Metalorganic Precursors for LED Manufacture: A Health and Safety Perspective. Semicon China March 21, 2012

Transcription

1 Metalorganic Precursors for LED Manufacture: A Health and Safety Perspective Semicon China March 21, 2012

2 We are the Electronic Materials Business Unit of The Dow Chemical Company Approximately 40 years experience with Metalorganic precursors 1972: Alfa Products, a subsidiary of Ventron, develops High Purity Metalorganics 1976: Ventron-Alpha acquired by Thiokol Corporation. 1982: Thiokol Corporation merges with Morton to form Morton Thiokol Corporation. 1989: Thiokol divested, resulting company named Morton International, Inc. 1998: Morton International, Inc., acquired by Rohm and Haas Company. 2001: High Purity Metalorganics business becomes part of Shipley Company, LLC. 2004: Shipley Company LLC changes name to Rohm and Haas Electronic Materials LLC. 2009: The Dow Chemical Company Acquires Rohm and Haas. The #1 priority of The Dow Chemical Company is Safety Page 2

3 Metalorganic Precursors Provided by Dow Aluminum Sources Trimethylaluminum (TMA) Gallium Sources Trimethylgallium (TMG) Triethylgallium (TEG) Indium Sources Trimethylindium (TMI) Magnesium Sources Biscyclopentadienyl Magnesium (Cp2Mg) Zinc Sources Dimethylzinc (DMZ) Diethylzinc (DEZ) Germanium liquid source Isobutylgermane Others Sources for Antimony, Arsenic, Carbon, Tellurium Page 3

4 Characteristics of Metalorganic Precursors CAS# Color/ Form Odor Density Vapor Press Flash point Trans port Hazard TMG Colorless/ Liquid Garlic Odor mm Pyrophoric UN 3394, Class 4.2 (4.3), Packing Group I Corrosive, Pyrophoric, Water Reactive TEG Colorless/ Liquid Garlic Odor mm Pyrophoric UN 3394, Class 4.2 (4.3), Packing Group I Corrosive, Pyrophoric, Water Reactive TMA Colorless/ Liquid Slight Pyrophoric UN 3394, Class 4.2 (4.3), Packing Group I Corrosive, Pyrophoric, Water Reactive TMI White/Crys talline Powder Slight Pyrophoric UN 3393, Class 4.2 (4.3), Packing Group I Corrosive, Pyrophoric, Water Reactive Cp2Mg White/ Crystals Characterist ic No data <1.0 mm Pyrophoric UN 3393, Class 4.2 (4.3), Packing Group I Corrosive, Pyrophoric, Water Reactive Refer to MSDS for additional information Page 4

5 Stability and Reactivity of Metalorganic Precursors Hazardous Reactions Ignites spontaneously if exposed to air. Reacts violently with water. Stable under recommended storage conditions. Conditions to avoid High temperatures Exposure to air or oxygen. Exposure to water or moisture Exposure to sunlight. Materials to avoid Air, Oxidizers, Water, Amines, Acids, Strong bases Hazardous decomposition products Metal oxides, Carbon monoxide, carbon dioxide, Hydrocarbons, acrid smoke and irritating fumes Polymerization Will not occur. Page 5

6 Pyrophorics Pyrophorics are self-reactive materials which will spontaneously ignite upon exposure to air or water. Some compounds can produce intense fires and copious amounts of smoke Pyrophorics react violently with water. They decompose into parent metal oxide residues (e.g., aluminum oxide, indium oxide, gallium oxide). Page 6

7 Nature of the Precursor Cylinders Dow s containers are built and maintained in accordance with DOT and UN regulations Recertified every 5 years Cylinder Ownership Cylinders are the property of The Dow Chemical Company They are intended for use only with Dow s chemical formulations Cylinders cannot be used for other purposes or with different chemistry Cylinders cannot be modified Once a cylinder has been emptied, it should be returned to Dow for refilling or proper disposition Page 7

8 Safety Throughout the Supply Chain DOW CUSTOMER Precursor Manufacturing Product Packaging Shipment/Transportation to the Customer Precursor Removal Cylinder Cleaning, Maintenance, Certification, and Reuse Customer Storage, Handling, and Use Customer Storage and Handling Product Use Cylinder Change out Dispensing Packaging Return Shipment Page 8

