1. Field of the Invention
The present invention relates to a vacuum vapor deposition system, and more particularly, to a vacuum vapor deposition system for producing an organic electroluminescence (EL) element.
2. Description of the Related Art
An organic EL element is generally an electronic element in which an organic thin film layer formed of a hole transport layer, an emission layer, an electron transport layer, and the like are provided between an electrode made of a transparent conductive film (for example, indium tin oxide) and an electrode made of metal (for example, Al). When excitons generated by the recombination of holes injected from the anode side and electrons injected from the cathode side in the emission layer respectively through the hole transport layer and the electron transport layer return to the ground state, the organic light-emitting element emits light.
Meanwhile, as one of the methods of producing an organic EL element, a vacuum vapor deposition method is known. For example, a constituent material (vapor deposition material) for an organic EL element is placed in a crucible and heated to a temperature equal to or more than a vaporization temperature of the vapor deposition material in a vacuum system to generate vapor of the vapor deposition material, and the vapor deposition material is deposited on a substrate serving as a base of the organic EL element to form an organic thin film layer.
It is known that, in the step of producing an organic EL element using the vacuum vapor deposition method, a vapor deposition rate is monitored by a film thickness sensor using a crystal oscillator to control the evaporation amount (generation amount of vapor) of the vapor deposition material. This is because, if the vapor deposition rate is not monitored, the adhesion amount of the vapor deposition material to the substrate during film formation (film thickness of a thin film to be formed on the substrate) is unclear, which makes it difficult to adjust the film thickness on the substrate to a target value.
However, as the adhesion amount of the vapor deposition material to the crystal oscillator increases, a difference is caused between the vapor deposition rate value indicated by the film thickness sensor and the adhesion amount of the vapor deposition material on the substrate. This is attributed to a change in frequency of the crystal oscillator along with an increase in the vapor deposition material adhering to the crystal oscillator. This phenomenon becomes a problem particularly in the case where the allowable range of an error of the film thickness of the thin film to be formed on the substrate with respect to the target value is small. As the film thickness per layer of the organic EL element is generally about tens of nm to 100 nm, the allowable range of an error of the film thickness with respect to the target value is on the order of several nanometers. Then, the difference between the vapor deposition rate value indicated and the adhesion amount of the vapor deposition material on the substrate (film thickness of the thin film formed on the substrate) may cause a decrease in production yield.
As means for solving the above-mentioned problem, there is known a vacuum vapor deposition system provided with a film thickness sensor for controlling a film thickness and a film thickness sensor for calibrating a film thickness, disclosed in Japanese Patent Application Laid-Open No. 2008-122200. In the vacuum vapor deposition system of Japanese Patent Application Laid-Open No. 2008-122200, a measurement error of the film thickness sensor for controlling a film thickness is calibrated by the film thickness sensor for calibrating a film thickness so as to keep the vapor deposition rate constant. Thus, the adhesion amount of the vapor deposition material to the substrate can fall within the target value stably.
Meanwhile, when film formation is performed using a film thickness sensor for calibration and a film thickness sensor for monitoring, there is a demand for enhancing the monitoring accuracy of any one of the film thickness sensors. In general, the distribution of the vapor deposition material evaporating from an opening of the vapor depositing source becomes an oval sphere (according to a COS rule). Considering this, when the calibration accuracy of a film thickness sensor for calibrating a film thickness to be used intermittently is to be enhanced, the arrangement of the sensors disclosed in Japanese Patent Application Laid-Open No. 2008-122200 may cause a decrease in the adhesion amount of the vapor deposition material entering the film thickness sensor for calibrating a film thickness, and hence is insufficient. The same holds true for enhancing the monitoring accuracy of the film thickness sensor for monitoring.
The present invention has been made to solve the above-mentioned problem. An object of the present invention is to provide a vacuum vapor deposition system, which enables a vapor deposition rate to be measured accurately and a film thickness to be controlled with higher accuracy.
