Metal Oxide Semiconductor Thin Film Research Articles

Research on correlation between metal oxide semiconductor target and magnetron sputtered film based on TFT application

The research on the intrinsic relationship between target quality and TFT (thin film transistor) performance is not perfect for magnetron sputtering processes. The systematic analysis of target-film-device still needs to be improved. This paper studied the internal relationship between metal oxide semiconductor targets, thin films, and TFT devices for the deterioration problem of device performance caused by the failure of the aging target. The experimental results showed that the target surface with a long cumulative sputtering time had apparent macroscopic concave, related to the electromagnetic field distribution. The concave region was the primary source of thin film composition, so the research object of this work was mainly the concave region. A multi-oxide target was used in this work, and its selective sputtering phenomenon was serious, mainly reflected in the sputtering rate of In2O3 grains with higher electrical conductivity than other components. There were many failure sites on the surface of the target, including nodules, holes, coating layers, and cracks. The failure sites would hinder the normal sputtering process and eventually form a vicious circle, failing the target. Due to the decline of target quality, sputtering particles would be in a state of insufficient kinetic energy, resulting in particle agglomeration, element segregation, weak M-O (metal-oxide) bonds, loose accumulation, and surface or block defects. Ultimately, the TFT performance with the aging target showed lower mobility, larger subthreshold swing, increased off-state current, and poorer stability. Clarifying the relationship between target quality and device performance is beneficial for the development of electronic devices.

Enhance hydrogen sulfide (H2S) gas sensor based on metal oxide semiconductor (NiO) thin films

Enhance hydrogen sulfide (H2S) gas sensor based on metal oxide semiconductor (NiO) thin films

PdRh-Sensitized Iron Oxide Ultrathin Film Sensors and Mechanistic Investigation by Operando TEM and DFT Calculation.

Metal oxide semiconductor (MOS) thin films are of critical importance to both fundamental research and practical applications of gas sensors. Herein, a high-performance H2 sensor based on palladium (Pd) and rhodium (Rh) co-functionalized Fe2 O3 films with an ultrathin thickness of 8.9nm deposited by using atomic layer deposition is reported. The sensor delivers an exceptional response of 105.9 toward 10ppm H2 at 230 °C, as well as high selectivity, immunity to humidity, and low detection limit (43 ppb), which are superior to the reported MOS sensors. Importantly, the Fe2 O3 film sensor under dynamic H2 detection is for the first time observed by operando transmission electron microscopy, which provides deterministic evidence for structure evolution of MOS during sensing reactions. To further reveal the sensing mechanism, density functional theory calculations are performed to elucidate the sensitization effect of PdRh catalysts. Mechanistic studies suggest that Pd promotes the adsorption and dissociation of H2 to generate PdHx , while Rh promotes the dissociation of oxygen adsorbed on the surface, thereby jointly promoting the redox reactions on the films. A wireless H2 detection system is also successfully demonstrated using the thin film sensors, certifying a great potential of the strategy to practical sensors.

P-Type Metal Oxide Semiconductor Thin Films: Synthesis and Chemical Sensor Applications.

This review focuses on the synthesis of p-type metal-oxide (p-type MOX) semiconductor thin films, such as CuO, NiO, Co3O4, and Cr2O3, used for chemical-sensing applications. P-type MOX thin films exhibit several advantages over n-type MOX, including a higher catalytic effect, low humidity dependence, and improved recovery speed. However, the sensing performance of CuO, NiO, Co3O4, and Cr2O3 thin films is strongly related to the intrinsic physicochemical properties of the material and the thickness of these MOX thin films. The latter is heavily dependent on synthesis techniques. Many techniques used for growing p-MOX thin films are reviewed herein. Physical vapor-deposition techniques (PVD), such as magnetron sputtering, thermal evaporation, thermal oxidation, and molecular-beam epitaxial (MBE) growth were investigated, along with chemical vapor deposition (CVD). Liquid-phase routes, including sol–gel-assisted dip-and-spin coating, spray pyrolysis, and electrodeposition, are also discussed. A review of each technique, as well as factors that affect the physicochemical properties of p-type MOX thin films, such as morphology, crystallinity, defects, and grain size, is presented. The sensing mechanism describing the surface reaction of gases with MOX is also discussed. The sensing characteristics of CuO, NiO, Co3O4, and Cr2O3 thin films, including their response, sensor kinetics, stability, selectivity, and repeatability are reviewed. Different chemical compounds, including reducing gases (such as volatile organic compounds (VOCs), H2, and NH3) and oxidizing gases, such as CO2, NO2, and O3, were analyzed. Bulk doping, surface decoration, and heterostructures are some of the strategies for improving the sensing capabilities of the suggested pristine p-type MOX thin films. Future trends to overcome the challenges of p-type MOX thin-film chemical sensors are also presented.

