A novel electrochemical cell is disclosed in multiple embodiments. The instant invention relates to an electrochemical cell design. In one embodiment, the cell design can electrolyze water into pressurized hydrogen using low-cost materials. In another embodiment, the cell design can convert hydrogen and oxygen into electricity. In another embodiment, the cell design can electrolyze water into hydrogen and oxygen for storage, then later convert the stored hydrogen and oxygen back into electricity and water. In some embodiments, the cell operates with a wide internal pressure differential.

Energy storage is required to maintain reliable electricity delivery from energy producers to their customers. As electrical loads on the grid change throughout the day, stored energy supplies electricity during increased power demand periods. Further, as more renewable and alternative energy sources are added, energy storage will maximize the usefulness of these technologies. As energy demands continue to expand, and more renewable energy, i.e., wind and solar, is added to the grid, new distributed energy storage technologies will be needed that are not dependent on geographic features.
Battery technologies can provide energy storage for some applications but are not economically well-suited for long-duration charge/discharge, such as load-leveling of renewable energy. Consequently, development of new energy storage devices will augment the existing grid and reduce the capital investment in construction upgrades. As ever-increasing renewable energy is implemented, lower-cost energy storage solutions for renewable energy will be necessary to keep electricity costs low for consumers.
Regenerative fuel cells offer a unique solution for grid energy storage. Unlike batteries, regenerative fuel cells can cost-effectively store a large amount of energy in the form of hydrogen. Energy in the form of hydrogen can be stored at a cost less than $20/kW-hr in large gas cylinders, significantly lower than the cost of batteries. Regenerative fuel cells or electrolysis systems could also provide an added benefit of hydrogen generation for fuel cell vehicles. Unfortunately, there are several limitations with existing technology for regenerative fuel cell and electrolysis systems.
Currently, two technologies are used commercially for water electrolysis. Alkaline electrolyzers are an established technology that rely on two electrodes in a liquid electrolyte. These electrodes are typically separated by a non-electrically-conductive porous layer, called the separator. Through application of a voltage, hydrogen and oxygen are evolved from the cathode and anode, respectively. Due to the permeability of the separator, the hydrogen gas cannot be pressurized substantially through electrochemical means. Small differences in pressure between the two sides of the cell can cause catastrophic cell failures. A mechanical compressor is typically used for hydrogen compression, requiring an additional system component that is exceedingly expensive for many scales and applications.
The second common method for water electrolysis is a proton exchange membrane (PEM) electrolyzer. This technology uses a gas-impermeable polymer membrane as the electrolyte. Water vapor or liquid water is fed to at least one of the electrodes. The gases can be easily compressed electrochemically with a PEM electrolyzer, and the cells can operate with pressure differences greater than 100 bar. PEM electrolyzers can also be made to operate reversibly, producing electricity and water from hydrogen and oxygen. The drawback of PEM electrolyzers and PEM reversible fuel cells is the cost of the components. The acidic electrolyte and electrolysis operating voltages necessitate the selection of expensive components for long-term stability. Platinum and Iridium may be used as electrode catalysts. Additionally, electrode current collectors must be fabricated of corrosion-resistant materials. PEM electrolysis systems are consequently too expensive for wide-scale commercial adoption for many grid-scale energy storage applications.
With the development of polymer membranes, known as Anion Exchange Membranes (AEMs), that conduct hydroxide ions and other anions, low-cost cells that can produce pressurized hydrogen have become possible. However, hydrocarbon-based AEMs have challenges with remaining conductive if operated in the absence of liquid water. Further, without liquid electrolyte present, ionomers in the electrode layer are required to introduce ion conduction beyond the 2-dimensional electrolyte/electrode interface, a necessity for obtaining high areal current density.
U.S. Pat. No. 7,943,258 discloses an AEM fuel cell design that illustrates the challenges found with AEM cell designs. This patent uses an AEM as the electrolyte and ionomer in the electrode layers. Those skilled in the art would appreciate that keeping an AEM hydrated and active for more than a few hours in the absence of liquid electrolyte is very challenging. In the '258 patent, the membrane is kept in a constant hydrated state by delivery of water to the edge of the membrane, outside of the active electrode area, through several unique designs. In the absence of liquid electrolyte, ionomers are required in the electrode layer of this cell design to enable ion conduction to permeate the electrode and operate at substantial current density. While the cell design would be expected to operate well as a fuel cell utilizing pure hydrogen and pure oxygen, it would be expected to slowly lose performance in the presence of carbon dioxide in the fuel or oxidant. Further, this cell design is not conducive to electrolysis operation for several reasons.
First, hydrocarbon ionomers used in the oxygen electrode would not be stable under typical electrolysis voltages. Second, the wicking mechanism used to deliver water to hydrate the membrane would not deliver water to the cell at a sufficient rate to match the water consumption during high current electrolysis.
Using liquid electrolytes, alkaline cell designs have been demonstrated for electrolysis and reversible fuel cell/electrolysis operation. U.S. Pat. No. 6,447,942 discloses a reversible fuel cell design with an alkaline liquid electrolyte. The design uses a porous separator between the electrodes. Another liquid electrolyte cell design is disclosed in United States Patent Application No. 2006/0057436A1. This design also utilizes a porous diaphragm separator. In both designs, the cells would be susceptible to carbon oxide contaminants in the fuel or oxidant when operated as a fuel cell. In the oxidant, over long-term operation, carbon dioxide would result in precipitation of carbonates in the cathode, thus blocking gas flow. In the fuel, anode catalysts, such as platinum or nickel, would be poisoned by carbon dioxide. Carbon dioxide could similarly precipitate as carbonates, blocking gas flow in the anode. In both cases, the cell designs would not permit significant pressurization of the product gases during electrolysis, because of the need for a porous separator. Consequently, while liquid electrolyte alkaline fuel cells and reversible alkaline fuel cells may work for many ideal cases, they have significant limitations.
A common design for electrolysis cells is the combination of a gas-impermeable membrane separator with electrodes flooded by water and/or electrolyte. U.S. Pat. No. 4,909,912 discloses such a design. This design is not practical for fuel cell operation because gas cannot be fed to catalysts in the flooded electrodes at a sufficient rate to generate high current density. Beyond not being useful as a fuel cell design, limitations with this cell design for electrolysis are that additional water and product gas separation steps are required to recover the product. Further, corrosion on the anode, i.e., the oxygen evolving electrode for water electrolysis, can be severe for any components in contact with the electrolyte. In this cell design, current collectors and bi-polar plates would be in contact with the electrolyte, exposing them to potentially corrosive electrochemical reactions.
Moreover, AEM degradation is also greater when in direct contact with the oxygen electrode. Patent application WO2011004343A1 discloses a traditional membrane electrolyzer design with an Anion Exchange Membrane (AEM), Membrane Electrode Assembly (MEA), and a dry hydrogen electrode. This approach has all the limitations mentioned above. Additionally, MEAs cannot be easily produced with all AEM material options because AEM expansion often occurs during hydration. Finally, the prior art for AEM designs is silent on handling high pressure differential between hydrogen and oxygen while maintaining a thin membrane with low resistance.
U.S. Patent Appl. 2010/0276299A1 discloses a cylindrical liquid alkaline cell design for generating high pressure hydrogen. The disclosed example uses a separator that is permeable to gases, thus pressure differential is not feasible with this design. The non-planar design would be difficult to manufacture at larger scales and would occupy greater space than planar designs. Additionally, similar to other existing low temperature electrolyzer designs, such a cell is not easily reversible.
U.S. Pat. No. 6,916,443B2 discusses designs for high pressure cell operation with a Proton Exchange Membrane (PEM) electrolysis cell based on using the electrode as a support for the membrane. Effective electrodes have a number of requirements, including porosity for gas transport, electrical conductivity, corrosion resistance in the gas/voltage/pH environment. Despite the array of options listed, few materials can effectively meet all of the requirements of both an electrode and a mechanical support. Porous titanium frit is generally used for PEM electrolyzers because it is porous, strong, and has low solubility in acid, thus minimizing membrane ion contamination. The limitations of this approach for pressure differential operation include the high cost of titanium or other metal porous frit options, high catalyst cost of platinum-iridium for the acidic environment, the high cost our fluorinated membrane, and the oxygen flammability of titanium frit, which would thus limit the ability to safely operate such an electrolyzer for producing pressurized oxygen. Further, PEM electrolyzers rely on membrane materials that have high hydrogen permeability relative to alkaline electrolyte on an equivalent conductivity basis, thus resulting in high hydrogen permeation at high pressure. Additionally, similar to most other existing low temperature electrolyzer designs, such a cell is not easily reversible.
Patent application WO2017054074 discusses the challenges of operating an electrolyzer at high pressure or high pressure differential between gases. The patent discloses a traditional PEM electrolyzer cell design. To address pressure differential the design uses off-set seal frame alignment, commonly used in fuel cells to prevent membrane tears along the edge, and titanium frit to support the membrane on the low-pressure side. As noted above, relying on metal frit for mechanical support introduces a number of limitations. Additionally, similar to most other existing low temperature electrolyzer designs, such a cell is not easily reversible.
U.S. Pat. No. 7,014,947 discloses a porous membrane support for a PEM electrolyzer in which the membrane support is percolated by the ion-conducting membrane material. This design relies on polymeric membrane material to conduct ions from one electrode to the next through the entire thickness of the support structure. Consequently, the design would have higher resistance compared to a thin membrane, a porous structure of similar thickness permeated with liquid electrolyte, or a combination of a thin membrane and a porous structure permeated with liquid electrolyte. Further, the design has all of the other limitations previously mentioned for a PEM electrolyzer.
In many instances of a reversible fuel cell and/or electrolyzer, it is desirable to generate high pressure gases. Electrochemical pressurization with the electrolyzer reduces system cost and efficiency losses associated with mechanically compressing gas to storage pressure. In some cases, it is desirable to compress hydrogen from 30 bar to greater than 700 bar, for more effective storage. For oxygen storage, pressures of 30 bar to 200 bar may be acceptable for storage. High oxygen pressure creates material flammability concerns, while lower pressures require more tank volume to store an equivalent mass of oxygen. Consequently, in many cases it is desirable to operate a water electrolyzer and/or reversible fuel cell under differential pressure conditions, in which the hydrogen and oxygen gas are produced at different pressures and subsequently stored at different pressures.
Proton-exchange membrane cells efficiently operate at limited hydrogen pressure, typically about 30 bar. PEM electrolysis membranes are quite permeable to hydrogen compared to alkaline electrolyte on an equivalent conductivity basis. At higher hydrogen pressures, more hydrogen permeates through the membrane, causing efficiency losses and safety concerns. To combat hydrogen permeability losses a thicker membrane may be used; however, this increases ionic resistance, resulting in ohmic efficiency losses. Cells with liquid alkaline electrolyte can theoretically achieve 38 times lower permeability at equivalent conductivity. Based on this fact, liquid alkaline electrolyzer systems could theoretically operate as efficiently as a PEM electrolyzer system at 38 times higher pressure, or >900 bar instead of 30 bar. However, traditional liquid electrolyte with a porous separator would not be able to safely handle significant pressure differences between hydrogen and oxygen. The combination of a gas impermeable membrane and liquid electrolyte, in series, in the instant invention thus solves the challenge of high hydrogen pressure and pressure differential for water electrolysis.
A further challenge with AEM-based water electrolyzers and reversible fuel cells is degradation of ionomers and the AEM. In particular, the high voltage oxygen electrode quickly degrades ionomers in the oxygen electrode during electrolysis. Highly active oxygen- and hydrogen-oxygen-containing intermediate species, such as free radical species, can attack and degrade the polymeric hydrocarbon AEMs that are immediately adjacent to the oxygen electrode. In the instant invention, having physical distance between the oxygen electrode and the AEM layer can extend AEM lifetime by allowing intermediate species to decompose before reaching the AEM. Having a tortuous path and/or a catalytic surface capable of decomposing oxygen intermediates between the AEM and oxygen electrode can thus further extend AEM lifetime.