A vacuum vapor deposition system of the present invention includes: a vacuum chamber; a substrate holding mechanism which holds a substrate; a vapor depositing source which releases vapor of a vapor deposition material to be formed into a film on the substrate through an opening; a film thickness sensor for monitoring which measures a vapor deposition rate of the vapor deposition material when the vapor deposition material is formed into a film on the substrate; a control system including a film thickness controller which connected to the film thickness sensor for monitoring and calculates the difference between a target vapor deposition rate and the vapor deposition rate measured by the film thickness sensor for monitoring; and a temperature controller which controls a temperature of the vapor depositing source for reducing the difference between a target vapor deposition rate and the vapor deposition rate measured by the film thickness sensor for monitoring obtained by the film thickness sensor for monitoring; and a film thickness sensor for calibration which measures the vapor deposition rate of the vapor deposition material and outputs a calibration value for calibrating the vapor deposition rate obtained by the film thickness sensor for monitoring to the control system, in which a distance from one film thickness sensor whose measurement accuracy is to be enhanced, out of the film thickness sensor for monitoring and the film thickness sensor for calibration, to a center of the opening of the vapor depositing source, is smaller than a distance from another film thickness sensor to the center of the opening of the vapor depositing source.
According to the present invention, it is possible to provide the vacuum vapor deposition system, which enables a vapor deposition rate to be measured accurately and a film thickness to be controlled with higher accuracy.
The vacuum vapor deposition system of the present invention can manage the vapor deposition rate of the vapor deposition material formed into a film on the substrate with high accuracy in accordance with the measurement accuracy of the film thickness sensor closer to the opening of the vapor deposition source and enhance the production yield of an organic EL element. For example, when the film thickness sensor for calibration is placed at a position with high measurement accuracy, and the vapor depositing source is controlled based on the measured data obtained by the film thickness sensor for monitoring to be calibrated intermittently, the vapor deposition rate of the vapor deposition material formed into a film on the substrate can be calibrated with high accuracy, and the production yield of an organic EL element can be enhanced. On the other hand, when the film thickness sensor for monitoring is placed at a position with high measurement accuracy, and the temperature of the vapor deposition source is controlled based on the measured data obtained by the film thickness sensor for monitoring, the vapor deposition rate during vapor deposition of the vapor deposition material formed into a film on the substrate is stabilized through the enhancement of monitoring accuracy, and a film can be formed with good accuracy with respect to a target film thickness.
Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the attached drawings.
A vacuum vapor deposition system of the present invention includes: a vacuum chamber; a substrate holding mechanism; a vapor depositing source; a film thickness sensor for monitoring; a control system; and a film thickness sensor for calibration.
Here, the substrate holding mechanism is a member for holding a substrate. The vapor depositing source is a member for generating vapor of a vapor deposition material to be formed into a film on the substrate. The film thickness sensor for monitoring is a member for measuring the vapor deposition rate of the vapor deposition material of interest and controlling the temperature of the vapor depositing source when the vapor deposition material is formed into a film on the substrate. The control system includes a temperature controller which controls a temperature of the vapor depositing source based on measured data obtained by the film thickness sensor for monitoring and a film thickness controller which is connected to the film thickness sensor for monitoring and calculates the vapor deposition rate. The film thickness sensor for calibration is a member for measuring the vapor deposition rate of the vapor deposition material and outputting a calibration value for calibrating the measured data obtained by the film thickness sensor for monitoring to the control system.
In the vacuum vapor deposition system of the present invention, a distance from one film thickness sensor whose measurement accuracy is to be enhanced, out of the film thickness sensor for monitoring and the film thickness sensor for calibration, to the center of the opening of the vapor depositing source is smaller than a distance from another film thickness sensor to the center of the opening of the vapor depositing source. That is, a distance from the center of the opening of the vapor depositing source to the film thickness sensor for monitoring and a distance from the center of the opening of the vapor depositing source to the film thickness sensor for calibration satisfy the following relationship (a) or (b).
(a) Relationship in which the distance from the center of the opening of the vapor depositing source to the film thickness sensor for monitoring is larger than the distance from the center of the opening of the vapor depositing source to the film thickness sensor for calibration (first aspect).
(b) Relationship in which the distance from the center of the opening of the vapor depositing source to the film thickness sensor for monitoring is smaller than the distance from the center of the opening of the vapor depositing source to the film thickness sensor for calibration (second aspect).
