm²) is much higher in the ultraviolet region than in the visible.     

Operation voltage reduction and gain enhancement in organic CMOS inverters with the TTC/gelatin bilayer dielectric

An air ambient operated organic complementary metal oxide semiconductor (CMOS) inverter has been fabricated on poly(ethylene terephthalate) (PET) using pentacene and N,N-dioctyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C₈) as active layers with a bilayer dielectric of tetratetracontane (TTC) and gelatin. The inverter performance is greatly improved by replacing the gelatin dielectric with the TTC/gelatin bilayer. With the TTC/gelatin bilayer, both types of organic field-effect transistor (OFET) show better pinch-off and current saturation in output characteristics and negligible hysteresis transfer characteristics. The organic CMOS inverter with the TTC/gelatin bilayer dielectric exhibits balanced motilities of 0.5 (pentacene) and 0.3 cm² V⁻¹ s⁻¹ (PTCDI-C₈) with low threshold voltages of −1 (pentacene) and 3 V (PTCDI-C₈). A high static gain of 60 may be achieved with sharp inversion.     

Energy level alignment and morphology of interfaces between molecular and polymeric organic semiconductors

Ultraviolet photoelectron spectroscopy (UPS) was used to determine the energy level alignment at organic–organic conductor–semiconductor and semiconductor–semiconductor hetero-interfaces that are relevant for organic optoelectronic devices. Such interfaces were formed by in situ vacuum sublimation of small molecular materials [C₆₀ and pentacene (PEN)] and ex situ spin-coating of poly(3-hexylthiophene) (P3HT), all on the common substrate poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS). We found that the deposition sequence had a significant impact on the interface energetics. The hole injection barrier (HIB) of C₆₀ on PEDOT:PSS could be changed from 1.0 eV (moderate hole injection) to 1.7 eV (good electron injection) by introducing a layer of P3HT. The HIB of P3HT/PEDOT:PSS was increased by 0.35 eV due to an interfacial PEN layer. However, PEN deposited on PEDOT:PSS and P3HT/PEDOT:PSS exhibited the same value. These observations are explained by material-dependent dipoles at the interfaces towards PEDOT:PSS and substrate dependent inter-molecular conformation.     

High thermal annealing effect on structural and optical properties of ZnO–SiO2 nanocomposite

The effect of annealing temperature on photoluminescence (PL) of ZnO–SiO₂ nanocomposite was investigated. The ZnO–SiO₂ nanocomposite was annealed at different temperatures from 600 °C to 1000 °C with a step of 100 °C. High Resolution Transmission Electron Microscope (HR-TEM) pictures showed ZnO nanoparticles of 5 nm are capped with amorphous SiO₂ matrix. Field Emission Scanning Electron Microscope (FE-SEM) pictures showed that samples exhibit spherical morphology up to 800 °C and dumbbell morphology above 800 °C. The absorption spectrum of ZnO–SiO₂ nanocomposite suffers a blue-shift from 369 nm to 365 nm with increase of temperature from 800 °C to 1000 °C. The PL spectrum of ZnO–SiO₂ nanocomposite exhibited an UV emission positioned at 396 nm. The UV emission intensity increased as the temperature increased from 600 °C to 700 °C and then decreased for samples annealed at and above 800^°C. The XRD results showed that formation of willemite phase starts at 800 °C and pure willemite phase formed at 1000 °C. The decrease of the intensity of 396 nm emission peak at 900 °C and 1000 °C is due to the collapse of the ZnO hexagonal structure. This is due to the dominant diffusion of Zn into SiO₂ at these temperatures. At 1000 °C, an emission peak at 388 nm is observed in addition to UV emission of ZnO at 396 nm and is believed to be originated from the willemite.     

The effects of carrier gas and substrate temperature on ZnO films prepared by ultrasonic spray pyrolysis

ZnO films were deposited on glass substrates in the temperature range of 350–470 °C under an atmosphere of compressed air or nitrogen (N₂) by using ultrasonic spray pyrolysis technique. Structural, electrical and optical properties of the ZnO films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical two-probe and optical transmittance measurements. The ZnO films deposited in the range of 350–430 °C were polycrystalline with the wurtzite hexagonal structure having preferred orientation depending on the substrate temperature. The ZnO films deposited below 400 °C had a preferred (100) orientation while those deposited above 400 °C mostly had a preferred (002) orientation. The resistivity values of ZnO films depended on the types of carrier gas. The ZnO thin films deposited under N₂ atmosphere in the range of 370–410 °C showed dense surface morphologies and resistivity values of 0.6–1.1 Ω-cm, a few orders of magnitude lower than those deposited under compressed air. Hydrogen substition in ZnO possibly contributed to decreasing resistivity in ZnO thin films deposited under N₂ gas. The Hall measurements showed that the behavior of ZnO films deposited at 410 °C under the N₂ atmosphere was n-type with a carrier density of 8.9–9.2×10¹⁶ cm^-3 and mobility of ～70 cm²/Vs. ZnO thin films showed transmission values at 550 nm wavelength in a range of 70–80%. The values of band gaps extrapolated from the transmission results showed bandgap shrinkage in an order of milli electron volts in ZnO films deposited under N₂ compared to those deposited under compressed air. The calculation showed that the bandgap reduction was possibly a result of carrier–carrier interactions.     

