Standard Operating Procedures Laboratory Specific Chemical: Nitrogen trifluoride Please fill out the form completely. Print a copy and insert into your Laboratory Safety Manual and Chemical Hygiene Plan. Refer to instructions for assistance. _____________________________________________________________________________ Department:________________________ Date when SOP was written:_______ Date when SOP was approved by the lab supervisor: ___________________ Principal Investigator:___________________________________________________ Internal Laboratory Safety Coordinator/Lab Manager:___________________________________ Laboratory Phone:____________________ Office Phone:_____________________ Emergency Contact:____________________________________________________ (Name and Phone Number) Location(s) covered by this SOP:__________________________________________ (Building/Room Number) _____________________________________________________________________________ Type of SOP: Process Hazardous Chemical Hazardous Class Purpose Material is highly volatile and may quickly form a concentrated atmosphere in confined or unventilated areas. Vapor is heavier than air and may displace and replace air in breathing zone, acting as a simple asphyxiant. It also works as an oxidizer for high-energy fuels and in chemical synthesis. Nitrogen trifluoride is mainly employed in the cleaning of the PECVD chambers in the high volume production of liquid crystal displays and silicon-based thin film solar cells. In these applications NF3 is initially broken down in situ, by a plasma, and the resulting fluorine atoms are used as the active cleaning agents that attack the polysilicon, silicon nitride and silicon oxide. Nitrogen trifluoride can be used as well with tungsten silicide, and tungsten produced by CVD. Recently, elemental fluorine has been introduced as an environmentally friendly replacement for nitrogen trifluoride in state-of-the-art high volume manufacturing of flat panel displays and solar cell manufacturing. Erroneously NF3 has been considered as an environmentally preferable substitute for perfluorocarbons such as hexafluoroethane and sulfur hexafluoride. The process utilization of the chemicals applied in plasma processes is typically below 20 %. Therefore, some of the PFCs and also of the NF3 always escape into the atmosphere. Physical & Chemical Properties/Definition of Chemical Group CAS#: 7783-54-2 1 Class: Strong oxidizer, toxic, contact with combustible material may cause fire, harmful by inhalation, irritating to eyes, risk of explosion if heated under confinement Molecular formula: NF3 Appearance: Colorless gas Boiling Point: -200°F Melting Point: -340°F Odor: Odorless Vapor pressure: >1 atm Potential Hazards/Toxicity Note: Nitrogen trifluoride has the potential to hydrolyze to nitrosyl fluoride and ultimately hydrofluoric acid (HF). Please consult the hydrofluoric acid SOP for information regarding the hazards of HF. Ingestion: Not normally a hazard due to physical form of product. Considered an unlikely route of entry in commercial/industrial environments. See above note regarding potential for hydrofluoric acid production. Eye: Not considered to be a risk because of the extreme volatility of the gas. This material can cause eye irritation and damage in some persons but toxic effects from inhalation of nitrogen trifluoride will occur before eye effects. See above note regarding potential for hydrofluoric acid production. Skin: There is some evidence to suggest that this material can cause inflammation of the skin on contact in some persons. See above note regarding potential for hydrofluoric acid production. Inhalation: Inhalation of vapors may cause drowsiness and dizziness, accompanied by narcosis, reduced alertness, loss of reflexes, lack of coordination and vertigo. There is some evidence to suggest that the material can cause respiratory irritation in some persons. The body's response to such irritation can cause further lung damage. The odor of nitrogen trifluoride will not provide sufficient warning of exposure and potentially dangerous amounts may be inhaled before an odor is detected. Material is highly volatile and may quickly form a concentrated atmosphere in confined or unventilated areas. Vapor is heavier than air and may displace and replace air in breathing zone, acting as a simple asphyxiant which can cause headache, dizziness, shortness of breath, muscular weakness, drowsiness and ringing in the ears. If the asphyxia is allowed to progress, there may be nausea and vomiting, further physical weakness and unconsciousness and, finally, convulsions, coma and death. Acute effects of fluoride inhalation include irritation of nose and throat, coughing and chest discomfort. A single acute over-exposure may even cause nose bleed. Acute inhalation exposures to hydrogen fluoride (hydrofluoric acid) vapors produce severe eye, nose, and throat irritation; delayed fever, cyanosis, and pulmonary edema; and may cause death. 2 See above note regarding potential for hydrofluoric acid production. Even fairly low airborne concentrations of hydrogen fluoride produce rapid onset of eye, nose, and throat irritation. Chronic health effects: Repeated exposure to nitrogen trifluoride may adversely affect the liver and kidneys. Irritation of airways to lung, with cough, and inflammation of lung tissue often occurs. Extended exposure to inorganic fluorides causes fluorosis, which includes signs of joint pain and stiffness, tooth discoloration, nausea and vomiting, loss of appetite, diarrhea or constipation, weight loss, anemia, weakness and general unwellness. There may also be frequent urination and thirst. Personal Protective Equipment (PPE) Respirator: Type ABEG-P Filter of sufficient capacity, if needed. (AS/NZS 1716 & 1715, EN 143:2000 & 149:2001, ANSI Z88 or national equivalent) Eye: Safety glasses with side shields or chemical goggles are recommended. Hands: When handling sealed and suitably insulated cylinders wear cloth or leather