Electrochemical cell and method of using same


A method of manufacturing a solid-state image sensor includes preparing a structure including a photoelectric converter formed in an image sensing region and a pad electrode formed in a pad region, forming a first organic film including a first organic portion arranged in the image sensing region of the structure in the image sensing region and the pad region, forming a color filter layer on the first organic portion, forming a second organic film in the image sensing region and the pad region, forming an inorganic film in the image sensing region and the pad region, and etching the inorganic film, the second organic film, and the first organic film so as to form an opening which communicates with the pad electrode.

1. Field of the Invention
The present invention relates to a solid-state image sensor, a method of manufacturing the same, and a camera.
2. Description of the Related Art
Japanese Patent Laid-Open No. 2003-229551 describes a solid-state image sensor which has a planarizing film arranged on a semiconductor substrate including a photoelectric conversion region and pad portion, a color filter film arranged on the planarizing film, and an on-chip microlens arranged on the color filter film. An opening is formed in a layer of the on-chip microlens and the planarizing film so as to expose the pad portion.
In recent years, as a pixel size is reduced, an amount of light which enters each photoelectric converter is decreased. Hence, in order to enhance an intensity of light entering each photoelectric converter, an antireflection film is formed on the surface of a microlens. However, after an inorganic film which forms the antireflection film was formed on an organic film which forms the microlens, when the inorganic film and organic film were plasma-etched to expose the pad portion, an insulation breakdown phenomenon of the organic film was observed although it occurred at a very low probability. This insulation breakdown may damage the pad portion. According to experiments of the present inventors, it was revealed that the insulation breakdown of the organic film occurred immediately after the inorganic film was penetrated by plasma etching. The present inventors estimated that the insulation breakdown of the organic film was caused since a breakdown voltage of the organic film was much lower than that of the inorganic film, a resist pattern formed on the inorganic film was charged by plasma, and a high voltage was applied between the resist pattern and pad portion. More specifically, the present inventors estimated that a high voltage was applied to the organic film below the inorganic film at an instance when the inorganic film was penetrated, thus causing the insulation breakdown of the organic film, and damaging the pad portion below the organic film. Also, the same problem may be posed not exclusively for an antireflection film but when an inorganic film is formed on a microlens formed of an organic substance. As such example, the problem occurs, for example, when a protection film or a planarizing film for implementation is formed.

Solid-state image sensor, method of manufacturing the same, and camera


In some examples, a splittable sheath includes a sheath body defining a lumen configured to receive an expandable balloon of a catheter, and a tab extending from a proximal end or a distal end of the sheath body. The tab includes a major surface having an outer edge defining a serpentine shape. Outward movement of the tab relative to a central longitudinal axis of the sheath body causes splitting of the sheath body.

Portions of the vasculature of a patient may be treated to restore adequate blood flow in an occluded blood vessel. Conditions for which blood-flow restoration may be indicated include atherosclerosis and other conditions that may cause narrowing of a lumen of a blood vessel. In some examples, a system for restoring adequate blood flow may include an expandable balloon positioned on a catheter and received within a sheath. During treatment, a clinician may advance the balloon through the sheath and into the vasculature of the patient, navigate the balloon to a treatment site within a target vessel, and then expand the balloon to restore patency of the target vessel. Some balloon sheaths may be configured to be longitudinally split into two portions to enable a clinician to remove the sheath from the catheter once the balloon has been advanced through the sheath. In some examples, expandable balloons may include a drug coating to help prevent re-stenosis of the target vessel.


A new cultivar of Coreopsis verticillata named ‘Electric Avenue’ characterized by its inflorescences that are clear yellow in color, its thread-leaf foliage, its high bud count, its height of 60 to 71 cm and an average spread of 60 cm, its cold hardiness in at least U.S.D.A. Zone 5, and its vigorous growth habit with heavy shoot production from over-wintered plants.

The present invention relates to a new and distinct cultivar of Coreopsis plant, botanically known as Coreopsis verticillata 'Electric Avenue' and will be referred to hereinafter by its cultivar name, 'Electric Avenue'. The new cultivar of Coreopsis is an herbaceous perennial grown for landscape and container use.
The new invention arose as a naturally occurring branch plant mutation of Coreopsis 'Route 66' (U.S. Plant Pat. No. 20,609) that was growing in a container in Alpharetta, Ga. in summer of 2009.
Asexual reproduction of the new cultivar was first accomplished by stem tip cuttings under the direction of one of the Inventors in Alpharetta, Ga. in the summer of 2009. The characteristics of this cultivar have been determined to be stable and are reproduced true to type in successive generations.


As shown in FIG. 2(a), according to the present invention, a quartz rod is used where, for example, the diameter of the end on the side to which an ultrasound probe attached is 0.58 mm, the diameter at the narrowest portion is 0.3 mm, the diameter at the end on the specimen side is 0.68 mm, and the length is 38 cm. As a result, the diameter on the side of fused quartz rod 20 to which ultrasound transducer 10 allows a favorable range of L (0,3) mode conversion efficiency; and in addition, the diameter of quartz rod 20 on the side coming into contact with specimen 50 is sufficiently large in comparison with wavelength, and in other portions it is set to be sufficiently narrow in order to obtain flexibility. FIG. 2(b) shows a transmission and a reception waveform.