Surfactant free hydrothermally derived ZnO nanowires,nanorods, microrods and their characterization

ZnO nanowires, nanorods and microrods have been prepared by an organic-free hydrothermal process using ZnSO₄ and NaOH/NH₄OH solutions. The powder X-ray diffraction (PXRD) patterns reveal that the ZnO nano/microrods are of hexagonal wurtzite structure. The Fourier transform infrared (FT-IR) spectrum of ZnO powder shows only one significant spectroscopic band at around 417 cm^?1 associated with the characteristic vibrational mode of Zn–O bonding. The thickness 75–300 nm for ZnO nanorods and 0.2–1.8 μm for microrods are identified from SEM/TEM images. UV–visible absorption spectra of ZnO nano/microrods show the blue shift. The UV band and green emission observed in photoluminescence (PL) spectra are due to free exciton emission and singly ionized oxygen vacancy in ZnO. Finally, the mechanism for organic-free hydrothermal synthesis of the ZnO nano/microrods is discussed.     

Facile synthetic route to implement a fully bendable organic metal–insulator–semiconductor device on polyimide sheet

Triblock copolymer surfactant, HO(CH₂CH₂O)₂₀(CH₂CH(CH₃)O)₇₀(CH₂CH₂O)₂₀H (i.e. P123)-based nanocrystalline (nc)-TiO₂ thin film had been synthesized on organic flexible polyimide (PI) sheet for their application in organic metal–insulator–semiconductor (MIS) device. The nc-TiO₂ film over PI was successfully deposited for the first time by a systematic solution proceeds dip-coating method and by the assistance of triblock copolymer surfactant. The effect of annealing temperature (270 °C, 5 h) on the texture, morphology and time-induced hydrophilicity was studied by X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contact angle system, respectively, to examine the chemical composition of the film and the contact angle. The surface morphology of the semiconducting layer of organic pentacene was also investigated by using AFM and XRD, and confirmed that continuous crystalline film growth had occurred on the nc-TiO₂ surface over flexible PI sheet. The semiconductor–dielectric interface of pentacene and nc-TiO₂ films was characterized by current–voltage and capacitance–voltage measurements. This interface measurement in cross-link MIS structured device yielded a low leakage current density of 8.7 × 10^?12 A cm^?2 at 0 to ?5 V, maximum capacitance of 102.3 pF at 1 MHz and estimated dielectric constant value of 28.8. Furthermore, assessment of quality study of nc-TiO₂ film in real-life flexibility tests for different types of bending settings with high durability (c.a. 30 days) demonstrated a better comprehension of dielectric properties over flexible PI sheet. We expected them to have a keen interest in the scientific study, which could be an alternate opportunity to the excellent dielectric–semiconductor interface at economic and low temperature processing for large-area flexible field-effect transistors and sensors.     

High-performance barrier using a dual-layer inorganic/organic hybrid thin-film encapsulation for organic light-emitting diodes

We report an inorganic/organic hybrid barrier that combines the alternating deposition of a layer of ZrO₂ using low temperature atomic layer deposition and a 16-μm-thick layer of UV-curable NOA63 epoxy using spin-coating. The effective water vapor transmission rates of single ZrO₂ film was improved by adding solution epoxy from 3.03 × 10⁻³ g/m² day to 1.27 × 10⁻⁴ g/m² day in the hybrid NOA63/ZrO₂/NOA63/ZrO₂ films at 20 °C and a relative humidity of 60%. In consequence, the organic light-emitting diodes encapsulated with inorganic/organic hybrid barriers were undamaged by environmental oxygen and moisture and their luminance decay time improved by a considerable extent.     

Scaling down of organic complementary logic gates for compact logic on foil

In this work, we realize complementary circuits with organic p-type and n-type transistor integrated on polyethylene naphthalate (PEN) foil. We employ evaporated p-type and n-type organic semiconductors spaced side by side in bottom-contact bottom-gate coplanar structures with channel lengths of 5 μm. The area density is 0.08 mm² per complementary logic gate. Both p-type and n-type transistors show mobilities >0.1 cm²/V s with V_on close to zero volt. Small circuits like inverters and 19-stage ring oscillators (RO) are fabricated to study the static and the dynamic performance of the logic inverter gate. The circuits operate at V_dd as low as 2.5 V and the inverter stage delay at V_dd = 10 V is as low as 2 μs. Finally, an 8 bit organic complementary transponder chip with data rate up to 2.7 k bits/s is fabricated on foil by successfully integrating 358 transistors.     

