Standard Operating Procedure

Laboratory Specific Chemical: Piranha Solution (Piranha

Etch)

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: Purpose

Process

Hazardous Chemical

Hazardous Class

Piranha solution, also known as piranha etch, is a mixture of sulfuric acid (H2SO4) and hydrogen peroxide (H2O2), used to clean organic residues off substrates. Because the mixture is a strong oxidizer, it will remove most organic matter, and it will also hydroxylate most surfaces (add OH groups), making them extremely hydrophilic (water compatible). Piranha solution is used frequently in the microelectronics industry, e.g. to clean photoresist residue from silicon wafers. Piranha solution is very dangerous, being both strongly acidic and a strong oxidizer. Before using Piranha, a chemist should attempt more stable methods of removing stains, tars or clogs. Often, glassware will "clean itself" if simply left with a rinse of a cleaning solution present. An immediate example for a suitable substitute, prior to using Piranha, is 98% sulfuric acid. Piranha solution can be an explosive. Mixing the solution is exothermic. The resultant heat can bring solution temperatures up to 120C. One must allow the solution to cool reasonably before applying any heat. The sudden increase in temperature can also lead to violent boiling, or even splashing of the extremely acidic solution. Also, explosions may occur if the peroxide solution concentration is more than 50%. 30% peroxide in water solution is more reasonable. Many different mixture ratios are commonly used, and all are called piranha. A typical mixture is 3:1 concentrated sulfuric acid to 30% hydrogen peroxide solution; other protocols may use a 4:1 or even 7:1 mixture. A closely related mixture, sometimes called "base piranha", is a 3:1 mixture of ammonium hydroxide (NH4OH) with hydrogen peroxide. Base piranha is also known under the name of TL1 cleaning.

The traditional piranha solution is a 3:1 mixture of sulfuric acid and 30% hydrogen peroxide. The solution may be mixed before application or directly applied to the material, applying the sulfuric acid first, followed by the peroxide. Piranha solutions are extremely energetic and may result in explosion or skin burns if not handled with extreme caution.

Physical & Chemical Properties/Definition of Chemical Group

Corrosive & oxidizer Potential explosive

Potential Hazards/Toxicity
Explosion hazards Splash hazards Container rupture/failure (due to pressure build-up) Skin burns Irritation of mucus membrane

Personal Protective Equipment (PPE)

Chemical safety goggles and face shield must be used Cotton based lab coat (fire resistant lab coats) Chemically resistant gloves (Nitrile or Neoprene gloves) Full length pants Close toed shoes

Engineering Controls
Fume hood or chemical wet bench (depending on the process).

First Aid Procedures

In case of skin contact: May cause skin burns. Flush the skin with copious amounts of water for at least 15 minutes. Seek medical attention. In case of eye contact: Piranha is corrosive and irritating to the eyes. Flush contaminated eye(s) immediately with copious quantities of water for at least 15 minutes. Seek medical attention immediately. In case of inhalation: May irritate the respiratory tract. Conscious persons should be assisted to an area with fresh, uncontaminated air. Seek medical attention in the event of respiratory irritation, cough, or tightness in the chest. Symptoms may be delayed. In case of ingestion: Not a likely route of exposure.

Special Handling and Storage Requirements

Always use glass (preferably Pyrex) containers. Piranha will melt plastics. Mix the solution in a fume hood with the sash between you and the solution. Wear gloves and eye protection.

When preparing the piranha solution, always add the peroxide to the acid. Piranha solution is very energetic and potentially explosive. It is very likely to become hot, more than 100 degrees C. Handle with care. Leave the hot piranha solution in an open container until cool. Never store piranha solutions for longer periods. Piranha stored in a closed container will likely explode. Adding any acids or bases to piranha or spraying it with water will accelerate the reaction. This also includes Photoresist, which is a strong base. Mixing hot piranha with organic compounds may cause an explosion. This includes acetone, photoresist, isopropyl alcohol (other organic solvents), and nylon. Piranha solution that is no longer being used should never be left unattended if hot. It should not be stored in a closed container. Adding anything to the piranha solution (such as a substrate that may have organic residue), must be done slowly and carefully, giving the solution time to stabilize.

