CIRCUPOSIT 71 Full Build Electroless Copper Nitrate Bath (Generic Concentrates) For Electronic Finishing Applications

Transcription

1 CIRCUPOSIT 71 Full Build Electroless Copper Nitrate Bath (Generic Concentrates) For Electronic Finishing Applications Regional Product Availability Description N. American Asia CIRCUPOSIT 71 Full Build Electroless Copper represents a major advance in full-build electroless copper. Smooth electroless copper deposits, 25 µm (1,000 µin) or greater in thickness, can be produced. CIRCUPOSIT 71 yields deposits that are smooth, bright and uniform in color. Advantages Ductile deposits Uniform, smooth, bright-pink deposit Excellent solution stability Easy to monitor and control Offers reproducible results Bath Make-Up Chemicals Required Metric (U.S.) Deionized (D.I.) water 763 ml/l (76.3% v/v) CIRCUPOSIT 71 E 170 ml/l (17% v/v) CIRCUPOSIT 71 A 15 ml/l (1.5% v/v) CIRCUPOSIT 71 U 10 ml/l (1.0% v/v) CIRCUPOSIT 71 T 20 ml/l (2.0% v/v) CUPOSIT Z 10 ml/l (1.0% v/v) CUPOSIT Y 10 ml/l (1.0% v/v) CIRCUPOSIT 71 S 2 ml/l (0.2% v/v) Make-Up Procedure 1. Add D.I. water to a clean tank and mix thoroughly. 2. Add CIRCUPOSIT 71 E Electroless Copper to tank and mix thoroughly. 3. Add CIRCUPOSIT 71 A to tank and mix thoroughly. 4. Add CIRCUPOSIT 71 U to tank and mix thoroughly. 5. Add CIRCUPOSIT 71 T to tank and mix thoroughly. 6. Add CUPOSIT TM Z Additive to tank and mix thoroughly. 7. Add CUPOSIT Y to tank and mix thoroughly. 8. Add CIRCUPOSIT 71 S to tank and mix thoroughly. 9. Dilute to final volume with D.I. water. 10. Heat solution to operating temperature. 11. Analyze the bath for copper, formaldehyde, sodium hydroxide and EDTA following the procedures in the Bath Maintenance section and adjust as necessary. 12. Dummy plate for at least 5 hours at approximately 0.5 dm 2 /L (0.2 ft 2 /gal.) until the hourly rate is 2 3 µm/hour ( µin/hour). Page 1 of 12

2 Bath Operation Metric Parameter Range Recommended Copper Metal g/l 3.05 g/l Sodium Hydroxide Conc g/l * g/l HCHO g/l * g/l EDTA 4Na g/l 43 g/l CIRCUPOSIT 71 U % 100% Electroless Copper CIRCUPOSIT 71 S % 75% CIRCUPOSIT 71 T % 110% ph Temperature C 70 C Specific Gravity Below 1.09 Loading Factor dm 2 /L Deposition Rate microns/minute Agitation Aeration is mandatory at all times; air flow rate is liters of air per liter of bath per minute during plating and liters of air for storage at ambient temperature Bath Operation U.S. Parameter Range Recommended Copper Metal oz./gal oz./gal. Sodium Hydroxide Conc oz./gal. * oz./gal. HCHO oz./gal. * oz./gal. EDTA 4Na oz./gal oz./gal. CIRCUPOSIT 71 U Electroless Copper % 100% CIRCUPOSIT 71 S % 75% CIRCUPOSIT 71 T % 110% ph Temperature F 158 F Specific Gravity Below 1.09 Loading Factor ft 2 /gal. Deposition Rate microinches/hour Agitation Aeration is mandatory at all times; air flow rate is gal. of air per liter of bath per minute during plating and gal. of air for storage at ambient temperature * NaOH Optimum and Deposition Rate: The deposition rate is the primary factor for assuring deposit quality and should be controlled, depending on the type of application, at a level between microns per minute (80 and 120 microinches per hour) with minimum fluctuation. The deposition rate is controlled by hourly analysis for total alkalinity (as NaOH) to hold ph constant and adjustment of the CUPOSIT Y Replenisher pump flow rate. Contact your Dow Electronic Materials Representative for details on rate determination and replenishment adjustment. Page 2 of 12