Electrical characterization of inorganic-on-organic diode based InP and poly(3,4-ethylenedioxithiophene)/poly(styrenesulfonate) (PEDOT:PSS)

The electronic properties of metal–organic semiconductor-inorganic semiconductor diode between InP and poly(3,4-ethylenedioxithiophene)/poly(styrenesulfonate) (PEDOT:PSS) polymeric organic semiconductor film have been investigated via current–voltage and capacitance–voltage methods. The Al/PEDOT:PSS/p-InP contact exhibits a rectification behavior with the barrier height value of 0.98 eV and with the ideality factor value of 2.6 obtained from their forward bias current voltage (I–V) characteristics at the room temperature greater than the conventional Al/p-InP (0.83 eV, n = 1.13). This increase in barrier height and ideality factor can be attributed to PEDOT:PSS film formed at Al/p-InP interface.     

Effect of UV light irradiation on photovoltaic characteristics of inverted polymer solar cells containing sol–gel zinc oxide electron collection layer

An inverted organic bulk-heterojunction solar cell containing a zinc oxide (ZnO) based electron collection layer with a structure of ITO/ZnO/[6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM): regioregular poly(3-hexylthiophene) (P3HT)/poly(3,4-ethylenedioxylenethiophene): poly(4-styrene sulfonic acid)/Au (ZnO cell) was fabricated. We examined the relationship between the heating temperature of the ZnO layer and the device performance under irradiation by simulated sunlight while cutting the UV light. The effects of the UV light contained in simulated sunlight were investigated by photocurrent–voltage (I–V) and alternating current impedance spectroscopy (IS) measurements. When the ZnO cells were irradiated with simulated sunlight, they exhibited a maximum power conversion efficiency (PCE) of over 3%, which hardly varied with the heating temperature of ZnO layers treated at 250 °C, 350 °C, and 450 °C. In contrast, when the ZnO cells were irradiated with simulated sunlight without UV content, their photovoltaic characteristics were very different. In the case of the cell with ZnO prepared by heating at 250 °C, PCE of 2.7% was maintained even under continuous irradiation with simulated sunlight without UV. However, for the cells with ZnO prepared by heating at 350 °C and 450 °C, the shapes of the I–V curves changed with the UV-cut light irradiation time, accompanying an increase in their series resistance. Overall, after UV-cut light irradiation for 1 h, the PCE of the cell with ZnO prepared by heating at 350 °C decreased to 1.80%, while that of the cell with ZnO prepared by heating at 450 °C fell to 1.35%. The photo IS investigations suggested that this performance change was responsible for the formation of charge-trapping sites at the ZnO/PCBM:P3HT interface which act as recombination centers for photo-produced charges in the PCBM:P3HT layer.     

A flexible moisture barrier comprised of a SiO2-embedded organic–inorganic hybrid nanocomposite and Al2O3 for thin-film encapsulation of OLEDs

We demonstrated a high performance flexible multi-barrier containing a silica nanoparticle-embedded organic–inorganic hybrid (S–H) nanocomposite and Al₂O₃. The multi-barrier was prepared by low-temperature Al₂O₃ atomic layer deposition and with a spin-coated S–H nanocomposite. The moisture barrier properties were investigated with a water vapor transmission rate (WVTR), estimated by a Ca test at 30 °C, 90% R.H.. Moisture diffusion was effectively suppressed by the sub-700 nm thick multi-barrier incorporating well-dispersed silica nanoparticles in the organic layer. A low WVTR of 1.14 × 10^?5 g/m² day and average transmittance of 85.8% in the visible region were obtained for the multi-barrier. After bending under tensile stress mode, the moisture barrier property of the multi-barriers was retained. The multi-barrier was successfully applied to thin-film encapsulation of OLEDs. The thin-film encapsulated OLEDs showed practicable current–voltage–luminance (I–V–L) characteristics and stable real operation over 700 h under ambient conditions.     

Optical strong coupling in microcavities containing J-aggregates absorbing in near-infrared spectral range

We present strong exciton–photon coupling at near-infrared wavelengths in an organic microcavity containing J-aggregates of a cyanine dye. Strong coupling is resolved using position-tuned transmission measurements, performed at room temperature at a constant angle. Clear anti-crossing around the organic exciton energy (1.57 eV = 789 nm) is observed with a Rabi splitting energy of 68 meV. Such systems will be of significant interest in the creation of hybrid semiconductor structures in which organic and inorganic excitons are electromagnetically coupled. We have also investigated the photostability of the J-aggregates used in the experiments and compare it with other cyanine dyes forming J-aggregates from water-based solutions. Our measurements suggest that the near-infrared dye is exceptionally stable in vacuum, especially at low temperatures.     