The distance used herein refers to a linear distance between two members. Specifically, in the case where the (center of the opening of) the vapor depositing source and each of the sensors (film thickness sensor for monitoring and film thickness sensor for calibration) are placed respectively at (x1, y1, z1) and (x2, y2, z2) in particular space coordinates (xyz space coordinates), the distance is represented by d in Expression (i) below.
d={(x2−x1)2+(y2−y1)2+(z2−z1)2}1/2 (i)
It should be noted that the coordinates (x2, y2, z2) on the sensor side specifically refer to coordinates of a center of the film formation surface of the sensor.
Hereinafter, a first embodiment for enhancing the calibration accuracy of a film thickness sensor for calibration 10 is described with reference to the drawings.
In the vacuum vapor deposition system 1 of
The vapor depositing source 30 includes a crucible for accommodating a vapor deposition material 31, a heater for heating the crucible, a lid, an opening 32 provided in the lid, and a reflector. The vapor deposition material 31 is heated in the crucible, and vapor is released through the opening 32 provided in the lid. The vapor of the vapor deposition material generated from the vapor depositing source 30 adheres to a film formation surface of the substrate 40 for forming a film through the mask 41. Thus, a thin film is formed in a predetermined area of the substrate 40.
The speed (vapor deposition rate) at which the vapor of the vapor deposition material generated from the vapor depositing source 30 is deposited on the substrate 40 is measured by the film thickness sensor for monitoring 20 provided with a crystal oscillator. The film thickness sensor for monitoring 20 outputs the measured data to the film thickness controller 61. The film thickness controller 61 controls the heater power of the vapor depositing source 30 using the temperature controller 62, based on the output measured data of the film thickness sensor for monitoring 20. Meanwhile, in order to output a calibration value for calibrating the measured data of the film thickness sensor for monitoring 20, the film thickness sensor for calibration 10 provided with the crystal oscillator is provided. Here, the two sensors (film thickness sensor for calibration 10 and film thickness sensor for monitoring 20) are placed at positions where the sensors do not block the vapor of the vapor deposition material generated from the vapor depositing source 30 and directed to the substrate 40.
Here, a distance from a center of the opening 32 to a center of a film formation surface of the film thickness sensor for calibration 10 is defined as L1. On the other hand, a distance from the center of the opening 32 to a center of a film formation surface of the film thickness sensor for monitoring 20 is defined as L2. In the vacuum vapor deposition system 1 of
Meanwhile, an angle formed by a perpendicular line from the center of the opening 32 to the film formation surface of the substrate 40 and a straight line connecting the center of the opening 32 to the center of the film formation surface of the film thickness sensor for calibration 10 is defined as θ1. On the other hand, an angle formed by a perpendicular line from the center of the opening 32 to the film formation surface of the substrate 40 and a straight line connecting the center of the opening 32 to the center of the film formation surface of the film thickness sensor for monitoring 20 is defined as θ2. In the vacuum vapor depositing system 1 of
In the vacuum vapor deposition system 1 of
In the vacuum vapor deposition system 1 of
A vacuum evacuation system (not shown) for evacuating the vacuum chamber 50 of air is desirably a vacuum evacuation system using a vacuum pump having an ability to evacuate the vacuum chamber of air to a high vacuum area rapidly. Here, in the case of using the vacuum vapor deposition system 1 of
The opening area, opening shape, material, and the like of the opening 32 provided in the lid of the vapor depositing source 30 may vary individually, and the opening shape may be any shape such as a circle shape, a rectangle shape, an oval shape. Due to the variation in the opening area and opening shape, the film thickness controllability on the substrate 40 may be enhanced further. Further, for the same reason, the shape, material, and the like of the crucible of the vapor depositing source 30 may vary individually.
An example of using the vacuum vapor deposition system 1 of
First, 10.0 g of tris (8-hydroxyquinolinato) aluminum (hereinafter, referred to as Alq3) as an organic EL material were loaded as the vapor deposition material 31 into a crucible of the vapor depositing source 30. Alq3 loaded into the crucible of the vapor depositing source 30 is evaporated from the vapor depositing source 30 via at least one opening 32 provided in the vapor depositing source 30. Here, the vapor depositing source 30 is placed opposed to the film formation surface of the substrate 40, and the substrate 40 is set in contact with the mask 41. Further, the distance from the center of the opening 32 of the vapor depositing source 30 to the film formation surface of the substrate 40 was set to 300 mm.