Multilayer Crossbar Array of Amorphous Metal-Oxide Semiconductor Thin Films for Neuromorphic Systems

A multilayer crossbar array has been developed using amorphous metal-oxide semiconductor (AOS) thin films and implemented into a neuromorphic system. The multilayer structure can be realized, because the AOS thin films can be deposited by a simple sputtering method without heat treatment, which does not damage the underlying structures. First, Au thin films are deposited by vapor evaporation as electrodes, an amorphous In-Ga-Zn-O (α-IGZO) thin film is deposited by a sputtering method as a conductance change layer, these processes are repeated, and a multilayer crossbar array is completed, where each of the three conductance change layers is sandwiched between the electrodes. Next, the multilayer crossbar array is implemented into a neuromorphic system with modified Hebbian learning, which enables autonomous learning without control circuitry, and an associative memory function is confirmed, which guarantees the possibility of further advanced functions. These results lead to astronomical large-scale integration (LSI) of synaptic elements in neuromorphic systems in the future.

Application of Laser Treatment in MOS-TFT Active Layer Prepared by Solution Method.

The active layer of metal oxide semiconductor thin film transistor (MOS-TFT) prepared by solution method, with the advantages of being a low cost and simple preparation process, usually needs heat treatment to improve its performance. Laser treatment has the advantages of high energy, fast speed, less damage to the substrate and controllable treatment area, which is more suitable for flexible and large-scale roll-to-roll preparation than thermal treatment. This paper mainly introduces the basic principle of active layer thin films prepared by laser treatment solution, including laser photochemical cracking of metastable bonds, laser thermal effect, photoactivation effect and laser sintering of nanoparticles. In addition, the application of laser treatment in the regulation of MOS-TFT performance is also described, including the effects of laser energy density, treatment atmosphere, laser wavelength and other factors on the performance of active layer thin films and MOS-TFT devices. Finally, the problems and future development trends of laser treatment technology in the application of metal oxide semiconductor thin films prepared by solution method and MOS-TFT are summarized.

Slot-die coating of silicon ink for volume production of CMOS polysilicon TFTs

A large-area polysilicon film was formed from slot-die coating of cyclopentasilane based silicon ink and laser crystallization. In this article a study of silicon ink preparation and selection, slot-die coater setup, coating and laser crystallization is described. The polysilicon film was applied to fabricate complementary metal oxide semiconductor (CMOS) thin film transistors (TFTs) which were used to develop and demonstrate near field communication devices. This was part of a hybrid process flow consisting of conventional lithography and printing to fabricate CMOS TFTs. Slot-die coating of silicon ink on a 300 mm square 100 μm thick stainless steel substrate is a key building block of this hybrid process flow to subtract and replace high capital cost plasma enhanced chemical vapor deposition (PECVD), ion implantation and silicon wafers. With slot-die coating of silicon ink, a silicon layer formation equivalent to PECVD in quality was achieved.

Oxygen Vacancy Dynamics in Highly Crystalline Zinc Oxide Film Investigated by PIERS Effect.

Surface-enhanced Raman spectroscopy (SERS) is commonly employed as an analysis or detection tool of biological and chemical molecules. Recently, an alternative section of the SERS field has appeared, called photo-induced enhanced Raman spectroscopy (PIERS). This PIERS effect is based on the production of the oxygen vacancies (V) in metal-oxide semiconductor thin-film (or other structures) by irradiation with UV light, thus enabling a Raman signal enhancement of chemical molecules through charge transfer processes between this photo-irradiated semiconductor film (or other structures) and these chemical molecules via metallic nanoparticles deposited on this photo-irradiated substrate. The PIERS technique can enable studying the dynamics of the oxygen vacancies under ambient and operando conditions compared to conventional tools of analysis. In this paper, we present the results obtained on the formation and healing rates of surface oxygen vacancies (V) in a highly crystalline ZnO film investigated by the PIERS effect, and we compare these results to the literature in order to study the effect of the crystallinity on these formation and healing rates of V in a ZnO film.