Charge injection in metal/organic/metal structures with ZnO:Al/organic interface modified by Zn1−xMgxO:Al layer

Aluminum-doped zinc oxide (ZnO:Al, AZO) electrodes were covered with very thin (∼6 nm) Zn_1−xMg_xO:Al (AMZO) layers grown by atomic layer deposition. They were tested as hole blocking/electron injecting contacts to organic semiconductors. Depending on the ALD growth conditions, the magnesium content at the film surface varied from x = 0 to x = 0.6. Magnesium was present only at the ZnO:Al surface and subsurface regions and did not diffuse into deeper parts of the layer. The work function of the AZO/AMZO (x = 0.3) film was 3.4 eV (based on the ultraviolet photoelectron spectroscopy). To investigate carrier injection properties of such contacts, single layer organic structures with either pentacene or 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine layers were prepared. Deposition of the AMZO layers with x = 0.3 resulted in a decrease of the reverse currents by 1–2 orders of magnitude and an improvement of the diode rectification. The AMZO layer improved hole blocking/electron injecting properties of the AZO electrodes. The analysis of the current-voltage characteristics by a differential approach revealed a richer injection and recombination mechanisms in the structures containing the additional AMZO layer. Among those mechanisms, monomolecular, bimolecular and superhigh injection were identified.     

Magneto-optical characteristics of Mn-doped ZnO films deposited by ultrasonic spray pyrolysis

This work considers a Mn-doped ZnO (ZnO:Mn) film deposited on a slide glass substrate by ultrasonic spray pyrolysis. ZnO:Mn (Mn at 1.5 at%) film with and without an applied magnetic field, is demonstrated to have absorption edges at 2.74 and 2.84 eV, respectively. These values are lower than that of a pure ZnO film because the Mn-doping causes the exchange of s–d and p–d interactions or high carrier concentration. When the ZnO:Mn film is placed in a magnetic field B_z of 0.5 T, an absorption edge and a photoluminescence (PL) shift of about 0.1 eV and 85 meV, respectively, are observed. This shift is attributed to the interband magneto-optic absorption associated with the Landau splitting. The observed shift increases with the amount of Mn dopant.     

Nanotribological properties of ALD-processed bilayer TiO2/ZnO films

TiO₂/ZnO films grown by atomic layer deposition (ALD) demonstrated nanotribological behaviors using scratch testing. TEM profiles obtained an amorphous structure TiO₂ and nanocrystalline structure ZnO, whereas the sample has significant interface between the TiO₂/ZnO films. The experimental results show the relative XRD peak intensities are mainly contributed by a wurtzite oxide ZnO structure and no signal from the amorphous TiO₂.With respect to tribology, increased friction causes plastic deformation between the TiO₂ and ZnO films, in addition to delamination and particle loosening. The plastic deformation caused by adhesion and/or cohesion failure is reflected in the nanoscratch traces. The pile-up events at a loading penetration of 30 nm were measured at 21.8 μN for RT, 22.4 μN for 300 °C, and 36 μN for 400 °C. In comparison to the other conditions, the TiO₂/ZnO films annealed at 400 °C exhibited higher scratch resistance and friction with large debris, indicating the wear volume is reduced with increased annealing temperature and loading.     

Influence of the sol gel synthesis parameters on the photoluminescence properties of ZnO nanoparticles

In this work, ZnO NPs were successfully synthesized by the sol–gel method without any organic additives or post annealing. The effect of the preparation process on the structural and optical properties of the resulting NPs was investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy. The structural characterization demonstrated clearly that the NPs crystallize in pure ZnO würtzite structure without any other secondary phases. Furthermore, we show that it is possible to perform the control of the crystalline growth orientation of ZnO NPs, which is a key parameter when seeking to develop ZnO NPs with piezoelectric properties for nano-transducer applications. In fact, TEM observations show that the reduction of the NaOH flow changes the NPs shape from hexagonal NPS to short nanorods grown along the c-axis. The PL spectra of the obtained NPs excited at 280 nm, present an UV emission centered at approximately 380 nm with a slight shift when varying the synthesis temperature and/or the NaOH flow. Moreover, as the visible region (from 400 to 650 nm) is concerned, it was shown that the increasing of the synthesis temperature affects strongly the kind of interstitial defects (O_i, Zn_i and V_oZn_i) formed in ZnO nanostructures. However, the excitation at 320 nm revealed a broad deep-level emission for all the samples that can be deconvoluted into two Gaussian peaks centered at 514 nm (P₁) and 581 nm (P₂). These last results have been discussed in the light of a physical mechanism based on the Schottky barrier.