3 Bath Maintenance Copper Metal Copper Metal Control Procedure The Dow Electronic Materials Process Controller has been developed to automatically and precisely control solutions such as the CIRCUPOSIT 71 Full Build Electroless Copper bath to offer instantaneous, real time deposition rate and thickness measurements. The use of one of these is recommended. Contact your Dow Electronic Materials Representative for details. Maintain copper metal concentration between g/l ( oz./gal.). To raise the copper content by 0.1 g/l (0.013 oz./gal.), add 0.50 ml/l CIRCUPOSIT 71 A Additive (0.050% v/v). Copper metal concentration can be determined following the control procedure below. I. Equipment a) 20 ml class A volumetric pipette b) 250 ml Erlenmeyer flask c) Two-50 ml graduated cylinders d) 50 ml burette e) Scale f) Hot plate II. Reagents a) Sulfuric acid, 20% b) Sulfamic acid, crystals, reagent A.C.S. c) Potassium iodide, crystals, reagent A.C.S. d) Potassium thiocyanate, 10% e) Starch indicator solution, 1% III. Titrant Sodium thiosulfate, 0.1N standardized IV. Procedure a) Pipette 10 ml of CIRCUPOSIT 71 Electroless Copper bath into a 250 ml Erlenmeyer flask. b) With gentle stirring, add 50 ml D.I. water, 40 ml sulfuric acid (20%), and approximately 0.5g sulfamic acid. c) Stir and heat sample to a boil. Boil sample for approximately one minute. d) Allow sample to cool for 5 minutes. e) Add approximately 2g potassium iodide and swirl. f) Titrate with 0.1N sodium thiosulfate to a light straw color. g) Add 20 ml potassium thiocyanate (10%), 5 ml starch indicator and mix. h) Continue the titration to an off white endpoint. i) Record ml titrant. V. Calculation copper metal g/l = ml titrant x copper metal oz./gal. = ml titrant x % copper = copper metal g/l x 32.8 Page 3 of 12

4 Sodium Hydroxide And Formaldehyde Sodium Hydroxide And Formaldehyde Control Procedure Sodium hydroxide should be maintained using CUPOSIT TM Z Additive. Formaldehyde should be maintained using CUPOSIT Y. To raise sodium hydroxide content by 1 g/l (0.13 oz./gal.), add 2.9 ml/l of CUPOSIT Z (0.29% v/v). To raise formaldehyde content by 1 g/l, add 4.0 ml/l of Cuposit Y (0.4% v/v). Sodium hydroxide and formaldehyde concentrations can be determined following the control procedure below. I. Equipment a) 5 ml class A volumetric pipette b) 250 ml beaker c) 50 ml burette d) ph meter II. Reagents a) Sodium sulfite, crystals, reagent A.C.S. b) ph 10 buffer solution III. Titrant Hydrochloric acid, 0.1N standardized IV. Procedure a) Check the ph of the sodium sulfite solution to ensure that it is between 9.5 and Prepare a fresh sodium sulfite solution if the ph is outside this range. b) Pipette 20 ml sample into a 250 ml beaker. c) Using a ph meter, standardize solution to ph 10.0 with buffer solution. d) Titrate to ph with 0.1N hydrochloric acid. e) Record ml titrant for the sodium hydroxide calculation (V1). f) Adjust the ph to with 0.1N hydrochloric acid and add approximately 1g sodium sulfite crystals. g) Stir the sample for 1 2 minutes. h) Refill the burette with 0.1N hydrochloric acid and titrate the sample to ph of (V2). i) Record ml titrant for the formaldehyde calculation. V. Calculation Total Alkalinity g/l = V1 x 0.20 Total Alkalinity oz./gal. = V1 x Free Formaldehyde g/l = V2 x 0.15 Free Formaldehyde oz./gal. = V2 x 0.02 EDTA EDTA Control Procedure: EDTA concentration should be maintained between g/l ( oz./gal.). To raise the EDTA concentration by 1 g/l, add 3.8 ml/l CIRCUPOSIT 71 E Electroless Copper (0.38% v/v). EDTA concentration can be determined following the control procedure below. I. Equipment a) 10 ml class A volumetric pipette b) 100 ml volumetric flask c) 50 ml graduated cylinder d) 50 ml burette II. Reagents a) Copper Sulfate; dissolve 10g of copper sulfate 5H 2 O, 136g of sodium acetate 3H 2 O and 32 ml of acetic acid in water; dilute to one liter and mix Page 4 of 12