The film thickness sensor for calibration 10 and the film thickness sensor for monitoring 20 were placed at positions where the sensors did not block the vapor directed to the substrate 40 and generated from the vapor depositing source 30. Specifically, in the film thickness sensor for calibration 10, L1 and θ1 were set to 200 mm and 30°. On the other hand, in the film thickness sensor for monitoring 20, L2 and θ2 were set to 300 mm and 45°. It should be noted that a sensor shutter (not shown) was provided in the vicinity of the film thickness sensor for calibration 10 so as to block the vapor of the vapor deposition material appropriately.
Meanwhile, the vapor amount of the vapor deposition material 31 generated from the vapor depositing source 30 is larger at a position having a shorter distance from the perpendicular line from the center of the opening 32 to the film formation surface of the substrate 40, and the vapor amount is larger at a position having a shorter distance from the center of the opening 32. Thus, when the film thickness sensor for calibration 10 is placed at a position having a larger vapor amount than the film thickness sensor for monitoring 20 according to the above-mentioned conditions, the entry amount of the vapor deposition material 31 to the film thickness sensor for calibration 10 increases. When the entry amount of the vapor deposition material 31 to the film thickness sensor for calibration 10 is increased in this manner, the difference from the thickness of a thin film to be formed on the substrate decreases, which can enhance the calibration accuracy of the film thickness sensor for calibration 10.
As the substrate 40, a glass substrate with a dimension of 100 mm×100 mm×0.7 mm (thickness) was set in a substrate stock device (not shown).
Next, the substrate stock device was evacuated to 1.0×10−4 Pa or less by a vacuum evacuation system (not shown). The vacuum chamber 50 was also evacuated to 1.0×10−4 Pa or less by the vacuum evaluation system (not shown), and after the evacuation, the vapor deposition material 31 was heated to 200° C. by a heater provided in the vapor depositing source 30. The heater power was controlled by the temperature controller 62 based on the temperature of a thermocouple (not shown) provided in the vapor depositing source 30.
Next, a calibration coefficient for correcting the difference between the monitored value displayed by each of the film thickness monitors and the actually measured value of the thickness of a film to be formed on the substrate is determined in advance before an actual film formation step. In the film thickness sensor for monitoring 20, the vapor deposition material 31 was heated to a temperature at which the vapor deposition rate reached 1.0 nm/sec. as a value indicated by the film thickness controller 61. Regarding the vapor deposition rate, the film thickness controller 61 receives a signal from the film thickness sensor for monitoring 20, converts the signal to a vapor deposition rate value, and outputs the vapor deposition rate value to a display portion of the film thickness controller 61. Further, the film thickness controller 61 calculates the difference between a target vapor deposition rate and the vapor deposition rate converted from the amount of the vapor deposition material actually adhering to the film thickness sensor for monitoring. Then, the film thickness controller 61 sends a signal for reducing the difference to the temperature controller 62 to control the heater power to the vapor depositing source 30. When the vapor deposition rate reached 1.0 nm/sec. in the film thickness sensor for monitoring 20, one substrate 40 was delivered from the substrate stock device (not shown) to the vacuum chamber 50 through a gate valve (not shown) using a substrate conveying mechanism (not shown), and film formation was performed. The film formation was performed until the film thickness of a thin film to be deposited on the film thickness sensor for monitoring 20 reached 100 nm, and the substrate 40 on which a film has been formed was taken out from the vacuum chamber 50 immediately. Here, the film thickness of the film formed on the substrate 40 was measured by an ellipsometer and compared with the film thickness value of the thin film deposited on the film thickness sensor for monitoring 20, and a new calibration coefficient b2 of the film thickness sensor for monitoring 20 was calculated by Expression (1) shown below.
b
2
=b
1×(t1/t2) (1)
In Expression (1), t1 represents a film thickness of the thin film on the substrate 40, t2 represents a target film thickness (here, 100 nm), b1 represents a calibration coefficient of the film thickness sensor for monitoring 20 previously set in the system, and b2 represents a new calibration coefficient of the film thickness sensor for monitoring 20.
By using the above-mentioned mathematical expression shown in Expression (1), the film thickness of the thin film on the substrate 40 can be matched with the film thickness on the film thickness sensor for monitoring 20.