The present invention relates to ultrasound transmission and reception utilizing, for example, ultrasound measurement and imaging in the field of medicine and the field of ultrasound measurement. In particular, it is related to ultrasound transmission and reception using pulse compression.
Conventionally, measurement has been performed and images obtained utilizing reflected ultrasound waves and the like. For example, with an ultrasound diagnosis apparatus, a tomogram of an organism is obtained by transmitting an impulse wave from an ultrasonic transducer, receiving back the reflected echo, and then being subjected to image processing. For such an ultrasound diagnosis apparatus, the deepest invasion depth and highest resolution possible is required.
There is a pulse compression technique that satisfies this requirement. With this, an originally long pulse is shortened and compressed by subjecting an ultrasonic signal that is to be transmitted to FM modulation (hereafter the resulting signal is referred to as a chirp signal) and upon reception, passing it through a filter corresponding to the chirp signal. An attempt is made to increase resolution due to the compression, and at the same time improve the signal-to-noise ratio, and improve the invasion depth.
With such pulse compression, since the transmitted signal and the received signal are temporally separate, it is necessary to separate the transducer from measurement subject. The region in between is called the separation region. For example, with an ultrasound microscope, the separation region is configured by a line that has a sufficiently large diameter in comparison to the signal wavelength and that is used as a delay medium. This line cannot be regarded as a waveguide because it may not be flexible due to the fact that it is allowed to have an infinitely large diameter. Here the waveguide is said to have no change in amplitude distribution within cross sections within the entire propagated distance. In this case, transmission/reception of a pulse having a long duration of 100 xcexcs or longer using the 20 Mhz band is practically difficult. In addition, since this line has no flexibility, it cannot be adapted for ultrasound endoscopes, etc. As a method in place of this, there is a method that uses separate probes for transmission and reception. In addition, a circulator is used with a 25 Mhz or higher band. However, a reflection occurring due to mismatch between the transducer and the transmission medium is additionally mixed into the reception system.
Pulse compression is widely used with the objective of attempting to increase transmission energy under the limitation of transmission peak-power in the field of radar and sonar in order to increase survey distance and/or gain higher resolution. Much research on introducing the pulse compression technique with similar objectives is also being carried out in the field of medical ultrasound. Notwithstanding benefits such as being able to improve resolution in a predetermined region in order to allow manipulation of the transmission signal spectrum in the time domain, this pulse compression technique has yet to reach realization in the field of medical ultrasound.
The biggest hurdle to bringing this into use is the need for a separation region, and the next hurdle is suppression of the side lobes after pulse compression. The problem with the latter is that due to the signal of a small reflective body becoming buried by the side lobes of a signal from a large reflective body.
Speaking of the separation region problem, with the pulse compression technique, the long pulse width of the transmitted pulse signal, which is hundreds of micro seconds long, causes separation to become great. A soft plastic board is ordinarily used to provide this region. In actuality, this method is very difficult to deal with. In addition, this method is not applicable to ultrasound endoscopes, etc. Another way of avoiding this method is using separate proves for transmission and reception. However when separate probes for transmission and reception are used, only a signal from the region where the transmitted ultrasound beam intersects the region where the reception transducer can receive, and the obtained image is poor. Furthermore, for reception of a mixed transmission signal and reception signal it is not practiceal because it requires an amplifier with extremely large dynamic range. Accordingly, a method of separating a transmission signal and a reception signal with an integrated transmission/reception probe is desirable.
The object of the present invention is to solve the following problems occurring in conventional ultrasound transmission and reception.
1. In pulse compression, a transmission signal and a reception signal having long duration cannot be temporally separated by a single transducer.
2. After compression, side lobe level suppression is insufficient.
Once these methods are developed, various applications such as detection of an extremely weak signal and Doppler measurement will become possible.
In order to achieve the above-mentioned object, an ultrasound transmission/reception apparatus, which performs pulse compression on a received ultrasound signal using a signal with temporally changing frequency as an ultrasound signal to be transmitted, is characterized by a transducer common for receiving and transmitting said ultrasound signal and a transmission line common for propagating said ultrasound signal, wherein a flexible waveguide transmission line is used as said transmission path, and said transmission line is used as a delay medium to temporally separate a received ultrasound signal and a transmitted ultrasound signal with long duration. A quartz rod where the center portion is made narrow can be used as this transmission line.
For said ultrasound signal to be transmitted, a signal where frequency changes but not dependent on time may be used. In this case, said signal to be transmitted may be a signal that becomes a signal where frequency changes in proportion to time when received. When the transmission line is long, a chirp signal with a changing frequency becomes distorted; however, by using a non-linear chirp signal where frequency changes but not in proportion to time, it becomes possible to reduce the distortion in the received signal.
Side lobe suppression can be performed after pulse compression of a received ultrasound signal, by taking the correlation with an ideal compression waveform during further compression.
By coding a plurality of ultrasound signals delayed a certain length of time in conformity with whether or not being sent according to a code series, and transmitting them, and after pulse compressing the received signals, they may be decoded in conformity with the code series that has been coded. In this manner, by transmitting a plurality of signals in accordance with the code series, two-step compression processing becomes possible, and a reception signal with an even higher SIN ratio can be obtained.
By using an up chirp signal and a down chirp signal as the ultrasound signal to be transmitted, and performing analysis of the time difference or spectrum of, for example, the compressed pulses obtained through processing said respective signals received, it is possible to accurately measure the Doppler effect.
In addition, the above mentioned transmission/reception configuration can be applied to configure an interluminary system.

Ultrasonic transmitter/receiver by pulse compression

Japan Science and Technology Corporation


The present invention relates to a compound of the Formula (I)

Organic light-emitting diodes (OLEDs), which are self-emitting devices, have a wide viewing angle, excellent contrast, quick response, high brightness, excellent driving voltage characteristics, and color reproduction. A typical OLED includes an anode, a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, the EML, and the ETL are thin films formed from organic and/or organometallic compounds.
When a voltage is applied to the anode and the cathode, holes injected from the anode electrode move to the EML, via the HTL, and electrons injected from the cathode electrode move to the EML, via the ETL. The holes and electrons recombine in the EML to generate excitons. When the excitons drop from an excited state to a ground state, light is emitted. The injection and flow of holes and electrons should be balanced, so that an OLED having the above-described structure has excellent efficiency.
EP 3 312 899 A1 relates to an organic light-emitting diode (OLED) including an ETL stack of at least two electron transport layers, wherein the first electron transport layer (135) comprises a charge transporting compound and the second electron transport layer (34) comprises an acridine compound and an alkali metal salt and/or alkali metal organic complex, a method of manufacturing the same and a device comprising the OLED.
WO 2015/083948 A1 provides: a novel compound capable of improving the luminous efficiency, stability and lifetime of an element; an organic electric element using the same; and an electronic device thereof.
KR 2016 0059 336 A provides: a compound which has high light-emitting efficiency of an element and low driving voltage of an element, and is capable of improving lifespan of an element; an organic electronic element using the same; and an electronic device thereof. In addition, the compound is represented by chemical formula 1

Acridine compounds which are symmetrically substituted on a heteroaryl comprised therein are used in organic electronics applications, especially as electron transport materials. Respective compounds often have very high melting points and no measurable glass transition temperature (Tg). Without being bound by theory, a very high melting point combined with a lack of Tg may be indicative of a compound with high crystallinity. High crystallinity is not preferred in applications in organic electronics, as crystallization may be detrimental to conductivity and morphological stability of an organic semiconducting layer. In particular, in an organic semiconducting layer further comprising a dopant, high crystallinity of the matrix compound may result in de-mixing of the composition. Furthermore, there is still a need to improve the electronic properties of respective compounds for use in organic electronic devices, in particular to provide compounds having a less negative LUMO.
It is therefore an object of the present invention to provide novel organic electronic devices and compounds for use therein overcoming drawbacks of the prior art, in particular to provide novel compounds having improved morphological properties, in particular melting points and/or glass transition temperatures and/or electronic properties which may be suitable to improve the performance of organic electronic devices, in particular when used in an electron transport layer.
The above object is achieved by a compound of the Formula (I)

wherein at least one of R1 to R10 and/or Ar4 is a group having the Formula (II)

wherein the asterisk symbol "*" in Formula (II) represents the position of binding of the group having the Formula (II);
L is selected from substituted or unsubstituted C6 to C18 arylene;
Ar1 is selected from the group consisting of substituted or unsubstituted C3 to C24 heteroaryl, wherein the heteroaryl comprises at least two N-atoms;
Ar2 and Ar3 are independently selected from the group consisting of substituted or unsubstituted C6 to C24 aryl and/or substituted or unsubstituted C4 to C24 heteroaryl, wherein Ar2 and Ar3 are selected differently from each other;
Ar4 is selected from the group consisting of substituted or unsubstituted C1 to C16 alkyl, substituted or unsubstituted C6 to C24 aryl, substituted or unsubstituted C2 to C24 heteroaryl, and a group having the general Formula (II);
R1 to R10 are independently selected from the group consisting of H, D, F, C1 to C20 alkyl, C6 to C20 aryl, C2 to C20 heteroaryl and a group having the Formula (II); and R1 and R2; or R2 and R3; or R3 and R4; or R5 and R6 may independently from each other form a fused ring or a system of fused rings;
wherein, in the respective substituted groups, the substituents each are independently selected from the group consisting of D, F, C1 to C20 linear alkyl, C3 to C20 branched alkyl, C3 to C20 cyclic alkyl, C1 to C20 linear alkoxy, C3 to C20 branched alkoxy, C1 to C12 linear fluorinated alkyl, C1 to C12 linear fluorinated alkoxy, C3 to C12 branched fluorinated cyclic alkyl, C3 to C20 fluorinated cyclic alkyl, C3 to C12 fluorinated cyclic alkoxy, CN, RCN, C6 to C20 aryl, C2 to C20 heteroaryl, OR, SR, (C═O)R, (C═O)NR2, SiR3, (S═O)R, (S═O)2R, (P═O)R2; wherein each R is independently selected from the group consisting of C1 to C20 linear alkyl, C1 to C20 alkoxy, C1 to C20 thioalkyl, C3 to C20 branched alkyl, C3 to C20 cyclic alkyl, C3 to C20 branched alkoxy, C3 to C20 cyclic alkoxy, C3 to C20 branched thioalkyl, C3 to C20 cyclic thioalkyl, C6 to C20 aryl and C2 to C20 heteroaryl.
In the above Formula, the single bond between the benzoacridine moiety and the respective Rn, respectively Ar4, group is the same single bond as that between the asteric symbol "*" and the moiety L.
Ar2 and Ar3 are selected differently from each other. That is, that Ar2 and Ar3 are chemically not identical. In other words, both groups are selected from substituted or unsubstituted C6 to C24 aryl or substituted or unsubstituted C4 to C24 heteroaryl but the selected group cannot be the same for Ar2 and Ar3. Compounds in which Ar2 and Ar3 are selected the same (not according to the invention and known from the prior art) are designated herein as "symmetrically substituted". Inventive compounds in which Ar2 and Ar3 are selected differently from each other are designated as "asymmetrically substituted".
It has surprisingly been found by the inventors that asymmetrically substituted compounds of Formula (I) have favorable melting points, glass transition temperatures, rate onset temperatures and/or electronic properties, in particular feature a less negative LUMO which improves the usability thereof in organic semiconducting materials and organic electronic devices.
With respect to the compound of Formula (I) it may be provided that one or more of the compounds respectively by following Formulas are excluded:

In the inventive compound L may be selected from the group consisting of phenylene, biphenylene, terphenylene, phenanthrylene, triphenylylene and naphthylene; alternatively from the group consisting of phenylene, biphenylene and naphthylene; alternatively from the group consisting of phenylene and biphenylene. In this way, fine tuning of the thermal properties and electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers.
In the inventive compound Ar1 may be selected from triazine and pyrimidine. Alternatively, Ar1 may be selected from triazine, pyrazine and pyrimidine. In this way, fine tuning of the electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers.
Ar1 may be free of carbazole and/or indolocarbazole groups.
In the inventive compound Ar3 may be biphenyl, naphthyl, dibenzofuranyl or dibenzothiophenyl; alternatively Ar3 may be selected from the following groups having the Formulas (III) and (IV)

In this way, fine tuning of the electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers.
In the inventive compound, Ar3 may be substituted phenyl or biphenyl, wherein the substituent on Ar3 is selected differently from the substituent on Ar2, if present. The substituent on Ar3 may be selected from CN. Alternatively, Ar3 is selected from —C6H5CN.
In the inventive compound Ar3 may be biphenyl, naphthyl, dibenzofuranyl or dibenzothiophenyl, substituted phenyl or substituted biphenyl; alternatively Ar3 may be selected from the following groups having the Formulas (III), (IV), (V) and (VI)

In this way, fine tuning of the electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers.
In the inventive compound, Ar1 may be triazine, pyrazine or pyrimidine and Ar3 may be selected from Formulas (III) to (VI); alternatively, Ar1 may be pyrimidine and Ar3 may be selected from Formulas (III) to (VI). In this way, fine tuning of the electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers. In the inventive compound Ar2 may be phenyl. In this way, fine tuning of the electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers.
In the inventive compound, it may be provided that Ar2 is phenyl and Ar3 is biphenyl or —C6H5CN. In this way, fine tuning of the electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers.
In the inventive compound Ar4 may be selected from the group consisting of phenyl, biphenyl, terphenyl and naphthyl and a group having the Formula (II); alternatively Ar4 is selected from Formula (II). In this way, fine tuning of the morphological properties and electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers.
In the inventive compound Ar4 may be selected from the group consisting of phenyl, biphenyl, terphenyl and naphthyl and R1 to R10, alternatively R9, are independently selected from the group consisting of H, D and a group having the Formula (II). In this way, fine tuning of the morphological properties and electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers.
In the inventive compound R1 and R2 may form together a fused ring, alternatively R1 and R2 form together a six-membered fused ring. In this way, fine tuning of the morphological properties and electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers.
The inventive compound of Formula (I) may have one of the following Formulas (Ia), (Ib), (Ic) and (Id)

In this way, fine tuning of the morphological properties and electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers.
L, Ar1, Ar2 and Ar3 may be unsubstituted. Thereby, particularly beneficial performance in organic electronic devices may be obtained, when the compound of formula (I) is evaporated and deposited on the substrate in high vacuum.
Compound of Formula (I) may have one of the Formulas (Ia), (Ib), (Ic) and (Id), wherein R1 to R10 are H and Ar4 is selected from Formula (II). Preferably, compound of Formula (I) may have Formula (Ia), wherein R3 to R10 are H and Ar4 is selected from Formula (II).
In the compound of Formula (I) R1 to R10 may be H and Ar4 may be Formula (II).
The inventive compound may have one of the following structures A-1 to A-15

