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New Approaches for Overcoming Current Issues of Plasma Sputtering Process During Organic-electronics Device Fabrication: Plasma Damage Free and Room Temperature Process for High Quality Metal Oxide Thin Film

  • Hong, Mun-Pyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.100-101
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    • 2012
  • The plasma damage free and room temperature processedthin film deposition technology is essential for realization of various next generation organic microelectronic devices such as flexible AMOLED display, flexible OLED lighting, and organic photovoltaic cells because characteristics of fragile organic materials in the plasma process and low glass transition temperatures (Tg) of polymer substrate. In case of directly deposition of metal oxide thin films (including transparent conductive oxide (TCO) and amorphous oxide semiconductor (AOS)) on the organic layers, plasma damages against to the organic materials is fatal. This damage is believed to be originated mainly from high energy energetic particles during the sputtering process such as negative oxygen ions, reflected neutrals by reflection of plasma background gas at the target surface, sputtered atoms, bulk plasma ions, and secondary electrons. To solve this problem, we developed the NBAS (Neutral Beam Assisted Sputtering) process as a plasma damage free and room temperature processed sputtering technology. As a result, electro-optical properties of NBAS processed ITO thin film showed resistivity of $4.0{\times}10^{-4}{\Omega}{\cdot}m$ and high transmittance (>90% at 550 nm) with nano- crystalline structure at room temperature process. Furthermore, in the experiment result of directly deposition of TCO top anode on the inverted structure OLED cell, it is verified that NBAS TCO deposition process does not damages to the underlying organic layers. In case of deposition of transparent conductive oxide (TCO) thin film on the plastic polymer substrate, the room temperature processed sputtering coating of high quality TCO thin film is required. During the sputtering process with higher density plasma, the energetic particles contribute self supplying of activation & crystallization energy without any additional heating and post-annealing and forminga high quality TCO thin film. However, negative oxygen ions which generated from sputteringtarget surface by electron attachment are accelerated to high energy by induced cathode self-bias. Thus the high energy negative oxygen ions can lead to critical physical bombardment damages to forming oxide thin film and this effect does not recover in room temperature process without post thermal annealing. To salve the inherent limitation of plasma sputtering, we have been developed the Magnetic Field Shielded Sputtering (MFSS) process as the high quality oxide thin film deposition process at room temperature. The MFSS process is effectively eliminate or suppress the negative oxygen ions bombardment damage by the plasma limiter which composed permanent magnet array. As a result, electro-optical properties of MFSS processed ITO thin film (resistivity $3.9{\times}10^{-4}{\Omega}{\cdot}cm$, transmittance 95% at 550 nm) have approachedthose of a high temperature DC magnetron sputtering (DMS) ITO thin film were. Also, AOS (a-IGZO) TFTs fabricated by MFSS process without higher temperature post annealing showed very comparable electrical performance with those by DMS process with $400^{\circ}C$ post annealing. They are important to note that the bombardment of a negative oxygen ion which is accelerated by dc self-bias during rf sputtering could degrade the electrical performance of ITO electrodes and a-IGZO TFTs. Finally, we found that reduction of damage from the high energy negative oxygen ions bombardment drives improvement of crystalline structure in the ITO thin film and suppression of the sub-gab states in a-IGZO semiconductor thin film. For realization of organic flexible electronic devices based on plastic substrates, gas barrier coatings are required to prevent the permeation of water and oxygen because organic materials are highly susceptible to water and oxygen. In particular, high efficiency flexible AMOLEDs needs an extremely low water vapor transition rate (WVTR) of $1{\times}10^{-6}gm^{-2}day^{-1}$. The key factor in high quality inorganic gas barrier formation for achieving the very low WVTR required (under ${\sim}10^{-6}gm^{-2}day^{-1}$) is the suppression of nano-sized defect sites and gas diffusion pathways among the grain boundaries. For formation of high quality single inorganic gas barrier layer, we developed high density nano-structured Al2O3 single gas barrier layer usinga NBAS process. The NBAS process can continuously change crystalline structures from an amorphous phase to a nano- crystalline phase with various grain sizes in a single inorganic thin film. As a result, the water vapor transmission rates (WVTR) of the NBAS processed $Al_2O_3$ gas barrier film have improved order of magnitude compared with that of conventional $Al_2O_3$ layers made by the RF magnetron sputteringprocess under the same sputtering conditions; the WVTR of the NBAS processed $Al_2O_3$ gas barrier film was about $5{\times}10^{-6}g/m^2/day$ by just single layer.