On the other hand, the film thickness on the substrate 40 can also be matched with the film thickness on the film thickness sensor for calibration 10 in the same way as in the film thickness sensor for monitoring 20. Specifically, the sensor shutter (not shown) of the film thickness sensor for calibration 10 is opened during the film formation step of the substrate 40, and the film thickness is matched by the above-mentioned mathematical expression (Expression (1)) in the same way as in the film thickness sensor for monitoring 20. Here, in the case of the film thickness sensor for calibration 10, b1 is replaced by b1′ (calibration coefficient of the film thickness sensor for calibration 10 previously set in the device), and b2 is replaced by b2′ (new calibration coefficient of the film thickness sensor for calibration 10). It should be noted that, after the completion of film formation, the opened sensor shutter (not shown) is closed.
The resultant new calibration coefficient of the film thickness sensor for monitoring 20 was replaced for the calibration coefficient of the film thickness sensor for monitoring 20 during film formation via the film thickness controller 61, and the vapor deposition material 31 was heated again to a temperature at which the vapor deposition rate reached 1.0 nm/sec. Then, the new calibration coefficient of the film thickness sensor for calibration 10 obtained at this time is also replaced for the calibration coefficient of the film thickness sensor for calibration 10 previously set in the system via the film thickness controller 61.
The steps of calculating the calibration coefficients described above were repeated until the difference between the film thickness of a thin film to be formed on the substrate 40 under the same film formation conditions and each of the thicknesses of films adhering to the film thickness sensor for calibration 10 and the film thickness sensor for monitoring 20 fell within ±2.0%.
Next, the step of calibrating the vapor deposition rate of the film thickness sensor for monitoring 20 using the film thickness sensor for calibration 10 is described. The vapor deposition rate was kept at be 1.0 nm/sec. using the film thickness sensor for monitoring 20, and films with a film thickness of 100 nm were formed successively on multiple substrates 40. During that time, every time the frequency of the crystal oscillator of the film thickness sensor for monitoring 20 decreased by 0.015 MHz, a film was formed by delivering a monitoring substrate. Before forming a film on the monitoring substrate 40, a sensor shutter (not shown) provided in the vicinity of the film thickness sensor for calibration 10 was opened, and a calibration value based on the vapor deposition rate measured by the film thickness sensor for calibration 10 was determined. Then, the vapor deposition rate of the film thickness sensor for monitoring 20 was calibrated using the calibration value. This step was repeated until the number of the monitoring substrates reached 10.
Hereinafter, a specific example of the step of calibrating the vapor deposition rate of the film thickness sensor for monitoring 20 (calibration step) is described with reference to the drawings.
First, thin films (vapor deposition films) of Alq3 were deposited respectively on the film thickness sensor for monitoring 20 and the film thickness sensor for calibration 10. At this time, the film thickness of the thin film adhering to each sensor was converted using the film thickness controller 61. Next, the film thickness of the thin film adhering to the film thickness sensor for monitoring 20 was compared with the film thickness of the thin film adhering to the film thickness sensor for calibration 10, and a new calibration coefficient a2 of the film thickness sensor for monitoring 20 was calculated by Expression (2) shown below.
a
2
=a
1×(T1/T2) (2)
In Expression (2), a1 represents a calibration coefficient of the film thickness sensor for monitoring 20 used during previous film formation, a2 represents a new calibration coefficient of the film thickness sensor for monitoring 20, T1 represents a film thickness of the thin film on the film thickness sensor for calibration 10, and T2 represents a film thickness of the thin film on the film thickness sensor for monitoring 20.
Here, assuming that T1 and T2 are thicknesses of films adhering within the same period of time, the film thickness of the thin film on the film thickness sensor for monitoring 20 can be matched with the film thickness of the thin film on the film thickness sensor for calibration 10 based on Expression (2) above. By performing the calibration step described above, an error of the vapor deposition rate involved in frequency attenuation of the film thickness sensor for monitoring 20 can be calibrated.
It should be noted that the sensor shutter (not shown) provided in the vicinity of the film thickness sensor for calibration 10 is closed after the film thickness (T1) of the thin film on the film thickness sensor for calibration 10 is converted. Then, the new calibration coefficient a2 of the film thickness sensor for monitoring 20 is replaced for the calibration coefficient a1 of the film thickness sensor for monitoring 20 during film formation of the film thickness controller 60, and the calibration coefficient a2 is used as the new calibration coefficient a1 of the film thickness sensor for monitoring 20.