In this way, fine tuning of the morphological properties and electronic structure of the compound of Formula (I) can be achieved to further improve the usability thereof in organic semiconducting layers of organic electronic devices in particular in electron transport layers.
The object is further achieved by an organic semiconducting layer comprising the inventive compound of Formula (I).
The organic semiconducting layer may consist of a compound of Formula (I).
The organic semiconducting layer comprising or consisting of the compound of Formula (I) may be non-emissive.
The organic semiconducting layer may further comprise a metal, a metal salt or an alkali or alkaline earth metal complex; alternatively an organic alkali or alkaline earth metal complex; alternatively 8-hydroxyquinolinolato lithium or alkali borate. Additionally, the object is achieved by an organic electronic device comprising the inventive organic semiconducting layer.
The organic electronic device comprising the inventive organic semiconducting layer may further comprise an anode, a cathode and an emission layer.
In the organic electronic device, the organic semiconducting layer comprising compound of Formula (I) may be arranged between the anode and the cathode.
The organic semiconducting layer may be arranged between the emission layer and the cathode. If the organic semiconducting layer is arranged in this way, it may function as electron transport layer.
In the organic electronic device, the organic semiconducting layer may be in direct contact with the emission layer.
The organic electronic device may further comprise a hole blocking layer, wherein the hole blocking layer is in direct contact with the emission layer and the organic semiconductor layer comprising the compound of Formula (I) is arranged between the hole blocking layer and the cathode.
The organic semiconducting layer may be arranged between the hole blocking layer and the cathode and may be in direct contact with the hole blocking layer and the cathode.
In the organic electronic device, the organic semiconducting layer may further comprise a metal, a metal salt or an alkali or alkaline earth metal complex, alternatively an organic alkali or alkaline earth metal complex, alternatively 8-hydroxyquinolinolato-lithium or an alkali borate.
The object is further achieved by an organic semiconducting material comprising a compound of Formula (I)
                wherein at least one of R1 to R10 and/or Ar4 is a group having the Formula (II)
                wherein the asterisk symbol "*" in Formula (II) represents the position of binding of the group having the Formula (II);        L is selected from substituted or unsubstituted C6 to C18 arylene;        Ar1 is selected from substituted or unsubstituted C3 to C24 heteroaryl, wherein the heteroaryl comprises at least two N-atoms;        Ar2 and Ar3 are independently selected from substituted or unsubstituted C6 to C24 aryl and/or substituted or unsubstituted C4 to C24 heteroaryl,        wherein Ar2 and Ar3 are selected differently from each other;        Ar4 is selected from the group consisting of substituted or unsubstituted C1 to C16 alkyl, substituted or unsubstituted C6 to C24 aryl, substituted or unsubstituted C2 to C24 heteroaryl and a group having the general Formula (II);        R1 to R10 are independently selected from the group consisting of H, D, F, C1 to C20 alkyl, C6 to C20 aryl, C2 to C20 heteroaryl and a group having the Formula (II); and R1 and R2; or R2 and R3; or R3 and R4; or R5 and R6 may independently from each other form a fused ring or a system of fused rings;        wherein, in the respective substituted groups, the substituents each are independently selected from the group consisting of D, F, C1 to C20 linear alkyl, C3 to C20 branched alkyl, C3 to C20 cyclic alkyl, C1 to C20 linear alkoxy, C3 to C20 branched alkoxy, C1 to C12 linear fluorinated alkyl, C1 to C12 linear fluorinated alkoxy, C3 to C12 branched fluorinated cyclic alkyl, C3 to C20 fluorinated cyclic alkyl, C3 to C12 fluorinated cyclic alkoxy, CN, RCN, C6 to C20 aryl, C2 to C20 heteroaryl, OR, SR, (C═O)R, (C═O)NR2, SiR3, (S═O)R, (S═O)2R, (P═O)R2; wherein each R is independently selected from the group consisting of C1 to C20 linear alkyl, C1 to C20 alkoxy, C1 to C20 thioalkyl, C3 to C20 branched alkyl, C3 to C20 cyclic alkyl, C3 to C20 branched alkoxy, C3 to C20 cyclic alkoxy, C3 to C20 branched thioalkyl, C3 to C20 cyclic thioalkyl, C6 to C20 aryl and C2 to C20 heteroaryl; and
a metal, a metal salt or an alkali or alkaline earth metal complex; alternatively an organic alkali or alkaline earth metal complex; alternatively 8-hydroxyquinolinolato lithium or alkali borate.
The object is further achieved by an organic semiconducting layer comprising the organic semiconducting material.
The organic semiconducting layer comprising or consisting of the organic semiconducting material may be non-emissive.
Additionally, the object is achieved by an organic electronic device comprising the inventive organic semiconducting layer comprising the organic semiconducting material.
The organic electronic device comprising the inventive organic semiconducting layer comprising the organic semiconducting material may further comprise an anode, a cathode and an emission layer.
In the organic electronic device, the organic semiconducting layer comprising the organic semiconducting material may be arranged between the anode and the cathode.
The organic semiconducting layer comprising the organic semiconducting material may be arranged between the emission layer and the cathode. If the organic semiconducting layer is arranged in this way, it may function as electron transport layer.
The organic electronic device may further comprise a hole blocking layer, wherein the hole blocking layer is in direct contact with the emission layer and the organic semiconductor layer comprising the organic semiconducting material is arranged between the hole blocking layer and the cathode.
The organic semiconducting layer comprising the organic semiconducting material may be arranged between the hole blocking layer and the cathode and may be in direct contact with the hole blocking layer and the cathode.
Furthermore, the object is achieved by a display device comprising the inventive organic electronic device.
Finally, the object is achieved by a lighting device comprising the inventive organic electronic device.
In accordance with the invention, the structures shown in table 1 below are most preferred.
Further Layers
In accordance with the invention, the organic electronic device may comprise, besides the layers already mentioned above, further layers. Exemplary embodiments of respective layers are described in the following:
Substrate
The substrate may be any substrate that is commonly used in manufacturing of, electronic devices, such as organic light-emitting diodes. If light is to be emitted through the substrate, the substrate shall be a transparent or semitransparent material, for example a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate may be both a transparent as well as a non-transparent material, for example a glass substrate, a plastic substrate, a metal substrate or a silicon substrate.
Anode Electrode
Either a first electrode or a second electrode comprised in the inventive organic electronic device may be an anode electrode. The anode electrode may be formed by depositing or sputtering a material that is used to form the anode electrode. The material used to form the anode electrode may be a high work-function material, so as to facilitate hole injection. The anode material may also be selected from a low work function material (i.e. aluminum). The anode electrode may be a transparent or reflective electrode. Transparent conductive oxides, such as indium tin oxide (ITO), indium zinc oxide (IZO), tin-dioxide (SnO2), aluminum zinc oxide (AlZO) and zinc oxide (ZnO), may be used to form the anode electrode. The anode electrode may also be formed using metals, typically silver (Ag), gold (Au), or metal alloys.
Hole Injection Layer
A hole injection layer (HIL) may be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) deposition, or the like. When the HIL is formed using vacuum deposition, the deposition conditions may vary according to the compound that is used to form the HIL, and the desired structure and thermal properties of the HIL. In general, however, conditions for vacuum deposition may include a deposition temperature of 100° C. to 500° C., a pressure of 10-8 to 10-3 Torr (1 Torr equals 133.322 Pa), and a deposition rate of 0.1 to 10 nm/sec.
When the HIL is formed using spin coating or printing, coating conditions may vary according to the compound that is used to form the HIL, and the desired structure and thermal properties of the HIL. For example, the coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm, and a thermal treatment temperature of about 80° C. to about 200° C. Thermal treatment removes a solvent after the coating is performed.
The HIL may be formed of any compound that is commonly used to form a HIL. Examples of compounds that may be used to form the HIL include a phthalocyanine compound, such as copper phthalocyanine (CuPc), 4,4′,4″-tris (3-methylphenylphenylamino) triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (Pani/CSA), and polyaniline)/poly(4-styrenesulfonate (PANI/PSS).
The HIL may comprise or consist of p-type dopant and the p-type dopant may be selected from tetrafluoro-tetracyanoquinonedimethane (F4TCNQ), 2,2′-(perfluoronaphthalen-2,6-diylidene) dimalononitrile or 2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) but not limited hereto. The HIL may be selected from a hole-transporting matrix compound doped with a p-type dopant. Typical examples of known doped hole transport materials are: copper phthalocyanine (CuPc), which HOMO level is approximately −5.2 eV, doped with tetrafluoro-tetracyanoquinonedimethane (F4TCNQ), which LUMO level is about −5.2 eV; zinc phthalocyanine (ZnPc) (HOMO=−5.2 eV) doped with F4TCNQ; α-NPD (N,N′-Bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine) doped with F4TCNQ. α-NPD doped with 2,2′-(perfluoronaphthalen-2,6-diylidene) dimalononitrile. The p-type dopant concentrations can be selected from 1 to 20 wt.-%, more preferably from 3 wt.-% to 10 wt.-%.
The thickness of the HIL may be in the range from about 1 nm to about 100 nm, and for example, from about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL may have excellent hole injecting characteristics, without a substantial penalty in driving voltage.
Hole Transport Layer
A hole transport layer (HTL) may be formed on the HIL by vacuum deposition, spin coating, slot-die coating, printing, casting, Langmuir-Blodgett (LB) deposition, or the like. When the HTL is formed by vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for the vacuum or solution deposition may vary, according to the compound that is used to form the HTL.
The HTL may be formed of any compound that is commonly used to form a HTL. Compounds that can be suitably used are disclosed for example in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010 and incorporated by reference. Examples of the compound that may be used to form the HTL are: carbazole derivatives, such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives, such as N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1-biphenyl]-4,4′-diamine (TPD), or N,N′-di(naphthalen-1-yl)-N,N′-diphenyl benzidine (alpha-NPD); and triphenylamine-based compound, such as 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit excitons from being diffused into the EML.
The thickness of the HTL may be in the range of about 5 nm to about 250 nm, preferably, about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 160 nm, further about 100 nm to about 160 nm, further about 120 nm to about 140 nm. A preferred thickness of the HTL may be 170 nm to 200 nm.
When the thickness of the HTL is within this range, the HTL may have excellent hole transporting characteristics, without a substantial penalty in driving voltage.
Electron Blocking Layer
The function of an electron blocking layer (EBL) is to prevent electrons from being transferred from an emission layer to the hole transport layer and thereby confine electrons to the emission layer. Thereby, efficiency, operating voltage and/or lifetime are improved. Typically, the electron blocking layer comprises a triarylamine compound. The triarylamine compound may have a LUMO level closer to vacuum level than the LUMO level of the hole transport layer. The electron blocking layer may have a HOMO level that is further away from vacuum level compared to the HOMO level of the hole transport layer. The thickness of the electron blocking layer may be selected between 2 and 20 nm.
If the electron blocking layer has a high triplet level, it may also be described as triplet control layer.
The function of the triplet control layer is to reduce quenching of triplets if a phosphorescent green or blue emission layer is used. Thereby, higher efficiency of light emission from a phosphorescent emission layer can be achieved. The triplet control layer is selected from triarylamine compounds with a triplet level above the triplet level of the phosphorescent emitter in the adjacent emission layer. Suitable compounds for the triplet control layer, in particular the triarylamine compounds, are described in EP 2 722 908 A1.
Emission Layer (EML)
The EML may be formed on the HTL by vacuum deposition, spin coating, slot-die coat-ing, printing, casting, LB deposition, or the like. When the EML is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for deposition and coating may vary, according to the compound that is used to form the EML.
It may be provided that the emission layer does not comprise the compound of Formula (I).
The emission layer (EML) may be formed of a combination of a host and an emitter dopant. Example of the host are Alq3, 4,4′-N,N′-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4′,4″-tris(carbazol-9-yl)-triphenylamine(TCTA), 1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracenee (TBADN), distyrylarylene (DSA) and bis(2-(2-hydroxyphenyl)benzo-thiazolate)zinc (Zn(BTZ)2).
The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters which emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.
Examples of red emitter dopants are PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited thereto. These compounds are phosphorescent emitters, however, fluorescent red emitter dopants could also be used.
Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.
Examples of phosphorescent blue emitter dopants are F2Irpic, (F2ppy)2Ir(tmd) and Ir(dfppz)3 and ter-fluorene. 4.4′-bis(4-diphenyl amiostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butyl perylene (TBPe) are examples of fluorescent blue emitter dopants.
The amount of the emitter dopant may be in the range from about 0.01 to about 50 parts by weight, based on 100 parts by weight of the host. Alternatively, the emission layer may consist of a light-emitting polymer. The EML may have a thickness of about 10 nm to about 100 nm, for example, from about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent light emission, without a substantial penalty in driving voltage.
Hole Blocking Layer (HBL)
A hole blocking layer (HBL) may be formed on the EML, by using vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, or the like, in order to prevent the diffusion of holes into the ETL. When the EML comprises a phosphorescent dopant, the HBL may have also a triplet exciton blocking function. The hole blocking layer may be the inventive organic semiconducting layer comprising or consisting of the inventive compound represented by the general Formula (I) as defined above.
The HBL may also be named auxiliary ETL or a-ETL.
When the HBL is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for deposition and coating may vary, according to the compound that is used to form the HBL. Any compound that is commonly used to form a HBL may be used. Examples of compounds for forming the HBL include oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives.
The HBL may have a thickness in the range from about 5 nm to about 100 nm, for example, from about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL may have excellent hole-blocking properties, without a substantial penalty in driving voltage.
Electron Transport Layer (ETL)
The OLED according to the present invention may comprise an electron transport layer (ETL). In accordance with the invention, the electron transport layer may be the inventive organic semiconducting layer comprising the inventive compound represented by the general Formula (I) as defined above.