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High Performance Flexible Inorganic Electronic Systems

  • Park, Gwi-Il;Lee, Geon-Jae
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.08a
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    • pp.115-116
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    • 2012
  • The demand for flexible electronic systems such as wearable computers, E-paper, and flexible displays has increased due to their advantages of excellent portability, conformal contact with curved surfaces, light weight, and human friendly interfaces over present rigid electronic systems. This seminar introduces three recent progresses that can extend the application of high performance flexible inorganic electronics. The first part of this seminar will introduce a RRAM with a one transistor-one memristor (1T-1M) arrays on flexible substrates. Flexible memory is an essential part of electronics for data processing, storage, and radio frequency (RF) communication and thus a key element to realize such flexible electronic systems. Although several emerging memory technologies, including resistive switching memory, have been proposed, the cell-to-cell interference issue has to be overcome for flexible and high performance nonvolatile memory applications. The cell-to-cell interference between neighbouring memory cells occurs due to leakage current paths through adjacent low resistance state cells and induces not only unnecessary power consumption but also a misreading problem, a fatal obstacle in memory operation. To fabricate a fully functional flexible memory and prevent these unwanted effects, we integrated high performance flexible single crystal silicon transistors with an amorphous titanium oxide (a-TiO2) based memristor to control the logic state of memory. The $8{\times}8$ NOR type 1T-1M RRAM demonstrated the first random access memory operation on flexible substrates by controlling each memory unit cell independently. The second part of the seminar will discuss the flexible GaN LED on LCP substrates for implantable biosensor. Inorganic III-V light emitting diodes (LEDs) have superior characteristics, such as long-term stability, high efficiency, and strong brightness compared to conventional incandescent lamps and OLED. However, due to the brittle property of bulk inorganic semiconductor materials, III-V LED limits its applications in the field of high performance flexible electronics. This seminar introduces the first flexible and implantable GaN LED on plastic substrates that is transferred from bulk GaN on Si substrates. The superb properties of the flexible GaN thin film in terms of its wide band gap and high efficiency enable the dramatic extension of not only consumer electronic applications but also the biosensing scale. The flexible white LEDs are demonstrated for the feasibility of using a white light source for future flexible BLU devices. Finally a water-resist and a biocompatible PTFE-coated flexible LED biosensor can detect PSA at a detection limit of 1 ng/mL. These results show that the nitride-based flexible LED can be used as the future flexible display technology and a type of implantable LED biosensor for a therapy tool. The final part of this seminar will introduce a highly efficient and printable BaTiO3 thin film nanogenerator on plastic substrates. Energy harvesting technologies converting external biomechanical energy sources (such as heart beat, blood flow, muscle stretching and animal movements) into electrical energy is recently a highly demanding issue in the materials science community. Herein, we describe procedure suitable for generating and printing a lead-free microstructured BaTiO3 thin film nanogenerator on plastic substrates to overcome limitations appeared in conventional flexible ferroelectric devices. Flexible BaTiO3 thin film nanogenerator was fabricated and the piezoelectric properties and mechanically stability of ferroelectric devices were characterized. From the results, we demonstrate the highly efficient and stable performance of BaTiO3 thin film nanogenerator.

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A study on the improvement of TiN diffusion barrier properties using Cu(Mg) alloy (Cu(Mg) alloy 금속배선에 의한 TiN 확산방지막의 특성개선)

  • 박상기;조범석;조흥렬;양희정;이원희;이재갑
    • Journal of the Korean Vacuum Society
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    • v.10 no.2
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    • pp.234-240
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    • 2001
  • The diffusion barrier properties of TiN by using Cu(Mg) alloy film have been investigated. Cu(Mg) alloy film was deposited on air-exposed TiN film. Upon annealing, interfacial MgO of 100 $\AA$ has been formed due to the reaction of Mg with oxygen existed on the surface of TiN. Combined MgO/TiN structure prevented the interdiffusion of Cu and Si up to $800^{\circ}C$. To improve the adhesion of Cu(Mg) alloy film to the TiN, TiN layer was treated by $O_2$ plasma, followed by vacuum annealing at $300^{\circ}C$. It was found that increased oxygen on the surface of TiN film by plasma treatment enhanced segregation of Mg toward the interface, resulting in the formation of dense MgO layer. Improved adhesion characteristics have been formed through this treatment. However, increased power of $O_2$ plasma led to the formation of TiO$_2$ and decreased the Mg content to be segregated to the interface, resulting in the decrease in adhesion property. In addition, the deposition of 50 ${\AA}$ Si on the TiN enhanced the adhesion of Cu(Mg) alloy to TiN without deteriorating the TiN diffusion barrier characteristics.

