Method and system for preparing perovskite CsPbBr3 nanoparticles in nitrogen atmosphere

Abstract

A method and system for preparing perovskite caesium lead bromide, CsPbBr3, nanoparticles from a caesium oleate stock solution under a nitrogen atmosphere. The method may include the following steps: into a three-necked flask, first add octadecene (ODE), followed by sequentially adding cesium carbonate, Cs2CO3, powder and oleic acid (OA); connecting a nitrogen cylinder to one end of the three-necked flask and introducing nitrogen for 0.5-1 hour to expel the air therein. Under a nitrogen atmosphere, the solution in the flask is heated to 120°C and this temperature maintained for 1-2 hours. In an additional three-necked flask, lead bromide, PbBr2, powder may be dissolved in octadecene in a nitrogen atmosphere at 120°C and then injected with oleic acid and oleylamine solution. After heating the PbBr2 solution to 160 °C, the previously made hot caesium oleate stock solution may be injected and the resulting solution rapidly cooled to form perovskite CsPbBr nanoparticles. Purification may be performed using centrifugation.

Description

TECHNICAL FIELD The present disclosure relates to the field of CsPbBra perovskites, and more particularly, to a method and system for preparing CsPbBrs nanoparticles in a nitrogen atmosphere. BACKGROUND Perovskite CsPbBrs has attracted widespread attention due to its high luminescent efficiency, which can reach over 95%. Perovskite CsPbBra possesses enormous application potential in optoelectronic semiconductor fields such as solar cells, lightemitting diodes, and photodetectors. Owing to the susceptibility of this type of perovskite to the loss of halogen elements, its structure tends to change under conditions such as humidity, light exposure, and heat, consequently leading to a reduction in its luminescent performance and affecting its application in optoelectronic devices. Therefore, this type of perovskites is generally prepared and stored in a glove box. Traditional methods for preparing perovskite CsPbBh nanoparticles typically involve mixing CsBr and PbBr2 in a solvent, followed by processing and washing steps to obtain the nanoparticles. There are technical problems in the traditional preparation methods: 1. Difficulty in Control of Reaction Conditions: Traditional preparation methods often have difficulty in controlling reaction conditions, such as reaction temperature and reaction time, which may result in unstable performance of the final product. 2. Complexity of the Preparation Process: In traditional preparation methods, multiple reaction steps and numerous washing steps are usually required, thereby not only increasing the complexity of the preparation process but also raising the production cost. 3. Low Quality of Nanoparticles: In traditional preparation methods, the quality of the nanoparticles is often compromised by unreacted chemical substances and other impurities, which may deteriorate the optoelectronic performance of the nanoparticles. 4. Low Production Efficiency: Due to the difficulty in controlling reaction conditions and the complexity of the preparation process, traditional preparation methods are often inefficient and are not conducive to large-scale production. The disclosure provides a new method for preparing perovskite CsPbBrs nanoparticles, which overcomes these problems associated with traditional methods. It proposes a more streamlined and efficient preparation scheme and, by precisely controlling the reaction conditions, enables the production of higher-quality nanoparticles. SUMMARY Based on the problems existing in the aforementioned background technology, the present disclosure proposes a method for preparing perovskite CsPbBr3 nanoparticles in a nitrogen atmosphere within a fume hood. The present disclosure is achieved by a method for preparing perovskite CsPbBr3 nanoparticles in a nitrogen atmosphere within a fume hood, wherein the method comprises preparing a cesium oleate stock solution and preparing perovskite CsPbBr3 nanoparticles. Further, the method comprises the following steps: into a three-necked flask with a volume of 100 mL, first adding an appropriate amount of octadecene (ODE), followed by sequentially adding CS2CO3 powder and oleic acid (OA); connecting a nitrogen cylinder to one end of the three-necked flask, and introducing nitrogen into the threenecked flask for 0.5-1 hour to expel the air therein; heating a solution in the threenecked flask to 120°C in a nitrogen atmosphere, and maintaining that temperature for 1-2 hours. Further, while maintaining the nitrogen atmosphere at 120°C, the solution is further heated to 150°C and kept at that temperature until all the CS2CO3 powder and oleic acid have fully reacted to form a cesium oleate solution. Further, into an additional three-necked flask, octadecene solution is first added, followed by gradual addition of an appropriate amount of PbBr2 powder; similarly, a nitrogen cylinder is connected to one end of the additional three-necked flask and nitrogen is introduced into the additional three-necked flask for 0.5-1 hour to expel the air therein. Further, a solution in the additional three-necked flask is heated to 120°C in a nitrogen atmosphere, and