Tungsten oxide thin films for highly sensitive triethylamine detection

Metal oxide semiconductor (MOS) thin films are promising sensing layer for integration in gas sensor devices for detecting toxic and harmful molecules. Herein, tungsten oxide (WO3) thin films are deposited on interdigital electrodes by vacuum thermal evaporation to realize batch fabrication of high-performance gas sensors. Subsequent annealing at different temperatures allows for regulation of the concentration of oxygen vacancies in the WO3 films, which has been found to exert a great influence on the sensor properties. In addition, the surface structure of WO3 films is also highly dependent on the annealing temperature. Gas sensing investigations show that the WO3 sensor annealed at 500 °C possesses the best sensing properties for detecting triethylamine (TEA) including very high response, good selectivity, fast response, and low limit of detection (63 ppb). The excellent sensor performances are attributed to the enhanced adsorption of oxidative oxygen species due to the presence of abundant oxygen vacancies. The scalable fabrication of WO3 thin film gas sensors and the oxygen vacancy engineering strategy proposed herein may shed some light to developing high performance environmental sensors.

Plasma-induced oxygen vacancies enabled ultrathin ZnO films for highly sensitive detection of triethylamine

Metal oxide semiconductor (MOS) thin films hold great promise for electronic devices such as gas sensors. However, the low surface activity of pristine MOS often leads to inferior sensitivity and the sensitization mechanism of ultrathin MOS films has received rare attention. Herein, we report a high performance gas sensor based on plasma-etched ZnO thin films. The ultrathin ZnO films (20 nm) were deposited on SiO2 wafers by atomic layer deposition (ALD), which enables high-throughput production of sensor devices. The ZnO sensor shows typical n-type conductivity, which is highly variable to the exposure of triethylamine (TEA). Annealing temperature of the films is found to impact the sensor response, revealing calcination at a moderate temperature, i.e. 700 °C, leads to the best response. Further treatment by Ar plasma results in a remarkable decrease of sensor working temperature from 300 °C of untreated films to 250 °C and nearly 4-fold enhancement in the sensor response to 10 ppm TEA. Notably, the plasma-treated ZnO sensor also shows decent response even at room temperature (RT), which has been seldom reported for ZnO-based sensors. Structure and mechanism investigations reveal that the superior sensor properties are derived from the abundant oxygen vacancies generated by Ar plasma etching.

Amorphous metal oxide semiconductor thin film, analog memristor, and autonomous local learning for neuromorphic systems

Artificial intelligence is a promising concept in modern and future societies. Presently, software programs are used but with a bulky computer size and large power consumption. Conversely, hardware systems named neuromorphic systems are suggested, with a compact computer size and low power consumption. An important factor is the number of processing elements that can be integrated. In the present study, three decisive technologies are proposed: (1) amorphous metal oxide semiconductor thin films, one of which, Ga–Sn–O (GTO) thin film, is used. GTO thin film does not contain rare metals and can be deposited by a simple process at room temperature. Here, oxygen-poor and oxygen-rich layers are stacked. GTO memristors are formed at cross points in a crossbar array; (2) analog memristor, in which, continuous and infinite information can be memorized in a single device. Here, the electrical conductance gradually changes when a voltage is applied to the GTO memristor. This is the effect of the drift and diffusion of the oxygen vacancies (Vo); and (3) autonomous local learning, i.e., extra control circuits are not required since a single device autonomously modifies its own electrical characteristic. Finally, a neuromorphic system is assembled using the abovementioned three technologies. The function of the letter recognition is confirmed, which can be regarded as an associative memory, a typical artificial intelligence application.

(Invited) Atomic Layer Deposited Amorphous Igzo Semiconductor with Vertical Composition Engineering for High Mobility Field Effect Transistor

Amorphous oxide semiconductors have been widely studied for the potential use in flat-panel displays such as active matrix liquid crystal display (LCD) and Organic light emitting didoes (OLEDs). Since reporting amorphous InGaZnO semiconductor thin film transistor (TFT) in 2003 & 2004, many multi-component oxide semiconductors have been intensively investigated and developed by physical vapor deposition (PVD) method. Very recently, the sputtered InGaZnO TFTs are already adopted in mass-production to fabricate AMOLED TVs. Also, semiconductor industries have looked at metal oxide semiconductor thin films as an alternative Si channel layer because this semiconductor exhibited extremely low-off current level (below 10-18A/um). It is the unique property to decrease power consumption for various semiconductor devices. However, there remain several problems such as enhancing field effect mobility, composition uniformity, bias-temperature stability, and p-type oxide semiconductor in order to go further for the future device applications.In this talk, I will introduce various oxide semiconductor materials with atomic layer deposition (ALD) methods. Unlike PVD, ALD method has unique properties, including controlling atomic-level-thickness, manipulating atomic-level-composition control, and depositing impurity-free & uniform films. The key materials such In2O3, ZnO, SnO2, and Ga2O3 will be summarized and then I will show the combinatorial research works in terms of amorphous InGaZnO semiconductor thin film transistors. Generally, electrical properties of amorphous oxide semiconductors are strongly dependent on each element composition. The indium (In) rich InGaZnO exhibited a high mobility of 50cm2/V.sec. However, the In-rich InGaZnO TFTs have the demerit of negative threshold voltage owing to intrinsically high carrier density. I will present that In-rich IGZO TFTs with vertical stacked InOx, ZnOx and GaOx atomic layers show excellent performances such as saturation mobility of ~ 74cm cm2/V.sec, threshold voltage of -1.3V, on/off ratio of 8.9 × 108, subthreshold swing of 0.26V/decade, and hysteresis of 0.2V, while keeping a reasonable carrier density of ~1017 cm-3. Flexible ALD InGaZnO TFTs on polymer substrates were also discussed depending on gate insulator materials, in terms of device performances. ALD technique will be a very promising candidate to improve oxide semiconductor materials as well as various device applications (Display & Semiconductor Industry) because it has not only unique nano-growth mechanism but also ultimate uniform property.