General handling & storage guidelines: Piranha solution may be prepared by adding the acid to the peroxide (following the usual rule of adding acid to water) although some authorities disagree. Once the mixture has stabilized, it can be further heated to sustain its reactivity. The hot (often bubbling) solution will clean organic compounds off substrates, and oxidize/hydroxylate most metal surfaces. Cleaning usually requires about 10 to 40 minutes, after which time the substrates can be removed from the solution. The solution may be mixed before application or directly applied to the material, applying the sulfuric acid first, followed by the peroxide. Due to the self-decomposition of hydrogen peroxide, piranha solution should be used freshly-prepared. Piranha solution should not be stored. Waste piranha solution should be neutralized and disposed in situ, instead of being accumulated in carboys. Oxygen given off during the self-decomposition, as well as the oxidation products of organic compounds can cause the container to rupture. Immersing a substrate (such as a wafer) into the solution should be done slowly to prevent thermal shock that may crack the substrate material. It is important to remember that the solution, whilst susceptible to aging, will remain a significant hazard as it drips off the item being cleaned. NOTE: Do not store piranha. Mix fresh solution for each use. Excess solution should be disposed of as hazardous waste with an online hazardous waste tag affixed. Note: The container used to store the piranha waste should have a vented cap (tiny hole like a pin hole in the container cap on the top) to prevent pressure build up in the container. VWR item no. 82013-170

Spill and Accident Procedure Chemical Spill Dial 911 and x59797 Spill Help contaminated or injured persons. Evacuate the spill area. Avoid breathing vapors.
Eliminate sources of ignition if the chemical is flammable. If possible, confine the spill to a small area using a spill kit or absorbent material. Keep others from entering contaminated area (e.g., use caution tape, barriers, etc.).

Small (<1 L) If you have training, you may assist in the clean-up effort. Use appropriate personal
protective equipment and clean-up material for chemical spilled. Double bag spill waste in clear plastic bags, label and take to the next chemical waste pick-up.

Large (>1 L) Dial 911 (or 310-825-1491 from cell phone) and EH&S at x59797 for assistance. Chemical Spill on Body or Clothes Remove clothing and rinse body thoroughly in emergency
shower for at least 15 minutes. 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 310825-1491 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.

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

The gases from the piranha solution must be allowed to dissipate, and the solution must be allowed to cool. Spent piranha solution is mainly concentrated sulfuric acid. Care must be taken not to allow the solution to be mixed with organic solvents (e.g. in waste solvent carboys), as this will cause a violent reaction and might even cause a substantial explosion. Never mix piranha solution waste with other chemical wastes. NOTE: Just before taking the piranha solution waste (i.e., container affixed with an on-line hazardous waste tag) to the routine EH&S waste pick-up, replace the vented cap with a non-vented cap. Please let the EH&S waste pick-up personnel know about this. Label Waste o Affix an on-line hazardous waste tag on all waste containers using the Online Tag Program http://otp.ucop.edu/ as soon as the first drop of waste is added to the container Store Waste o Store hazardous waste in containers with a vented cap, in secondary containment and in a designated location

o Double-bag dry waste (if generated during spill clean-up. Example: Sorbent pads, gloves
etc.) by using transparent bags http://map.ais.ucla.edu/go/1002774 o Waste must be under the control of the person generating & disposing of it Dispose of Waste o Dispose of regularly generated chemical waste within 90 days o Call EH&S at x61887 for questions o Empty Containers General Note (not applicable for Piranha solution): Dispose as hazardous waste if the containers once held extremely hazardous waste (irrespective of the container size) http://ehs.ucla.edu/Pub/ExtremelyHazardousWaste.pdf Consult waste pick-up schedule http://ehs.ucla.edu/pub/HazWaste%20Pickup %20Schedule.pdf Prepare for transport to pick-up location Check on-line waste tag

o
o

Close the piranha solution waste container with a non-vented cap just before transporting the waste to the pick-up location. Mark the date of pick-up on the waste tag Use secondary containment Wear eye protection & closed toe shoes; bring gloves

Material Safety Data Sheet (MSDS) Location

(State the location of MSDS) Hardcopy or electronic copy MSDS from the same manufacturer must be available for Sulfuric acid and Hydrogen peroxide. 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)

Prior to conducting any work with Piranha solution, designated personnel must provide training to
his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures.

The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a
copy of the Piranha solution chemicals MSDS provided by the manufacturer. The Principal Investigator must ensure that his/her laboratory personnel have attended appropriate laboratory safety training or refresher training within the last two years. I have read and understand the content of this SOP:

Name
________________________________

Signature
____________________________

Date
____________

________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________

____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________ ____________________________

____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________ ____________

________________________________ ________________________________

____________________________ ____________________________

____________ ____________