maintained at that temperature for 1-2 hours, after which an oleic acid (OA) solution and an oleylamine (OLA) solution is injected from another end. Further, after injecting the oleic acid (OA) solution and the oleylamine (OLA) solution, the PbBr2 in the mixture is allow to completely dissolve, thereafter, the temperature of the solution is raised to 160°C, followed by injection of hot cesium oleate solution, 5-10 seconds post-injecting, the mixed solution is rapidly cooled by an ice-water bath. Further, aftercooling the mixed solution, it is subjected to centrifugation at a speed of 3000 RPM for 30 minutes, the supernatant is removed, and toluene is added to the precipitate, followed by further centrifugation at 3000 RPM for 20 minutes, again removing the supernatant, and placing the precipitate in a toluene solution. Further, the two centrifugation steps are carried out to remove unreacted impurities and smaller-sized nanoparticles; subsequently, the precipitate is placed again into the toluene solution to obtain the toluene solution of perovskite CsPbBra nanoparticles. The prepared perovskite exhibits high luminescence efficiency and may be applied in the fields of photodetectors and LEDs. Another object of the present disclosure is to provide a system for preparing perovskite CsPbBra nanoparticles, wherein the system comprises: a) a three-necked flask with a volume of 100 mL, configured for receiving octadecene (ODE), CS2CO3 powder, and oleic acid (OA); b) a nitrogen cylinder connecting device, connected to the three-necked flask, configured for introducing nitrogen into the three-necked flask to create a nitrogen atmosphere; c) heating equipment fitted with a temperature controller, configured for heating a solution within the three-necked flask to a specific temperature; d) an additional three-necked flask, configured for receiving octadecene solution and PbBrz powder. Further, the heating equipment is capable of controlling a temperature range from room temperature to 150°C and can stably maintain a preset temperature, to ensure that all the CS2CO3 powder and oleic acid fully react to form a cesium oleate solution, and also the octadecene solution and the PbBr2 powder is appropriately heated in the additional three-necked flask with an additional heating equipment. In conjunction with the above technical solutions and the technical problems to be solved, the advantages and positive effects provided by the technical solutions sought to be protected by the present disclosure are as follows: Firstly, the present disclosure provides a method for preparing perovskite CsPbBra nanoparticles in a nitrogen atmosphere within a fume hood. Compared to traditional preparation methods, this method is more streamlined and easier to operate, and can be performed on a laboratory scale. The method of the present disclosure provides a detailed description of the preparation process for cesium oleate stock solution. Through precise control of the reaction conditions, it ensures the quality and purity of the cesium oleate stock solution, thereby improving the performance of the final nanoparticles. The present disclosure further adjusts the reaction conditions to ensure the CS2CO3 powder is thoroughly mixed with the oleic acid, thereby ensuring the stability and reactivity of the cesium oleate stock solution, which is key to the quality of perovskite CsPbBrs nanoparticles. The present disclosure provides the operating procedure in an additional threenecked flask. The steps and parameter settings in this process aim to ensure complete dissolution of PbBr2 powder, thereby improving the quality of the final product. The present disclosure, by adding oleic acid (OA) solution and oleylamine (OLA) solution under conditions at 120°C, optimizes the properties of the reaction mixture, further enhancing the quality of the nanoparticles. The present disclosure describes an efficient reaction process where, by elevating and cooling the temperature, the reaction can be completed more quickly, saving both time and energy. The present disclosure utilizes centrifugation and washing steps to effectively remove unreacted impurities and smaller-sized nanoparticles, thereby improving the purity and quality of the nanoparticles. The final processing steps of the present disclosure ensure the preparation of high-purity and high-quality perovskite CsPbBrs nanoparticles, providing efficient raw materials for the manufacture of photodetectors and LEDs, among other devices, and contributing to the enhancement of device performance. Secondly, the method provides an efficient and controllable approach for preparing perovskite CsPbBrs nanoparticles. Through the use of advanced nitrogen displacement technology, it ensures that the chemical reaction environment within the three-necked flask is anhydrous and oxygen-free, thereby eliminating any adverse reactions with oxygen and water in the air, and enhancing the quality and purity of the nanoparticles. At the specified operating temperature, the use of oleic acid as a stabilizer ensures that the morphology and size of the perovskite CsPbBrs nanoparticles remain within the nanometer range, thereby producing nanoparticles with superior optical properties. At the same time, the