According to various embodiments the OLED may comprise an electron transport layer or an electron transport layer stack comprising at least a first electron transport layer and at least a second electron transport layer.
By suitably adjusting energy levels of particular layers of the ETL, the injection and transport of the electrons may be controlled, and the holes may be efficiently blocked. Thus, the OLED may have long lifetime.
The electron transport layer of the organic electronic device may comprise the compound represented by general Formula (I) as defined above as the organic electron transport matrix (ETM) material. The electron transport layer may comprise, besides the compound represented by the general Formula (I), further ETM materials known in the art. Likewise, the electron transport layer may comprise as the only electron transport matrix material the compound represented by general Formula (I). In case that the inventive organic electronic device comprises more than one electron transport layers, the compound represented by the general Formula (I) may be comprised in only one of the electron transport layers, in more than one of the electron transport layers or in all of the electron transport layers. In accordance with the invention, the electron transport layer may comprise, besides the ETM material, at least one additive as defined below.
Further, the electron transport layer may comprise one or more n-type dopants. The additive may be an n-type dopant. The additive can be alkali metal, alkali metal compound, alkaline earth metal, alkaline earth metal compound, transition metal, transition metal compound or a rare earth metal. In another embodiment, the metal can be one selected from a group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. In another embodiment, the n-type dopant can be one selected from a group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Eu and Yb. In an embodiment the alkali metal compound may be 8-Hydroxyquinolinolato-lithium (LiQ), Lithium tetra(1H-pyrazol-1-yl)borate or Lithium 2-(diphenylphosphoryl)phenolate. Suitable compounds for the ETM (which may be used in addition to the inventive compound represented by the general Formula (I) as defined above) are not particularly limited. In one embodiment, the electron transport matrix compounds consist of covalently bound atoms. Preferably, the electron transport matrix compound comprises a conjugated system of at least 6, more preferably of at least 10 delocalized electrons. In one embodiment, the conjugated system of delocalized electrons may be comprised in aromatic or heteroaromatic structural moieties, as disclosed e.g. in documents EP 1 970 371 A1 or WO 2013/079217 A1.
Electron Injection Layer (EIL)
An optional EIL, which may facilitates injection of electrons from the cathode, may be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include lithium 8-hydroxyquinolinolate (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg which are known in the art. Deposition and coating conditions for forming the EIL are similar to those for formation of the HIL, although the deposition and coating conditions may vary, according to the material that is used to form the EIL. The EIL may be the organic semiconducting layer comprising the compound of Formula (I).
The thickness of the EIL may be in the range from about 0.1 nm to about 10 nm, for example, in the range from about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL may have satisfactory electron-injecting properties, without a substantial penalty in driving voltage.
Cathode Electrode
The cathode electrode is formed on the EIL if present. The cathode electrode may be formed of a metal, an alloy, an electrically conductive compound, or a mixture thereof. The cathode electrode may have a low work function. For example, the cathode electrode may be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), or the like. Alternatively, the cathode electrode may be formed of a transparent conductive oxide, such as ITO or IZO.
The thickness of the cathode electrode may be in the range from about 5 nm to about 1000 nm, for example, in the range from about 10 nm to about 100 nm. When the thickness of the cathode electrode is in the range from about 5 nm to about 50 nm, the cathode electrode may be transparent or semitransparent even if formed from a metal or metal alloy.
It is to be understood that the cathode electrode is not part of an electron injection layer or the electron transport layer.
Charge Generation Layer/Hole Generating Layer
The charge generation layer (CGL) may comprise a p-type and an n-type layer. An interlayer may be arranged between the p-type layer and the n-type layer.
Typically, the charge generation layer is a pn junction joining an n-type charge generation layer (electron generating layer) and a hole generating layer. The n-side of the pn junction generates electrons and injects them into the layer which is adjacent in the direction to the anode. Analogously, the p-side of the p-n junction generates holes and injects them into the layer which is adjacent in the direction to the cathode.
Charge generating layers are used in tandem devices, for example, in tandem OLEDs comprising, between two electrodes, two or more emission layers. In a tandem OLED comprising two emission layers, the n-type charge generation layer provides electrons for the first light emission layer arranged near the anode, while the hole generating layer provides holes to the second light emission layer arranged between the first emission layer and the cathode.
Suitable matrix materials for the hole generating layer may be materials conventionally used as hole injection and/or hole transport matrix materials. Also, p-type dopant used for the hole generating layer can employ conventional materials. For example, the p-type dopant can be one selected from a group consisting of tetrafluore-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), derivatives of tetracyanoquinodimethane, radialene derivatives, iodine, FeCl3, FeF3, and SbCl5. Also, the host can be one selected from a group consisting of N,N′-di(naphthalen-1-yl)-N,N-diphenyl-benzidine (NPB), N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1-biphenyl-4,4′-diamine (TPD) and N,N′,N′-tetranaphthyl-benzidine (TNB). The p-type charge generation layer may consist of CNHAT.
The n-type charge generating layer may be the layer comprising the compound of Formula (I). The n-type charge generation layer can be layer of a neat n-type dopant, for example of an electropositive metal, or can consist of an organic matrix material doped with the n-type dopant. In one embodiment, the n-type dopant can be alkali metal, alkali metal compound, alkaline earth metal, alkaline earth metal compound, a transition metal, a transition metal compound or a rare earth metal. In another embodiment, the metal can be one selected from a group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. More specifically, the n-type dopant can be one selected from a group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Eu and Yb. Suitable matrix materials for the electron generating layer may be the materials conventionally used as matrix materials for electron injection or electron transport layers. The matrix material can be for example one selected from a group consisting of triazine compounds, hydroxyquinoline derivatives like tris(8-hydroxyquinoline)aluminum, benzazole derivatives, and silole derivatives.
The hole generating layer is arranged in direct contact to the n-type charge generation layer.
Organic Light-Emitting Diode (OLED)
The organic electronic device according to the invention may be an organic light-emitting device.
According to one aspect of the present invention, there is provided an organic light-emitting diode (OLED) comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an emission layer, an organic semiconducting layer comprising a compound of formula (I) and a cathode electrode.
According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer, an organic semiconducting layer comprising a compound of formula (I) and a cathode electrode.
According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer, an organic semiconducting layer comprising a compound of Formula (I), an electron injection layer, and a cathode electrode.
According to various embodiments of the present invention, there may be provided OLEDs layers arranged between the above mentioned layers, on the substrate or on the top electrode.
According to one aspect, the OLED can comprise a layer structure of a substrate that is adjacent arranged to an anode electrode, the anode electrode is adjacent arranged to a first hole injection layer, the first hole injection layer is adjacent arranged to a first hole transport layer, the first hole transport layer is adjacent arranged to a first electron blocking layer, the first electron blocking layer is adjacent arranged to a first emission layer, the first emission layer is adjacent arranged to a first electron transport layer, the first electron transport layer is adjacent arranged to an n-type charge generation layer, the n-type charge generation layer is adjacent arranged to a hole generating layer, the hole generating layer is adjacent arranged to a second hole transport layer, the second hole transport layer is adjacent arranged to a second electron blocking layer, the second electron blocking layer is adjacent arranged to a second emission layer, between the second emission layer and the cathode electrode an optional electron transport layer and/or an optional injection layer are arranged.
The organic semiconducting layer according to the invention may be the electron transport layer, first electron transport layer, n-type charge generation layer and/or second electron transport layer.
For example, the OLED according to FIG. 2 may be formed by a process, wherein on a substrate (110), an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), an emission layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180) and the cathode electrode (190) are subsequently formed in that order.
Organic Electronic Device
An organic electronic device according to the invention comprises an organic semiconducting layer comprising a compound according to Formula (I).
An organic electronic device according to one embodiment may include a substrate, an anode layer, an organic semiconducting layer comprising a compound of Formula (I) and a cathode layer.
An organic electronic device according to one embodiment comprises at least one organic semiconducting layer comprising at least one compound of Formula (I), at least one anode layer, at least one cathode layer and at least one emission layer, wherein the organic semiconducting layer is preferably arranged between the emission layer and the cathode layer.
An organic light-emitting diode (OLED) according to the invention may include an anode, a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL) comprising at least one compound of Formula (I), and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, the EML, and the ETL are thin films formed from organic compounds.
An organic electronic device according to one embodiment can be a light emitting device, thin film transistor, a battery, a display device or a photovoltaic cell, and preferably a light emitting device.
According to another aspect of the present invention, there is provided a method of manufacturing an organic electronic device, the method using:                at least one deposition source, preferably two deposition sources and more preferred at least three deposition sources.
The methods for deposition that can be suitable comprise:                deposition via vacuum thermal evaporation;        deposition via solution processing, preferably the processing is selected from spin-coating, printing, casting; and/or        slot-die coating.
According to various embodiments of the present invention, there is provided a method using:                a first deposition source to release the compound of Formula (I) according to the invention, and        a second deposition source to release the metal, a metal salt or an alkali or alkaline earth metal complex; alternatively an organic alkali or alkaline earth metal complex; alternatively 8-hydroxyquinolinolato lithium or alkali borate;
the method comprising the steps of forming the organic semiconducting layer; whereby for an organic light-emitting diode (OLED):                the organic semiconducting layer is formed by releasing the compound of Formula (I) according to the invention from the first deposition source and a metal, a metal salt or an alkali or alkaline earth metal complex; alternatively an organic alkali or alkaline earth metal complex; alternatively 8-hydroxyquinolinolato lithium or alkali borate, from the second deposition source.
According to various embodiments of the present invention, the method may further include forming on the anode electrode, an emission layer and at least one layer selected from the group consisting of forming a hole injection layer, forming a hole transport layer, or forming a hole blocking layer, between the anode electrode and the first electron transport layer.
According to various embodiments of the present invention, the method may further include the steps for forming an organic light-emitting diode (OLED), wherein                on a substrate a first anode electrode is formed,        on the first anode electrode an emission layer is formed,        on the emission layer an electron transport layer stack is formed, optionally a hole blocking layer is formed on the emission layer and an organic semiconducting layer is formed,        and finally a cathode electrode is formed,        optional a hole injection layer, a hole transport layer, and a hole blocking layer, formed in that order between the first anode electrode and the emission layer,        optional an electron injection layer is formed between the organic semiconducting layer and the cathode electrode.
According to various embodiments of the present invention, the method may further comprise forming an electron injection layer on the organic semiconducting layer. However, according to various embodiments of the OLED of the present invention, the OLED may not comprise an electron injection layer.
According to various embodiments, the OLED may have the following layer structure, wherein the layers having the following order:
anode, hole injection layer, first hole transport layer, second hole transport layer, emission layer, optional hole blocking layer, organic semiconducting layer comprising a compound of Formula (I) according to the invention, optional electron injection layer, and cathode.
According to another aspect of the invention, it is provided an electronic device comprising at least one organic light emitting device according to any embodiment described throughout this application, preferably, the electronic device comprises the organic light emitting diode in one of embodiments described throughout this application. More preferably, the electronic device is a display device.
In one embodiment, the organic electronic device according to the invention comprising an organic semiconducting layer comprising a compound according to Formula (I) may further comprise a layer comprising a radialene compound and/or a quinodimethane compound.
In one embodiment, the radialene compound and/or the quinodimethane compound may be substituted with one or more halogen atoms and/or with one or more electron withdrawing groups. Electron withdrawing groups can be selected from nitrile groups, halogenated alkyl groups, alternatively from perhalogenated alkyl groups, alternatively from perfluorinated alkyl groups. Other examples of electron withdrawing groups may be acyl, sulfonyl groups or phosphoryl groups.
Alternatively, acyl groups, sulfonyl groups and/or phosphoryl groups may comprise halogenated and/or perhalogenated hydrocarbyl. In one embodiment, the perhalogenated hydrocarbyl may be a perfluorinated hydrocarbyl. Examples of a perfluorinated hydrocarbyl can be perfluormethyl, perfluorethyl, perfluorpropyl, perfluorisopropyl, perfluorobutyl, perfluorophenyl, perfluorotolyl; examples of sulfonyl groups comprising a halogenated hydrocarbyl may be trifluoromethylsulfonyl, pentafluoroethylsulfonyl, pentafluorophenylsulfonyl, heptafluoropropylsufonyl, nonafluorobutylsulfonyl, and like.
In one embodiment, the radialene and/or the quinodimethane compound may be comprised in a hole injection, hole transporting and/or a hole generation layer.
In one embodiment, the radialene compound may have Formula (XX) and/or the quinodimethane compound may have Formula (XXIa) or (XXIb):