Thermal-assisted brush printing of water-based In-Ga-Zn oxide transistors

As an environment-friendly technique, the water-based solution process has attracted numerous attention. Due to the ability to fabricate oxide semiconductor films for transistors with acceptable electric properties at relatively low temperatures (~200 °C lower compared with organic solvent), it has great potential in future display technology, and various correlation technologies are keeping emerging. Here, an efficient and facile water route thermal-assisted brush printing is demonstrated, which can be applied to fabricate the semiconductor layer of indium gallium zinc oxide (IGZO) thin-film transistors (TFTs) by the solution process. The synergistic effects of thermal-annealing and brush printing on the film formation process were comprehensively investigated, implying the synergistic effects induce the acceleration of the evaporation of the precursor solvent and promotes the lower surface roughness of as-prepared thin-film, resulting in improved transistor properties. Mechanically, the proposed film-forming model of thermal-assisted brush printing is also elaborated, which is expected to be a general guideline for the solution processing of metal-oxide semiconductor thin-films.

Research Progress of High Dielectric Constant Zirconia-Based Materials for Gate Dielectric Application

The high dielectric constant ZrO2, as one of the most promising gate dielectric materials for next generation semiconductor device, is expected to be introduced as a new high k dielectric layer to replace the traditional SiO2 gate dielectric. The electrical properties of ZrO2 films prepared by various deposition methods and the main methods to improve their electrical properties are introduced, including doping of nonmetal elements, metal doping design of pseudo-binary alloy system, new stacking structure, coupling with organic materials and utilization of crystalline ZrO2 as well as optimization of low-temperature solution process. The applications of ZrO2 and its composite thin film materials in metal oxide semiconductor field effect transistor (MOSFET) and thin film transistors (TFTs) with low power consumption and high performance are prospected.

Oxygen Vacancies Enabled Porous SnO2 Thin Films for Highly Sensitive Detection of Triethylamine at Room Temperature.

Detection of volatile organic compounds (VOCs) at room temperature (RT) currently remains a challenge for metal oxide semiconductor (MOS) gas sensors. Herein, for the first time, we report on the utilization of porous SnO2 thin films for RT detection of VOCs by defect engineering of oxygen vacancies. The oxygen vacancies in the three-dimensional-ordered SnO2 thin films, prepared by a colloidal template method, can be readily manipulated by thermal annealing at different temperatures. It is found that oxygen vacancies play an important role in the RT sensing performances, which successfully enables the sensor to respond to triethylamine (TEA) with an ultrahigh response, for example, 150.5-10 ppm TEA in a highly selective manner. In addition, the sensor based on oxygen vacancy-rich SnO2 thin films delivers a fast response and recovery speed (53 and 120 s), which can be further shortened to 10 and 36 s by elevating the working temperature to 120 °C. Notably, a low detection limit of 110 ppb has been obtained at RT. The overall performances surpass most previous reports on TEA detection at RT. The outstanding sensing properties can be attributed to the porous structure with abundant oxygen vacancies, which can improve the adsorption of molecules. The oxygen vacancy engineering strategy and the on-chip fabrication of porous MOS thin film sensing layers deliver great potential for creating high-performance RT sensors.