use of octadecene (ODE) further ensures the smooth progression of the chemical reaction, reduces the generation of harmful by-products, and increases the selectivity and efficiency of the entire reaction process. Furthermore, by precisely controlling the order of addition of chemical raw materials, reaction temperature, and time, the method ensures the consistency and repeatability of the perovskite CsPbBra nanoparticles. Overall, this method provides the technical foundation for the large-scale production of high-quality perovskite CsPbBrs nanoparticles, laying a solid groundwork for applications in photovoltaics, optoelectronics, and other fields. Thirdly, the technical solution of the present disclosure fills a technological gap both domestically and internationally. The disclosure simplifies the preparation conditions for perovskite CsPbBrs, allowing for the preparation of CsPbBra nanoparticles within a fume hood. The resulting CsPbBrs nanoparticles can be well-preserved when placed in a toluene solution. Moreover, the obtained perovskite exhibits good luminescent properties, with photoluminescence phenomena observable even under natural light. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram showing an experimental apparatus provided by an embodiment of the present disclosure; Figure 2 is a Scanning Electron Microscopy (SEM) image of the perovskite CsPbBrs nanoparticles provided by an embodiment of the present disclosure; Figure 3 is a luminescence image of the perovskite CsPbBr3 nanoparticles provided by an embodiment of the present disclosure. DETAILED DESCRIPTION In order to make the objectives, technical solutions, and advantages of the present disclosure clearer, the following provides a detailed description of the disclosure in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present disclosure and are not intended to limit the scope of the present disclosure. In conjunction with the accompanying drawings of the embodiments of the present disclosure, a clear and complete description of the technical solutions in the embodiments of the present disclosure will be provided below. It is evident that the described embodiments are only a portion of the embodiments of the present disclosure, and not all of the embodiments. All other embodiments that those skilled in the art may obtain, without creative effort, fall within the scope of protection of the present disclosure. The present disclosure proposes a method for preparing CsPbBrs nanoparticles in a nitrogen atmosphere, comprising the following steps: S1: adding an appropriate amount of octadecene (ODE) into a three-necked flask with a volume of 100 mL, followed by sequentially adding CS2CO3 powder and oleic acid (OA) into the three-necked flask; S2: first connecting a nitrogen cylinder to one end of the three-necked flask and introducing nitrogen into the flask for 0.5-1 hour to expel air; subsequently, heating the solution in the flask to 120°C under a nitrogen atmosphere and maintaining it for 1-2 hours; S3: further heating the solution to 150°C under a nitrogen atmosphere; S4: sequentially adding octadecene solution and an appropriate amount of PbBr2 powder into an additional three-necked flask; S5: similarly expelling air by introducing nitrogen at one end for 0.5-1 hour, and then heating the above-mentioned solution to 120°C under a nitrogen atmosphere and maintaining for 1-2 hours; S6: subsequently injecting oleic acid (OA) solution and oleylamine (OLA) solution from the other end, and once all the PbBr2 in the solution has dissolved, raising the temperature to 160°C; S7: injecting the hot cesium oleate solution into the mixture, and after reaction for 5-10 seconds, rapidly cooling the mixed solution using an ice-water bath; S8: centrifuging the solution at a speed of 3000 RPM for 30 minutes, removing the supernatant, and adding toluene to the precipitate, followed by further centrifuging at 3000 RPM for 20 minutes; S9: after centrifugation, removing the supernatant again and placing the precipitate in a toluene solution. Further, in step S1, 2.5 mmol of CS2CO3 powder, 2.5 mL of oleic acid, and 40 mL of octadecene are added to the three-necked flask with a volume of 100 mL. Further, in step S2, the nitrogen is introduced for a duration of 1 hour, and the solution is heated to 120°C under a nitrogen atmosphere and maintained for 1 hour. Further, in step S3, the solution is heated to 150°C until all of the CS2CO3 powder has fully reacted with the oleic acid, forming a cesium oleate solution. Further, in step S4, 10 mL of octadecene solution and 0.38 mmol of PbBr2 powder are added to the additional three-necked flask. Further, in step S5, the nitrogen is introduced for 1 hour to expel air, and the solution is heated to 120°C under a nitrogen atmosphere and maintained for 1 hour. Further, in step S6, 1 mL of oleic acid solution and 1 mL of oleylamine solution are added. Further, in step S7, 1 mL of hot cesium oleate solution is injected, and after reaction for 10 seconds, the mixture is rapidly cooled using an ice-water bath. Further, in step S8, the two centrifugations are performed to remove unreacted impurities and smaller-sized nanoparticles. Further, in step S9, the precipitate is again placed in a toluene solution, resulting in a toluene solution of CsPbBr3 nanoparticles. Further, uniformly-sized and fully-shaped CsPbBr3 nanoparticles are produced, with a size of around 100 nm. Further, uniformly-sized and fully-shaped CsPbBr3 nanoparticles are prepared under a nitrogen atmosphere. The perovskite thus prepared exhibits high luminescence efficiency and holds promise for applications in photodetectors and LED fields. Example 1: Preparation of Cesium Oleate Stock Solution 1. Into a three-necked flask with a volume of 100 mL, 10 mL of octadecene (ODE) was first added, followed by the sequential addition of 1.0 g of CS2CO3 powder and 10 mL of oleic acid (OA). 