gloves. Other: Lab coat. Plastic personal protective equipment (PPE) (e.g. gloves, aprons, overshoes) are not recommended as they may produce static electricity. For large scale or continuous use tight-weave non-static clothing (no metallic fasteners, cuffs or pockets) and non-sparking safety footwear is recommended. Engineering Controls Areas where cylinders are stored require good ventilation and, if enclosed, need discrete/ controlled exhaust ventilation. Secondary containment and exhaust gas treatment may be required by certain jurisdictions. First Aid Procedures Ingestion: Not considered a normal route of entry. Eye: If product comes in contact with eyes remove the patient from gas source or contaminated area. Take the patient to the nearest eye wash, shower or other source of clean water. Skin: Immediately remove all contaminated clothing, including footwear. Flush skin and hair with running water (and soap if available). Inhalation: Following exposure to gas, remove the patient from the gas source or contaminated area. NOTE: Personal Protective Equipment (PPE), including positive pressure self-contained breathing apparatus may be required to assure the safety of the rescuer. Notes to physician: Establish a patent airway with suction where necessary. Watch for signs of respiratory insufficiency and assist ventilation as necessary. 3 Special Handling and Storage Requirements Procedure for handling: Consider use in closed pressurized systems, fitted with temperature, pressure and safety relief valves which are vented for safe dispersal. Check regularly for spills or leaks. Keep valves tightly closed but do not apply extra leverage to hand wheels or cylinder keys.DO NOT transfer gas from one cylinder to another. Recommended storage methods: Most metals are satisfactory for handling nitrogen trifluoride up to temperatures of approximately 70 ºC. Nickel and Monel are recommended for higher temperatures. Wetted surfaces should be passivated with an "active" fluorine compound to establish a metal fluoride coating as additional protection. Teflon and Kel-F are preferred gasket materials. Keep equipment scrupulously dry. Many of the metal fluorides are water soluble so that the passive film corrosion protection may be destroyed if wetted with water. Ensure the use of equipment rated for cylinder pressure. Storage requirements: Cylinders should be stored in a purpose-built compound with good ventilation, preferably in the open. Such compounds should be sited and built in accordance with statutory requirements. Spill and Accident Procedure Chemical Leak Dial 911 and x59797 Spill – Help contaminated or injured persons. Evacuate the leak area. Avoid breathing vapors utilizing a self-contained breathing apparatus. Eliminate sources of ignition if the chemical is flammable. Provide ventilation. Prevent spreading of vapors through sewers, ventilation systems and confined areas. Evacuate unnecessary personnel. Keep others from entering contaminated area (e.g., use caution tape, barriers, etc.) Small leak – Avoid breathing vapor and any contact with liquid or gas. Protective equipment including respirator should be used to evacuate. DO NOT enter confined spaces were gas may have accumulated. Large leak – Dial 911 (or 310-825-1491 from cell phone) and EH&S at x59797 for assistance. Chemical Spill on Body or Clothes – Unlikely to occur due to the nature of the chemical. If the compound is allowed to hydrolyze hydrofluoric acid may be formed. If exposed to hydrofluoric acid remove clothing and rinse body thoroughly in emergency shower for at least 15 minutes. After shower apply/massage calcium gluconate gel to affected area every 15 minutes and seek medical attention immediately. Seek medical attention. Notify supervisor and EH&S at x59797 immediately. Chemical Splash Into Eyes – Immediately rinse eyeball and inner surface of eyelid with water for 15 minutes by forcibly holding the eye open. Seek medical attention. Notify supervisor and EH&S at x59797 immediately. Medical Emergency Dial 911 or x52111 Life Threatening Emergency, After Hours, Weekends And Holidays – Dial 911 (or 310-8251491 from cell phone) or contact the Ronald Reagan UCLA Medical Center (emergency room) directly at x52111 (located at 757 Westwood Plaza, enter from Gayley Avenue). Note: All serious injuries must be reported to EH&S at x59797 within 8 hours. 4 Non-Life Threatening Emergency– Go to the Occupational Health Facility (OHF), x56771, CHS room 67-120 (This is on the 6th floor, 7th corridor, room 120. Enter through the School of Dentistry on Tiverton Drive and proceed to the “O” elevator to the 6th floor.)Hours: M - F, 7:30 a.m. to 4:30 p.m. At all other times report to Ronald Regan UCLA Medical Center (emergency room) at x52111. Note: All serious injuries must be reported to EH&S at x59797 within 8 hours. Needle stick/puncture exposure (as applicable to chemical handling procedure)– Wash the affected area with antiseptic soap and warm water for 15 minutes. For mucous membrane exposure, flush the affected area for 15 minutes using an eyewash station. Page the needle stick nurse by dialing 231 from a campus phone, enter 93333 when prompted and then enter your extension. Hours: M – F, 8:00 a.m. to 4:00 p.m. At all other times report to Ronald Regan UCLA Medical Center (emergency room) at x52111. Note: All needle stick/puncture exposures must be reported to EH&S at x59797 within 8 hours. Decontamination/Waste Disposal Procedure All waste must be handled in accordance with local, state and federal regulations. Return empty containers to supplier. Material Safety Data Sheet (MSDS) Location (State the location of MSDS) Hardcopy or electronic copy must be available. Online MSDS can be accessed at http://msds.ehs.ucla.edu. Protocol/Procedure (Add specific description of procedure.) Note: Any deviation from this SOP requires written approval from PI. Documentation of Training (signature of all users is required) I have read and understand the content of this SOP: Name Signature 5 Date