wherein R1, R2, R3, R4, R5, R6, R7, R8, R11, R12, R15, R16, R20, R21 are independently selected from above mentioned electron withdrawing groups and R9, R10, R13, R14, R17, R18, R19, R22, R23 and R24 are independently selected from H, halogen and above mentioned electron withdrawing groups.
Hereinafter, the embodiments are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following examples. Reference will now be made in detail to the exemplary aspects.

Compound and organic semiconducting layer, organic electronic device, display device and lighting device comprising the same

Abstract: wherein the asterisk symbol “*” in Formula (II) represents the position of binding of the group having the Formula (II); L is selected from substituted or unsubstituted C6 to C18 arylene; Ar1 is selected from substituted or unsubstituted C3 to C24 heteroaryl, wherein the heteroaryl comprises at least two N-atoms; Ar2 and Ar3 are independently selected from substituted or unsubstituted C6 to C24 aryl and/or substituted or unsubstituted C4 to C24 heteroaryl, wherein Ar2 and Ar3 are selected differently from each other; Ar4 is selected from the group consisting of substituted or unsubstituted C1 to C16 alkyl, substituted or unsubstituted C6 to C24 aryl, substituted or unsubstituted C2 to C24 heteroaryl and a group having the general Formula (II); R1 to R10 are independently selected from the group consisting of H, D, F, C1 to C20 alkyl, C6 to C20 aryl, C2 to C20 heteroaryl and a group having the Formula (II); and R1 and R2; or R2 and R3 or R3; and R4; or R5 and R6 may independently from each other form a fused ring or system of fused rings; a semiconducting layer comprising the same, an organic electronic device comprising the same as well as a display or a lighting device comprising the organic electronic device.


The present invention provides a magneto-resistance effect (hereinafter, referred to as MR) type composite head. The head includes a reproduction head including an MR element arranged between a first and a second magnetic shield; and a recording head arranged next to the reproduction head so as to use the second magnetic shield as a first magnetic pole film and having a second magnetic pole film opposing to the first magnetic pole via a magnetic gap; the MR element including: a center region including a ferromagnetic tunnel junction magneto-resistance effect film (hereinafter, referred to as a TMR film) having: a first ferromagnetic layer and a second ferromagnetic layer for generating a magneto-resistance effect using the first and the second magnetic shields as electrodes so that a current flows in a an almost vertical direction between the first and the second magnetic shields; and a tunnel barrier layer provided between the first and the second ferromagnetic layer; and an end region arranged to sandwich the center region from both sides for applying a bias magnetic field to the center region.