2. A nitrogen cylinder was connected to one end of the three-necked flask and nitrogen was introduced for 1 hour to expel the air from the flask. 3. Under a nitrogen atmosphere, the solution in the three-necked flask was heated to 120°C and maintained at this temperature for 2 hours. 4. While the nitrogen atmosphere was maintained at 120°C, the solution was further heated to 150°C and maintained at this temperature for 1 hour until all CS2CO3 powder has reacted fully with the oleic acid to form a cesium oleate solution. This cesium oleate solution served as an essential precursor for the subsequent preparation of perovskite CsPbBrs nanoparticles. Example 2: Preparation of Perovskite CsPbBra Nanoparticles 1. Into an additional three-necked flask, 10 mL of octadecene was added, followed by the gradual addition of 2.0 g of PbBr2 powder. 2. A nitrogen cylinder was connected to one end of the additional three-necked flask and nitrogen was introduced for 1 hour to expel the air from the flask. 3. Under a nitrogen atmosphere, the solution was heated in the additional threenecked flask to 120°C and this temperature was maintained for 2 hours. Then, 10 mL of oleic acid (OA) solution and 10 mL of oleylamine (OLA) solution was injected from another end. 4. After the oleic acid (OA) solution and oleylamine (OLA) solution was injected and all PbBr2 in the mixed solution completely dissolved, the solution temperature was raised to 160°C, followed by injection of the hot cesium oleate solution. After 5 seconds of reaction, the mixed solution was rapidly cooled using an ice water bath. 5. After cooling the mixed solution, it was subjected to centrifugation at a speed of 3000 RPM for 30 minutes. The supernatant was removed and 30 mL of toluene was added to the precipitate. The solution was subjected to centrifugation again at 3000 RPM for 20 minutes. The supernatant was removed again and the precipitate was placed in 30 mL of toluene solution. 6. Finally, the precipitate was placed into the toluene solution again to obtain a toluene solution of perovskite CsPbBra nanoparticles. The above two examples provide detailed descriptions of how to prepare perovskite CsPbBrs nanoparticles on a laboratory scale. This preparation method is not only straightforward and easy to operate, but also yields nanoparticles of high quality and purity that can meet the demands of photodetectors and LEDs, among other devices. Figure 3 presents the photoluminescence spectrum of the prepared perovskite CsPbBra nanoparticles. As seen in the figure, strong luminescence was observed under 473 nm laser excitation, with the center position of the luminescence spectrum located at 522 nm. Therefore, it can be applied in various optoelectronic devices such as solar cells, photodetectors, and LEDs. Figure 1 illustrates the apparatus for preparing perovskite CsPbBra nanoparticles. Uniformly-sized and fully-shaped perovskite CsPbBra nanoparticles can also be obtained in a nitrogen atmosphere within a fume hood, as shown in Figure 2. Moreover, storing the prepared perovskite CsPbBra nanoparticles in a toluene solution facilitates the preservation of the perovskite. The prepared perovskite CsPbBra nanoparticles have a size of around 100 nm and exhibit strong luminescence, as depicted in their photoluminescence spectrum shown in Figure 3. In the description of the present disclosure, unless otherwise specified, the term "multiple" means two or more. The terms "upper," "lower," "left," "right," "inner," "outer," "front end," "rear end," "head," "tail," and the like indicate directional or positional relationships based on those shown in the accompanying drawings. These are solely for the convenience of describing the disclosure and simplifying the description, and should not be construed as indicating or implying that the devices or components referred to must have a specific orientation, or be constructed and operated in a particular orientation. Thus, such terms should not be construed as limitations on the present disclosure. Furthermore, the terms "first," "second," "third," etc., are used merely for descriptive purposes and should not be construed as indicating or implying their relative importance. The foregoing descriptions merely represent specific embodiments of the present disclosure, and the scope of protection of the present disclosure is not limited thereto. Any modifications, equivalent replacements, or improvements made within the spirit and principle of the present disclosure by anyone skilled in the art should fall within the scope of protection of the present disclosure.