Metal oxide semiconductor thin-films and related devices

Metal oxide semiconductor thin-films and related devices

Expeditious, scalable solution growth of metal oxide films by combustion blade coating for flexible electronics

Metal oxide (MO) semiconductor thin films prepared from solution typically require multiple hours of thermal annealing to achieve optimal lattice densification, efficient charge transport, and stable device operation, presenting a major barrier to roll-to-roll manufacturing. Here, we report a highly efficient, cofuel-assisted scalable combustion blade-coating (CBC) process for MO film growth, which involves introducing both a fluorinated fuel and a preannealing step to remove deleterious organic contaminants and promote complete combustion. Ultrafast reaction and metal-oxygen-metal (M-O-M) lattice condensation then occur within 10-60 s at 200-350 °C for representative MO semiconductor [indium oxide (In2O3), indium-zinc oxide (IZO), indium-gallium-zinc oxide (IGZO)] and dielectric [aluminum oxide (Al2O3)] films. Thus, wafer-scale CBC fabrication of IGZO-Al2O3 thin-film transistors (TFTs) (60-s annealing) with field-effect mobilities as high as ∼25 cm2 V-1 s-1 and negligible threshold voltage deterioration in a demanding 4,000-s bias stress test are realized. Combined with polymer dielectrics, the CBC-derived IGZO TFTs on polyimide substrates exhibit high flexibility when bent to a 3-mm radius, with performance bending stability over 1,000 cycles.

Electric field modified Arrhenius description of charge transport in amorphous oxide semiconductor thin film transistors

While it is known that the charge-carrier mobility in amorphous metal oxide semiconductor thin film transistors (TFT) deviates from Arrhenius temperature dependence, we found that the Hall mobility measured in amorphous In-Ga-Zn-O (a-IGZO) follows an Arrhenius relation surprisingly well. We explain these observations by the effect of strong vertical electric field created by the gate voltage, which facilitates direct tunneling of trapped carriers into the conductive band and leads to virtually temperature independent mobility. We present a generalized Arrhenius model based on the effective temperature concept. We show that our model allows quantitative description of the temperature dependence of the mobility in a-IGZO TFTs over a broad temperature range.

Nano gold-coated surface patterned mesoporous titanium tin oxide sol–gel thin film: fabrication, optical and photoelectrochemical properties

Nano noble metal coating on surface patterned mesoporous semiconductor thin film can play an important role in enhancing visible light harvesting efficiency (LHE) towards improvement in photoelectrochemical (PEC) activity of the material. In this work, one-dimensional (1D) and two-dimensional (2D) mesoscale surface patterns have been created on sol–gel-based titanium tin oxide (TSO) nanostructured thin film on pure silica/indium tin oxide-coated glass by soft lithography. The TSO film matrix is observed to be mesoporous and semicrystalline as evidenced from the structural characterization by transmission electron microscopy and measurement of atmospheric ellipso-porosimetry, respectively. The 2D patterned film exhibits maximum LHE value in visible wavelength region. Further film surface modification has been carried out by depositing nano Au coating onto the bare patterned TSO films by a low temperature solution technique. Under visible light, a significant improvement in PEC activity is found and the gold-coated patterned 2D film shows higher visible LHE as well as >2.7 times higher photocurrent density than bare 2D film. This facile fabrication strategy can create an avenue toward improvement in LHE vis-a-vis the PEC activity of mesoporous mixed metal oxide semiconductor thin film.

Metal Composition and Polyethylenimine Doping Capacity Effects on Semiconducting Metal Oxide-Polymer Blend Charge Transport.

Charge transport and film microstructure evolution are investigated in a series of polyethylenimine (PEI)-doped (0.0-6.0 wt%) amorphous metal oxide (MO) semiconductor thin film blends. Here, PEI doping generality is broadened from binary In2O3 to ternary (e.g., In+Zn in IZO, In+Ga in IGO) and quaternary (e.g., In+Zn+Ga in IGZO) systems, demonstrating the universality of this approach for polymer electron doping of MO matrices. Systematic comparison of the effects of various metal ions on the electronic transport and film microstructure of these blends are investigated by combined thin-film transistor (TFT) response, AFM, XPS, XRD, X-ray reflectivity, and cross-sectional TEM. Morphological analysis reveals that layered MO film microstructures predominate in PEI-In2O3, but become less distinct in IGO and are not detectable in IZO and IGZO. TFT charge transport measurements indicate a general coincidence of a peak in carrier mobility (μpeak) and overall TFT performance at optimal PEI doping concentrations. Optimal PEI loadings that yield μpeak values depend not only on the MO elemental composition but also, equally important, on the metal atomic ratios. By investigating the relationship between the MO energy levels and PEI doping by UPS, it is concluded that the efficiency of PEI electron-donation is highly dependent on the metal oxide matrix work function in cases where film morphology is optimal, as in the IGO compositions. The results of this investigation demonstrate the broad generality and efficacy of PEI electron doping applied to electronically functional metal oxide systems and that the resulting film microstructure, morphology, and energy level modifications are all vital to understanding charge transport in these amorphous oxide blends.