Next, after the new calibration coefficient of the film thickness sensor for monitoring 20 was input to the film thickness controller 61, the vapor depositing source 30 was controlled by the temperature controller 62 so that the vapor deposition rate reached 1.0 nm/sec. as a target rate. Then, after the target rate reached 1.0 nm/sec. in the film thickness sensor for monitoring 20, the film formation on the substrate 40 was performed.
Film formation is performed by the above-mentioned method and the film thicknesses in the vicinity of the centers of the resultant ten monitoring substrates were measured by an ellipsometer. As a result, the measured film thickness fell within a range of 100 nm±2.0% with respect to the target film thickness of 100 nm. This shows that the phenomenon in which the frequency of the crystal oscillator is attenuated to cause a deviation from the target film thickness along with the adhesion of the vapor deposition material 31 to the film thickness sensor for monitoring 20 was overcome by the film thickness sensor for calibration 10 placed at a position with high calibration accuracy. It was found from this result that the Alq3 film was able to be formed with good accuracy with respect to the target film thickness over a long period of time.
As described above, by forming a thin film constructing an organic EL element using the vacuum vapor deposition system of this example in producing an organic EL element, an organic EL element with the film thickness of each layer controlled can be produced.
In this example, the construction illustrated in each of
In order to verify the effects of Example 1, a comparative test in the case of forming a film by a conventional vacuum vapor deposition system disclosed in Japanese Patent Application Laid-Open No. 2008-122200 was conducted. In this comparative example, considering the figure of Japanese Patent Application Laid-Open No. 2008-122200, a film thickness sensor for calibration and a film thickness sensor for monitoring were placed respectively so as to satisfy relationships of L1=L2 and θ1>θ2. In this construction, vapor of Alq3 was generated from a vapor depositing source toward an object on which a film is formed in a vacuum chamber, and the vapor depositing source was heated to a temperature at which the vapor deposition rate reached 1.0 nm/sec. in the film thickness sensor for monitoring. The film formation on the monitoring substrate was performed by the same method as that of the present invention, and the film thickness in the vicinity of the center of ten substrate was measured by an ellipsometer. As a result, the measured film thickness did not fall within a range of ±2.0% in some cases with respect to a target film thickness of 100 nm. This is probably because the relative positions of the vapor depositing source, the film thickness sensor for calibration, and the film thickness sensor for monitoring were unclear, and hence it was difficult to decrease a film thickness distribution range. It was found from these results that the vacuum vapor deposition system of the present invention was more excellent than the conventional vacuum vapor deposition system in forming a vapor deposition material into a film with a predetermined film thickness on a substrate.
In the vacuum vapor deposition system 2 of
In the vacuum vapor deposition system 3 of
An example of using the vacuum vapor deposition system 3 of
A method of using the vacuum vapor deposition system 3 of
The film thickness in the vicinity of the center of the monitoring substrate was measured by an ellipsometer, and as a result, the measured film thickness fell within a range of 100 nm±2.0% with respect to the target film thickness of 100 nm. Compared with Example 1, the vapor deposition rate change in the film thickness sensor for monitoring 20 during vapor deposition on the substrate 40 was reduced to 1.0 nm/sec±0.1%.
In this example, as the film thickness sensor for monitoring 20 was placed at a position where the entry amount of the vapor deposition material 31 increased, the difference in film thickness between the thin film to be formed on the film thickness sensor for monitoring 20 and the thin film to be formed on the substrate became small. This was able to enhance the monitoring accuracy of the film thickness sensor for monitoring 20. Further, it was found that, due to the enhancement of monitoring accuracy, the vapor deposition rate during vapor deposition on the substrate 40 was stabilized and film formation was able to be performed with good accuracy with respect to the target film thickness of Alq3.
In the vacuum vapor deposition system 4 of
Although, for example, the construction illustrated in each of
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
This application claims the benefit of Japanese Patent Application No. 2010-247825, filed Nov. 4, 2010, and No. 2011-211798, filed Sep. 28, 2011 which are hereby incorporated by reference herein in their entirety.
Number | Date | Country | Kind |
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2010-247825 | Nov 2010 | JP | national |
2011-211798 | Sep 2011 | JP | national |