Claims

1. A method for preparing perovskite CsPbBra nanoparticles in a nitrogen atmosphere within a fume hood, wherein the method comprises preparing a cesium oleate stock solution and preparing perovskite CsPbBra nanoparticles.

2. The method of claim 1, wherein the method comprises the following steps: into a three-necked flask with a volume of 100 mL, first adding an appropriate amount of octadecene, followed by sequentially adding CS2CO3 powder and oleic acid; connecting a nitrogen cylinder to one end of the three-necked flask, and introducing nitrogen into the three-necked flask for 0.5-1 hour to expel the air therein; heating a solution in the three-necked flask to 120°C in a nitrogen atmosphere, and maintaining that temperature for 1-2 hours.

3. The method of claim 2, wherein the method further comprises, while maintaining the nitrogen atmosphere at 120°C, further heating the solution to 150°C and keeping at that temperature until all the CS2CO3 powder and the oleic acid have fully reacted to form a cesium oleate solution.

4. The method of claim 1, wherein the method comprises, into an additional threenecked flask, first adding octadecene solution, followed by gradually adding an appropriate amount of PbBr2 powder; connecting a nitrogen cylinder to one end of the additional three-necked flask and introducing nitrogen into the additional three-necked flask for 0.5-1 hour to expel the air therein.

5. The method of claim 4, wherein the method further comprises, heating the solution in the additional three-necked flask to 120°C in a nitrogen atmosphere, and maintaining that temperature for 1-2 hours, after which injecting an oleic acid solution and an oleylamine solution from another end.

6. The method of claim 5, wherein the method further comprises, after injecting the oleic acid solution and the oleylamine solution, allowing the PbBr2 in the mixed solution to completely dissolve, and raising the temperature of the solution to 160°C, followed by injecting the hot cesium oleate solution, and 5-10 seconds post-injecting, rapidly cooling the mixed solution using an ice-water bath.

7. The method of claim 6, wherein the method further comprises, after cooling the mixed solution, centrifuging it at a speed of 3000 RPM for 30 minutes, removing the supernatant, and adding toluene to the precipitate, followed by further centrifuging at 3000 RPM for 20 minutes; again removing the supernatant, and placing the precipitate in a toluene solution.

8. The method of claim 7, wherein the two centrifugation steps are carried out to remove unreacted impurities and smaller-sized nanoparticles; and wherein the method further comprises, subsequently, placing the precipitate again into the toluene solution to obtain the toluene solution of perovskite CsPbBra nanoparticles.

9. A system for preparing perovskite CsPbBrs nanoparticles, wherein the system comprises:a) a three-necked flask with a volume of 100 mL, configured for receiving octadecene, CS2CO3 powder, and oleic acid;b) a nitrogen cylinder connecting device, connected to the three-necked flask, configured for introducing nitrogen into the three-necked flask to create a nitrogen atmosphere;c) heating equipment fitted with a temperature controller, configured for heating the solution within the three-necked flask to a specific temperature;d) an additional three-necked flask, configured for receiving octadecene solution and PbBr2 powder.