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Chromaticity(b*), Sheet Resistance and Transmittance of SiO2-ITO Thin Films Deposited on PET Film by Using Roll-to-Roll Sputter System (롤투롤시스템을 이용하여 PET 필름위에 제조된 SiO2-ITO 박막의 색도(b*), 면저항과 투과도 연구)

  • Park, Mi-Young;Kang, Bo-Gab;Kim, Jung-Soo;Kim, Hye-Young;Kim, Hu-Sik;Lim, Woo-Taik;Choi, Sik-Young
    • Korean Journal of Materials Research
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    • v.21 no.5
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    • pp.255-262
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    • 2011
  • This paper has relatively high technical standard and experimental skill. The fabrication of TCO film with high transparency, low resistance and low chromaticity require exact control of several competing factors. This paper has resolved these problems reasonably well, thus recommended for publication. Indium tin oxide(ITO) thin films were by D.C. magnetron roll-to-roll sputter system utilizing ITO and $SiO_2$ targets of ITO and $SiO_2$. In this experiment, the effect of D.C. power, winding speed, and oxygen flow rate on electrical and optical properties of ITO thin films were investigated from the view point of sheet resistance, transmittance, and chromaticity($b^*$). The deposition of $SiO_2$ was performed with RF power of 400W, Ar gas of 50 sccm and the deposition of ITO, DC power of 600W, Ar gas of 50 sccm, $O^2$ gas of 0.2 sccm, and winding speed of 0.56m/min. High quality ITO thin films without $SiO_2$ layer had chromaticity of 2.87, sheet resistivity of 400 ohm/square, and transmittance of 88% and $SiO_2$-doped ITO Thin film with chromaticity of 2.01, sheet resistivity of 709 ohm/square, and transmittance of more than 90% were obtained. As a result, $SiO_2$ was coated on PET before deposition of ITO, their chromaticity($b^*$) and transmittance were better than previous results of ITO films. These results show that coating of $SiO_2$ induced arising chromaticity($b^*$) and transmittance. If the thickness of $SiO_2$ is controlled, sheet resistance value of ITO film will be expected to be better for touch screen. A four point probe and spectrophotometer are used to investigate the properties of ITO thin films.

An effect of component layers on the phases and dielectric properties in $PbTiO_3$ thin films prepared from multilayer structure (다층구조박막으로부터 $PbTiO_3$ 박막 제조시 요소층이 상형성 및 유전특성에 미치는 영향)

  • Do-Won Seo;Song-Min Nam;Duck-Kyun Choi
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.4 no.4
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    • pp.378-387
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    • 1994
  • To improve the properties of $PbTiO_3$ thin films successfully grown by thermal diffusion of 3 component layers of $Ti0_2/Pb/TiO_2(900{\AA}/900{\AA}/900{\AA})$ in preceding research, 3, 5, 7, 9, and 11 multilayer structures $(TiO_2/Pb/.../Tio_2)$ with thinner component layer of $200~300 {\AA}$ thick were deposited on Si substrate by RF sputtering, which were followed by RTA to form $PbTiO_3$ thin films. As a result, $PbTiO_3$ single phase was formed above $500^{\circ}C$. When the thickness of component layer reduced and the number of component layers increased, suppression of Pb-silicate and voids formation resulted in relatively sharp interfaces and the film composition became more homogeneous. Relative dielectric constants in MIM structure were independent of the annealing condition, but they increased with increasing thickness of the $PbTiO_3$ thin films. The maximum breakdown field in MIS structure reached 150kV/cm.

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The effects of TiO2 interlayer phase transition on structural and electrical properties of PLZT Thin Films (TiO2 Interlayer의 상변화에 따른 PLZT 박막의 구조 및 전기적 특성)

  • Lee, Chul-Su;Yoon, Ji-Eon;Hwang, Dong-Hyun;Cha, Won-Hyo;Sona, Young-Gook
    • Journal of the Korean Vacuum Society
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    • v.16 no.6
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    • pp.446-452
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    • 2007
  • [ $(Pb_{1.1},La_{0.08})(Zr_{0.65}.Ti_{0.35})O_3$ ] thin films on the $Pt/Ti/SiO_2/Si$, $TiO_2(interlayer)/Pt/Ti/SiO_2/Si$ substrate were fabricated by the R.F. magnetron-sputtering method and considered their characteristics depending on $TiO_2$ interlayer. Changing the deposition conditions of $TiO_2$ interlayer, we obtained $TiO_2$ anatase single phase and rutile single phase. PLZT was deposited on these substrates and analyzed by x-ray diffraction(XRD) for there crystallinity and orientation. To investigate $PLZT-TiO_2$, $TiO_2-Pt$ interface, glow discharge spectrometer(GDS) analysis was carried out and we performed electrical measurements for dielectric properties of PLZT thin films. The PLZT thin film on $TiO_2$ anatase interlayer was found to have (110)-preferred orientation and 12.6 ${\mu}C/cm^2$ remaining polarization value.