1. Field of the Invention
The present invention relates to a thin film magnetic head used in a magnetic disc apparatus and in particular, to a magnetic recording/reproduction head using the magneto-resistance effect obtained by ferromagnetic tunnel junction.
2. Description of Related Arts
As the magnetic recording apparatus reduces its size and increases capacity, a magneto-resistance effect type head (hereinafter, referred to as an MR head) having a large reproduction output has been used in practice. Such an MR head is already described in "A Magnetoresistivity Readout Transducer", IEEE Trans. On Magn., MAG7, 1971, page 150 [1].
In order to improve the conventional MR head, there has been developed a GMR head using a giant magneto-resistance effect (hereinafter, referred to as GMR) capable of realizing a further increased reproduction output. This GMR uses the magneto-resistance effect called spin-valve effect in which a resistance change corresponds to a cosine of a magnetization direction of two adjacent magnetization layers. This enables to obtain a large resistance change with a small operation magnetic field. The MR head using the spin-valve effect is described in "Design, Fabrication & Testing of Spin-Valve Read Heads for High Density Recording", IEEE Trans. On Magn., Vol. 30, No. 6, 1994, page 3801 [2]. However, the magneto-resistance change ratio obtained by the spin-valve effect that can be applied to an actual MR head is only several percents. When reducing a track width for increasing the recording density, it is necessary to obtain a magneto-resistance effect having a greater resistance change ratio.
The ferromagnetic tunnel junction has a configuration including two ferromagnetic layers sandwiching a tunnel barrier layer made from a thin insulator body having a thickness of several nanometers. In this configuration, when a constant current flows between the ferromagnetic layers while an external magnetic field is applied into the ferromagnetic layers, a magneto-resistance effect phenomenon can be seen. That is, a resistance value is changed according to a relative angle of magnetization directions of the two magnetic layers. This is called a ferromagnetic tunnel junction magneto-resistance effect (TMR). The resistance value is minimum when the magnetization directions are parallel to each other, and maximum when the magnetization directions are anti-parallel to each other. That is, the parallel and the anti-parallel states can be obtained depending on the intensity of the magnetic field. Accordingly, it is possible to detect a magnetic field according to a change of the resistance value.
Recently, there has been developed a TMR element exhibiting a magneto-resistance change ratio near to 20% by forming an Al oxide surface film on the tunnel barrier layer. This increases the possibility to apply the TMR element to a magnetic head and a magnetic memory. An example of such a large magneto-resistance change ratio is described in "Journal of Applied Physics", Vol. 79, 1996, page 4724 to 4729 [3].
That is, using a deposition mask, a first ferromagnetic layer of CoFe is formed on a glass substrate by way of vacuum deposition. Subsequently, the deposition mask is exchanged, and an Al layer is formed to have a thickness of 1.2 to 2.0 nm. This Al surface is subjected to an oxygen glow discharge so as to form a tunnel barrier layer of Al.sub.2 O.sub.3. After this, a second ferromagnetic layer of Co is formed on this tunnel barrier layer over the first ferromagnetic layer, thus completing a cross electrode type ferromagnetic tunnel element. This method enables to obtain a magneto-resistance change ratio as large as 18%.
Various TMR elements are disclosed in Japanese Patent Publication (Unexamined) No. A-5-63254 [4], Japanese Patent Publication (Unexamined) No. A-6-244477 [5], Japanese Patent Publication (Unexamined) No. A-8- 70148 [6], Japanese Patent Publication (Unexamined) No. A-8-70149 [7], Japanese Patent Publication (Unexamined) No. A-8-316548 [8], and "1997 Journal of Japan Applied Magnetism Society, vol. 21, pp. 493 to 496 [9]. These documents give a description on a method in which the Al layer formed is exposed to the atmosphere for epitaxy of Al.sub.2 O.sub.3.
When applying the TMR element to a device such as a magnetic head and memory, it is necessary to reduce affects from a thermal noise. In this case, it is necessary to have a sufficiently low resistance value in practical element dimensions. However, in the conventional tunnel barrier formation method, it is difficult to realize this. Moreover, in application to a magnetic head of high-density design, the signal output voltage becomes a key point. However, with the conventional technique, it is impossible to obtain a sufficiently high density without deteriorating the element characteristic. Furthermore, with the conventional technique, there has been a problem that characteristic fluctuations among elements in a wafer or between lots are too great to obtain a sufficient yield for practical use.
The aforementioned problems are considered to come from the conventional tunnel barrier layer formation method. In the method using the oxygen glow discharge, active oxygen in the radical state or ion is used for oxidation of the conductive layer and accordingly, it is difficult to control the thickness of the oxide film, i.e., element resistance. Moreover, there is a problem that the tunnel barrier layer is contaminated with activated impurities gas generated simultaneously. On the other hand, the method using natural oxidation in the atmosphere also have various problems. For example, a pin hole may be generated in the tunnel barrier layer by dusts in the atmosphere, and the tunnel barrier layer is contaminated wuth humidity, carbon oxide, or nitrogen oxide, similarly in the oxygen glow discharge method.
Japanese Patent Application No. 9-209292 [10] discloses a TMR element production method having a practically sufficient resistance value and signal output voltage characteristic with an improved yield. This method includes: a step for successively forming a first ferromagnetic layer, a tunnel barrier layer, and a second ferromagnetic layer; a step for forming a conductive layer of a metal or semiconductor; and a step for introducing oxygen into vacuum for natural oxidation of a surface of this conductive layer so as to form a tunnel barrier layer.
Furthermore, Document [10] discloses a TMR element production method for successively forming a first ferromagnetic layer, a tunnel barrier layer, and a second ferromagnetic layer while maintaining a vacuum. After the first ferromagnetic layer is formed, an oxygen is introduced to oxidize a surface of the first ferromagnetic layer while maintaining the vacuum, and after formation of a conductive layer of metal or semiconductor, an oxygen is introduced into the vacuum for natural oxidization of a surface of this conductive layer to form the tunnel barrier layer.
With reference to FIG. 11, explanation will be given on the TMR film production method disclosed in Document [10]. Firstly, an undercoat layer 10, a first ferromagnetic layer 11, and a conductive layer 12 are successively formed in a vacuum (FIG. 11A). A pure oxygen is introduced without breaking the vacuum, for natural oxidation of a surface of the conductive layer 12 to form a tunnel barrier layer 13 (FIG. 11B). It should be noted that FIG. 11B shows that even after the oxidation of the conductive layer, there is left an un-oxidized portion on the boundary with the first ferromagnetic layer 11. It is also possible to completely oxidize the conductive layer by setting the oxidation conditions as such. After exhausting the oxygen, the second ferromagnetic layer 14 is formed to complete the basic configuration of the TMR film (FIG. 11C). Next, an antiferromagnetic layer 15 is formed to complete the basic configuration of the TMR element (FIG. 11D).
In the a forementioned method, it is possible to obtain an epitaxy of an oxide layer while maintaining a thermal equilibrium in a clean atmosphere not affected by a gas from impurities, thus enabling to control to form a high-quality tunnel barrier layer. Moreover, by controlling the oxygen pressure and the substrate temperature, it is possible to obtain an element of a low resistance and a high current density required for application to a device such as a magnetic head. Furthermore, it is possible to obtain a uniform element characteristic within a wafer and stable repeatability between lots. When the ferromagnetic layer contains Fe, Co, Ni or an alloy containing them and if the conductive layer is made from an Al material having a surface free energy smaller than that of the ferromagnetic layer, it is possible to obtain a preferable coating with respect to the first ferromagnetic layer serving as an undercoat layer. As a result, in an element completed, it is possible to obtain a preferable characteristic having no electrical short-circuit between the ferromagnetic layers due to a pin hole. Moreover, the free energy required for oxidation of Al per one oxygen atom is greater than Fe, Co, Ni, and accordingly, the Al.sub.2 O.sub.3 serving as the tunnel barrier is thermally stabilized on the junction boundary. When Mg or a metal of lanthanoid is selected for the conductive layer, it is possible, from the same reason, to obtain a preferable coating characteristic with respect to the first ferromagnetic layer serving as the undercoat as well as to obtain a thermally stable tunnel barrier.
Referring to FIG. 12, explanation will be given on the conventional TMR element production method disclosed in Document [10]. After formation of the first ferromagnetic layer 11 (FIG. 12A), oxygen is introduced into the vacuum for forming an oxide layer 21 on the surface of the first ferromagnetic layer 11 (FIG. 12B). When forming the conductive layer 12 in the next step, oxygen is diffused from the first ferromagnetic layer 11 into the conductive layer 12 (FIG. 12C), and an oxide layer 23 is also formed at the side of the conductive layer 12. In this method, the oxide layer 24 of the conductive layer 12 is formed on both boundaries in contact with the ferromagnetic layers, enabling to exhibit an excellent thermal stability. After exhausting the oxygen, the second ferromagnetic layer 14 is formed (FIG. 12E) and the antiferromagnetic layer 15 is formed to complete the basic configuration of the TMR element (FIG. 12F). In order to form a stable oxide layer at the side of the conductive layer 12, the conductive layer 12 should have a greater free energy for oxidization per one oxygen atom than an element constituting the ferromagnetic layer 11. When the ferromagnetic layer contains Fe, Co, Ni, or an alloy containing them, it is effective that the conductive layer 12 uses Al, Mg, or a metal belonging to lanthanoid.
FIG. 10 shows a configuration example of an air bearing surface (ABS) of a magnetic head using the conventional TMR element which is described in "Nikkei Electronics", No. 686, Apr. 7, 1997 [11]. The TMR element including a TMR film having electrodes formed at its ends is contained through an insulation film in a magnetic shield.
In the apparatus having the configuration shown in FIG. 10, the TMR element 119 including upper and lower electrode films 118 is present between the magnetic shields which determine the resolution of a reproduction head. Accordingly, it is possible to reduce the distance between the shields while maintaining a sufficient insulation between the TMR element and the upper and lower magnetic shields. However, it is difficult to prepare a thin insulation film and it is impossible to reduce the distance between the magnetic shields smaller than the thickness of the TMR element. Furthermore, for reducing the track width, the electrodes (right and left) need be patterned on the top and bottom of the TMR film so as to make the distance between the electrodes in the order of submicrons, which is quite difficult in the process using a photo-resist. Furthermore, to cope with a noise increase caused by reduction in size of the TMR element, it is necessary to apply a certain bias magnetic field.

Magneto-resistance effect type composite head and production method thereof


An optical pick-up device includes a laser diode, an objective lens for focusing a light beam emitted from the laser diode on an optical disc, an optical detector for receiving a reflected beam from the optical disc, a beam splitter for causing the light beam emitted from the laser diode and a reflected beam to pass therethrough or reflect, a front monitor for receiving the light beam emitted from the laser diode, and a front monitor light-guiding plate for guiding a part of the light beam emitted from the laser diode to the front monitor. The front monitor light-guiding plate is arranged between the laser diode and the objective lens and has a region having a predetermined shape for causing the part of the light incident thereon to change a traveling direction thereof by refraction and then reach the front monitor.

The present invention relates to a technical field concerning optical information processing.
In recent years, optical disc drives capable of recording information on and reproducing the information from CD-R/RW (Compact Disc-Recordable/Rewritable), DVD-R/RW (Digital Versatile Disc-Recordable/Rewritable), or the like have become widely spread. In the optical disc drive, in order to record the information, a light beam is irradiated onto an optical disc by an optical pick-up device contained in the optical disc drive. Then, in order to read the information, the light beam reflected from the optical disc is detected by the optical pick-up device.
In order to perform stable recording and reproduction processing during the recording and reproduction of the information by the optical pick-up device, it is necessary to accurately control the light amount of the light beam irradiated onto the optical disc. For this reason, the optical pick-up device has a unit for detecting the light amount of the light beam emitted from a laser diode. By feedbacking the detected light amount to the laser diode, the light amount of the light beam irradiated onto the optical disc is accurately controlled.
In order to detect the light amount of the light beam emitted from the laser diode, it is a common practice to provide a light reception element that receives a part of the light beam emitted forward from the laser diode. Herein, the light reception element that receives the light beam emitted forward from the chip of the laser diode will be referred to as a "front monitor".
Various units for guiding the light beam from the laser diode to the front monitor are known.
Among these, an optical pick-up device disclosed in FIG. 1 of JP-A-2001-184709, for example, has a configuration in which a light beam is emitted from a laser diode, and a part of the emitted light beam outside the effective diameter of an objective lens is detected by a front monitor.
In this configuration, the light beam outside the effective diameter of the objective lens is monitored. Thus, it is possible to avoid a problem that a light amount detected by the front monitor is greatly varied. This problem occurs due to interference between the light beam emitted from the laser diode and a light beam reflected from the optical disc on the detection surface of the front monitor.
An optical pick-up device disclosed in FIG. 1 of JP-A-2003-77170, for example, has a configuration in which a diffraction element is arranged between an objective lens and a laser diode, so that the light amount of the light beam outside the effective diameter of an objective lens is led more to the front monitor.

Optical information processing apparatus, optical pick-up device and optical recording disc system