10. The system of claim 9, wherein, the heating equipment is capable of controlling a temperature range from room temperature to 150°C and can stably maintain a preset temperature, to ensure that all the CS2CO3 powder and the oleic acid fully react to form a cesium oleate solution, and also to appropriately heat the octadecene solution and PbBr2 powder in the additional three-necked flask.Amendments to the Claims have been filed as follows:09 05 24CLAIMS1. A method for preparing perovskite CsPbBra nanoparticles in a nitrogen atmosphere within a fume hood, wherein the method comprises preparing a cesium oleate stock solution and preparing perovskite CsPbBrs nanoparticles, and wherein the method comprises the steps of:into a three-necked flask with a volume of 100 mL, first adding an appropriate amount of octadecene, followed by sequentially adding CS2CO3 powder and oleic acid; connecting a nitrogen cylinder to one end of the three-necked flask, and introducing nitrogen into the three-necked flask for 0.5-1 hour to expel the air therein; heating a solution in the three-necked flask to 120°C in a nitrogen atmosphere, and maintaining that temperature for 1-2 hour; andwhile maintaining the nitrogen atmosphere at 120°C, further heating the solution to 150°C and keeping at that temperature until all the CS2CO3 powder and the oleic acid have fully reacted to form a cesium oleate solution.

2. The method of claim 1, wherein the method further comprises, into an additional three-necked flask, first adding octadecene solution, followed by gradually adding an appropriate amount of PbBr2 powder; connecting a nitrogen cylinder to one end of the additional three-necked flask and introducing nitrogen into the additional three-necked flask for 0.5-1 hour to expel the air therein.

3. The method of claim 2, wherein the method further comprises, heating the solution in the additional three-necked flask to 120°C in a nitrogen atmosphere, and maintaining that temperature for 1-2 hours, after which injecting an oleic acid solution and an oleylamine solution from another end.

4. The method of claim 3, wherein the method further comprises, after injecting the oleic acid solution and the oleylamine solution, allowing the PbBr2 in the mixed solution09 05 24to completely dissolve, and raising the temperature of the solution to 160°C, followed by injecting the hot cesium oleate solution, and 5-10 seconds post-injecting, rapidly cooling the mixed solution using an ice-water bath.

5. The method of claim 4, wherein the method further comprises, after cooling the mixed solution, centrifuging it at a speed of 3000 RPM for 30 minutes, removing the supernatant, and adding toluene to the precipitate, followed by further centrifuging at 3000 RPM for 20 minutes; again removing the supernatant, and placing the precipitate in a toluene solution.

6. The method of claim 5, wherein the two centrifugation steps are carried out to remove unreacted impurities and smaller-sized nanoparticles; and wherein the method further comprises, subsequently, placing the precipitate again into the toluene solution to obtain the toluene solution of perovskite CsPbBrs nanoparticles.Application No: GB2317268.7Examiner: Dr Craig JamesClaims searched: 1-8Date of search: 23 February 2024Patents Act 1977: Search Report under Section 17Documents considered to be relevant:Category Relevant to claims Identity of document and passage or figure of particular relevance X 1-8 WO 2023 / 092515 Al (UNIV S00CH0W) Paragraphs 0005, 0009 and 0035-0038. X 1-8 US 2018 / 0312754 Al (PAN et al.) Paragraphs 0004, 0068, 0073 and 0100-0106. X 1-8 US 2021 / 0292642 Al (LI et al.) Paragraphs 0002 and 0174. v A 1-8 US 2021 / 0171828 Al (LIU et al.) Paragraphs 0017, 0019 and 0024-0026. X 1-8 CN 112375567 A (UNIV HEFEI TECHNOLOGY) WPI abstract, accession number 2021-20344K and steps 1 to 2. v A 1-8 CN 109142290 B (UNIV FOSHAN) WPI abstract, accession number 2019-05315R, summary of invention and steps SI to S3.Categories:X Document indicating lack of novelty or inventive step A Document indicating technological background and / or state of the art. Y Document indicating lack of inventive step if P Document published on or after the declared priority date but combined with one or more other documents of same category. before the filing date of this invention. & Member of the same patent family E Patent document published on or after, but with priority date earlier than, the filing date of this application.Field of Search:International Classification:Subclass Subgroup Valid From C09K 0011 / 66 01 / 01 / 2006 B82Y 0040 / 00 01 / 01 / 2011 C09K 0011 / 08 01 / 01 / 2006 B82Y 0020 / 00 01 / 01 / 2011

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