Electrical Properties in $Pt/SrTiO_3/Pb_x(Zr_{0.52}, Ti_{0.48})O_3/SrTiO_3/Si$ Structure and the Role of $SrTiO_3$ Film as a Buffer Layer ($Pt/SrTiO_3/Pb_x(Zr_{0.52}, Ti_{0.48})O_3/SrTiO_3/Si$ 구조의 전기적 특성 분석 및 $SrTiO_3$박막의 완충층 역할에 관한 연구)

  • 김형찬;신동석;최인훈
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.11 no.6
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    • pp.436-441
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    • 1998
  • $Pt/SrTiO_3/Pb_x(Zr_{0.52}, Ti_{0.48})O_3/SrTiO_3/Si$ structure was prepared by rf-magnetron sputtering method for use in nondestructive read out ferroelectric RAM(NDRO-FEAM). PBx(Zr_{0.52}Ti_{0.48})O_3}$(PZT) and $SrTiO_3$(STO) films were deposited respectively at the temperatures of $300^{\circ}C and 500^{\circ}C$on p-Si(100) substrate. The role of the STO film as a buffer layer between the PZT film and the Si substrate was studied using X-ray diffraction (XRD), Auger electron spectroscopy (ASE), and scanning electron microscope(SEM). Structural analysis on the interfaces was carried out using a cross sectional transmission electron microscope(TEM). For PZT/Si structure, mostly Pb deficient pyrochlore phase was formed due to the serious diffusion of Pb into the Si substrate. On the other hand, for STO/PZT/STO/Si structure, the PZT film had perovskite phase and larger grain size with a little Pb interdiffusion. the interfaces of the PZT and the STO film, of the STO film and the interface layer and $SiO_2$, and of the $SiO_2$ and the Si substate had a good flatness. Across sectional TEM image showed the existence of an amorphous layer and $SiO_2$ with 7nm thickness between the STO film and the Si substrate. The electrical properties of MIFIS structure was characterized by C-V and I-V measurements. By 1MHz C-V characteristics Pt/STO(25nm)/PZT(160nm)/STO(25nm)/Si structure, memory window was about 1.2 V for and applied voltage of 5 V. Memory window increased by increasing the applied voltage and maximum voltage of memory window was 2 V for V applied. Memory window decreased by decreasing PZT film thickness to 110nm. Typical leakage current was abour $10{-8}$ A/cm for an applied voltage of 5 V.

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저온 공정 온도에서 $Al_2O_3$ 게이트 절연물질을 사용한 InGaZnO thin film transistors

  • 우창호;안철현;김영이;조형균
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2010.06a
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    • pp.11-11
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    • 2010
  • Thin-film-transistors (TFTs) that can be deposited at low temperature have recently attracted lots of applications such as sensors, solar cell and displays, because of the great flexible electronics and transparent. Transparent and flexible transistors are being required that high mobility and large-area uniformity at low temperature [1]. But, unfortunately most of TFT structures are used to be $SiO_2$ as gate dielectric layer. The $SiO_2$ has disadvantaged that it is required to high driving voltage to achieve the same operating efficiency compared with other high-k materials and its thickness is thicker than high-k materials [2]. To solve this problem, we find lots of high-k materials as $HfO_2$, $ZrO_2$, $SiN_x$, $TiO_2$, $Al_2O_3$. Among the High-k materials, $Al_2O_3$ is one of the outstanding materials due to its properties are high dielectric constant ( ~9 ), relatively low leakage current, wide bandgap ( 8.7 eV ) and good device stability. For the realization of flexible displays, all processes should be performed at very low temperatures, but low temperature $Al_2O_3$ grown by sputtering showed deteriorated electrical performance. Further decrease in growth temperature induces a high density of charge traps in the gate oxide/channel. This study investigated the effect of growth temperatures of ALD grown $Al_2O_3$ layers on the TFT device performance. The ALD deposition showed high conformal and defect-free dielectric layers at low temperature compared with other deposition equipments [2]. After ITO was wet-chemically etched with HCl : $HNO_3$ = 3:1, $Al_2O_3$ layer was deposited by ALD at various growth temperatures or lift-off process. Amorphous InGaZnO channel layers were deposited by rf magnetron sputtering at a working pressure of 3 mTorr and $O_2$/Ar (1/29 sccm). The electrodes were formed with electron-beam evaporated Ti (30 nm) and Au (70 nm) bilayer. The TFT devices were heat-treated in a furnace at $300^{\circ}C$ and nitrogen atmosphere for 1 hour by rapid thermal treatment. The electrical properties of the oxide TFTs were measured using semiconductor parameter analyzer (4145B), and LCR meter.