9 Customer Storage and Handling Cylinder Storage Store in original container. Keep away from heat and sources of ignition. Storage area should be: cool dry well ventilated out of direct sunlight Practice good personal hygiene to prevent accidental exposure. Follow local regulations Cylinder Handling Wear appropriate Personal Protective equipment (PPE) Do not handle by valves Hold from bottom of the cylinder. Do not lift >50 lbs Use carts to transport large/heavy cylinders Use local exhaust ventilation. Keep container tightly closed. Eliminate all possible sources of ignition. Handle open cylinders in glovebox/bag under inert atmosphere. Page 9

10 Fire Fighting/Fire Protection - Pyrophorics Suitable extinguishing media Do not use wet chemical, water or foam. Use dry chemical powder followed by sand or dolomite (powdered limestone). Specific hazards during firefighting Pyrophorics can ignite spontaneously when exposed to air at normal or slightly elevated temperatures. Smoke may contain various hydrocarbons and hazardous metallic oxides. Special protective equipment for firefighters Firefighters should wear positive pressure, self-contained breathing apparatus (SCBA) with an approved full-face mask and Wear full protective firefighting clothing. Further information Reacts violently with water resulting in flammable vapor and metal oxide(s) Be aware of re-ignition. Gently agitate the sand or powdered limestone to slowly expose and burn off any unreacted metalorganic material. Once the fire has been extinguished and cooled, transfer decomposed material into suitable containers for disposal. Fire Protection There are several options available for building fire protection systems. Work with your local fire department and local authorities to determine the system/media which meets local regulations and permitting requirements for your specific situation Page 10

11 Metalorganic Precursor Use Customers process Dow Metalorganic products by bubbling inert gas through cylinder Nitrogen, argon or hydrogen are typical carrier gases Carrier gas sweeps metalorganic vapors into the deposition reactor The metalorganic product facilitates the deposition of the active layers of the LED Precursors decompose at 600 to 1200 degrees Celsius in reactor Reacts with other chemicals Page 11

12 Returning Depleted Cylinders to Dow Original pail and all packing materials are retained by customer for returning cylinder to Dow. Only qualified individuals, certified in hazardous material shipping, should undertake this responsibility, following appropriate local regulations. Carefully read the MSDS sheet for the product contained to understand its hazard and shipping classification. Be sure to identify the acceptable mode of shipment. IMPORTANT Most Metalorganic Precursors cannot be shipped by air Page 12

13 Packaging/Return Shipment 1. Contact your regional Sales Office prior to return of any cylinders. 2. Carefully close valves and seal caps on each VCR fitting. 3. Seal the cylinder in a plastic bag for cleanliness. 4. For the outer container use only pails that are in good condition and are designated UN1A2/X. 5. Use sealed bag vermiculite only and line the sides and bottom of the pail. Page 13

14 Packaging/Return Shipment (Cont d) 6. Place the cylinder in an upright position in the center of vermiculite. Place additional vermiculite bags on top. 7. Attach the lid to the pail and secure the lever lock ring. 8. Pail hazard labels should be the same as those that arrived with the original shipment. Ensure product ID label is correct. Page 14

15 Safety in Practice - Documented Operating Procedures Written operating procedures should give stepwise directions to employees and contractors involved in handling metalorganic precursors. A management-of-change program is recommended to help ensure that all changes are properly reviewed and documented before implementation. Documented training is necessary for maintaining a good safety, health, and environmental program. Training Regularly held meetings which cover safety, health, and environmental issues are an essential part of training. Page 15

16 Safety in Practice - Written Emergency Response Plans Written emergency response plans are recommended for potential releases, fires and all potential unplanned events. These emergency response plans should be written by qualified personnel and reviewed by a multifunctional team. The written emergency response plans should be periodically reviewed and updated by a multifunctional team. These emergency response plans should be covered in safety, health, and environmental reviews and made part of the documented training program. Documented drills are suggested as part of the emergency training program. Corrective action and communication should always be addressed in the written emergency response plans. Page 16

17 VAPORSTATION TM Central Delivery System Significantly reduces the risk of safety incidents associated with individual cylinder installation on reactors Continuous precursor delivery to multiple reactors simultaneously Reduced MOCVD Cost of Ownership Eliminates need to shut down reactors for individual precursor cylinder changes Reduced number of individual cylinder changes Reduced presence of pyrophorics in reactor facility Page 17

18 Dow - Delivering Safety to Your Workplace Shared responsibility for safety in using metalorganic precursors between supplier and customer Customized Metalorganic Precursor delivery solutions Cylinder sizes and types Based upon products used and volume consumed Vaporstation installations Provide safety awareness training to your organization Share best practices Page 18

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