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Temperature Dependence on Dry Etching of $ZrO_2$ Thin Films in $Cl_2/BCl_3$/Ar Inductively Coupled Plasma ($Cl_2/BCl_3$/Ar 유도 결합 플라즈마에서 온도에 따른 $ZrO_2$ 박막의 식각)

  • Yang, Xue;Kim, Dong-Pyo;Lee, Cheol-In;Um, Doo-Seung;Kim, Chang-Il
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.11a
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    • pp.145-145
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    • 2008
  • High-k materials have been paid much more attention for their characteristics with high permittivity to reduce the leakage current through the scaled gate oxide. Among the high-k materials, $ZrO_2$ is one of the most attractive ones combing such favorable properties as a high dielectric constant (k= 20 ~ 25), wide band gap (5 ~ 7 eV) as well as a close thermal expansion coefficient with Si that results in good thermal stability of the $ZrO_2$/Si structure. During the etching process, plasma etching has been widely used to define fine-line patterns, selectively remove materials over topography, planarize surfaces, and trip photoresist. About the high-k materials etching, the relation between the etch characteristics of high-k dielectric materials and plasma properties is required to be studied more to match standard processing procedure with low damaged removal process. Among several etching techniques, we chose the inductively coupled plasma (ICP) for high-density plasma, easy control of ion energy and flux, low ownership and simple structure. And the $BCl_3$ was included in the gas due to the effective extraction of oxygen in the form of $BCl_xO_y$ compounds. During the etching process, the wafer surface temperature is an important parameter, until now, there is less study on temperature parameter. In this study, the etch mechanism of $ZrO_2$ thin film was investigated in function of $Cl_2$ addition to $BCl_3$/Ar gas mixture ratio, RF power and DC-bias power based on substrate temperature increased from $10^{\circ}C$ to $80^{\circ}C$. The variations of relative volume densities for the particles were measured with optical emission spectroscopy (OES). The surface imagination was measured by scanning emission spectroscope (SEM). The chemical state of film was investigated using energy dispersive X-ray (EDX).

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Magnetoresistance of Bi Nanowires Grown by On-Film Formation of Nanowires for In-situ Self-assembled Interconnection

  • Ham, Jin-Hee;Kang, Joo-Hoon;Noh, Jin-Seo;Lee, Woo-Young
    • Proceedings of the Korean Magnestics Society Conference
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    • 2010.06a
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    • pp.79-79
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    • 2010
  • Semimetallic bismuth (Bi) has been extensively investigated over the last decade since it exhibits very intriguing transport properties due to their highly anisotropic Fermi surface, low carrier concentration, long carrier mean free path l, and small effective carrier mass $m^*$. In particular, the great interest in Bi nanowires lies in the development of nanowire fabrication methods and the opportunity for exploring novel low-dimensional phenomena as well as practical application such as thermoelectricity[1]. In this work, we introduce a self-assembled interconnection of nanostructures produced by an on-film formation of nanowires (OFF-ON) method in order to form a highly ohmic Bi nanobridge. A Bi thin film was first deposited on a thermally oxidized Si (100) substrate at a rate of $40\;{\AA}/s$ by radio frequency (RF) sputtering at 300 K. The sputter system was kept in an ultra high vacuum (UHV) of $10^{-6}$ Torr before deposition, and sputtering was performed under an Ar gas pressure of 2m Torr for 180s. For the lateral growth of Bi nanowires, we sputtered a thin Cr (or $SiO_2$) layer on top of the Bi film. The Bi thin films were subsequently put into a custom-made vacuum furnace for thermal annealing to grow Bi nanowires by the OFF-ON method. After thermal annealing, the Bi nanowires cannot be pushed out from the topside of the Bi films due to the Cr (or $SiO_2$) layer. Instead, Bi nanowires grow laterally as a mean s of releasing the compressive stress. We fabricated a self-assembled Bi nanobridge (d=192 nm) device in-situ using OFF-ON through annealing at $250^{\circ}C$ for 10hours. From I-V measurements taken on the Bi nanobridge device, contacts to the nanobridge were found highly ohmic. The quality of the Bi nanobridge was also proved by the high MR of 123% obtained from transverse MR measurements. These results manifest the possibility of self-assembled nanowire interconnection between various nanostructures for a variety of applications and provide a simple device fabrication method to investigate transport properties on nanowires without complex patterning and etching processes.

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