5 III. IV. b) Sodium Thiosulfate Anhydrous; dissolve 70g of sodium thiosulfate anhydrous in water; dilute to one liter and mix Procedure a) Pipette 5 ml of CIRCUPOSIT 71 Electroless Copper into a 100 ml volumetric flask. b) Add 10 ml of the copper sulfate solution. c) Add 10 ml of the sodium thiosulfate solution and shake. d) Dilute to exactly 100 ml with D.I. water. e) Measure absorbance, ABS (730 nm; D.I. Water reference). f) Obtain the concentration from the calibration curve. Calculation Formula for linear portion of Dow Electronic Materials calibration curve from 25 to 45 g/l. EDTA g/l = 75.5 (ABS) V. Calibration Curve 0.7 Absorbance vs. EDTA 4Na Content ABS EDTA (g/l) CIRCUPOSIT TM 71 U Electroless Copper CIRCUPOSIT TM 71 U Electroless Copper Control Procedure The CIRCUPOSIT 71 U Electroless Copper concentration should be between %. To raise the U content by 10%, add 1.0 ml/l of CIRCUPOSIT 71 U. CIRCUPOSIT 71 U concentration can be determined following the control procedure below. I. Equipment a) 200 ml beaker b) 100 ml graduated cylinder c) Two-250 ml separatory funnels d) 100 ml beaker e) Hot plate f) UV spectrophotometer II. Reagents a) Tri-sodium phosphate 12H 2O powder b) Sodium hydroxide, 1N c) Sulfuric acid, 1N d) Trichloroethylene e) Fe No. 1 solution; dissolve 3g of Mohr s salt (ferrous ammonium sulfate 6H 2 O), 10g of L- ascorbic acid, 40g of sodium chloride and 86 ml of acetic acid (99.5%) in water; dilute to one liter and mix f) Fe No. 2 solution; dissolve 40g of sodium acetate anhydrous in water; dilute to one liter and mix Note: Store reagents (e) and (f) in the refrigerator and use within one month. Page 5 of 12

6 III. Procedure a) Accurately measure a 100 ml sample of CIRCUPOSIT TM 71 Electroless Copper bath into a 200 ml beaker. b) Add 5g of Tri-sodium phosphate 12H 2 O powder and dissolve. c) After the powder has dissolved, confirm the ph at (Adjust with 1N NaOH or 1N H 2 SO 4 if necessary.) d) Decant into a 250 ml separatory funnel. e) Add approximately 50 ml of trichloroethylene. f) Shake for at least 5 minutes and allow to stand for at least 10 minutes. g) Decant only the trichloroethylene layer that contains the U component (bottom layer) into another 250 ml separatory funnel. h) Place 20 ml of Fe No. 1 solution (e) and 20 ml of Fe No. 2 solution (f) into a 100 ml beaker. Heat to C ( F) and add while hot to the above trichloroethylene solution. i) Immediately shake three times to let the vapor out. Color of the solution turns pink. j) Shake for at least 10 minutes and allow to stand for at least 15 minutes. k) Separate and dispose of the bottom trichloroethylene layer. l) Decant the red upper layer into a 200 ml beaker. m) Heat to approximately 60 C (140 F) with occasional stirring. n) As the slightly cloudy whitened-red solution becomes clear, decant into a 50 ml volumetric flask. o) After cooling to room temperature, dilute with D.I. water to 50 ml. p) Measure absorbance, ABS (520 nm; D.I. water reference). q) Obtain the concentration from the calibration curve. IV. Calculation Formula for linear portion of Dow Electronic Materials calibration curve from 50 to 150%. CIRCUPOSIT 71 U % = (ABS) (ABS) (ABS) 3 V. Calibration Curve 2.0 Absorbance vs. U Content % ABS Ingredient U Content (%) CIRCUPOSIT TM 71 S Electroless Copper The CIRCUPOSIT 71 S Electroless Copper concentration should be between %. To raise the S content by 10%, add 0.2 ml/l of CIRCUPOSIT 71 S. CIRCUPOSIT 71 S concentration can be determined following the control procedure below. Page 6 of 12

7 CIRCUPOSIT TM 71 S Electroless Copper Control Procedure I. Equipment a) 100 ml beaker b) 10 ml graduated pipette c) 5 ml graduated pipette d) 250 ml separatory funnel e) 50 ml volumetric flask f) UV spectrophotometer II. Reagents a) ph 3.5 buffer solution; dissolve 40g of sodium acetate anhydrous and 300 ml of acetic acid (99.5%) in water; dilute to one liter b) Orange II Indicator; dissolve 1g of Orange II indicator in water; dilute to one liter c) Concentrated hydrochloric acid d) Trichloroethylene e) NaCl III. Procedure a) Pipette a 10 ml sample of CIRCUPOSIT 71 Electroless Copper bath into a beaker. b) Dilute to 50 ml with D.I. water. c) Add and dissolve 5 ml of ph 3.5 buffer solution and 5g of NaCl. d) Add 3 ml of 0.1% Orange II indicator. e) Adjust to ph 3.5 with concentrated HCl. f) Decant into a 250 ml separatory funnel. g) Add 40 ml of trichloroethylene. h) Shake for at least 5 minutes and allow to stand for at least 10 minutes. (Release gas at beginning of shaking.) i) Decant the trichloroethylene layer (bottom layer, orange color) into a dry 50 ml volumetric flask. j) Bring to 50 ml total with trichloroethylene and shake. k) Immediately measure absorbance (485 nm; Trichloroethylene reference). l) Obtain the concentration from the calibration curve. IV. Calculation Formula for linear portion of Dow Electronic Materials calibration curve from 0 to 200%. CIRCUPOSIT 71 S % = 230(ABS) V. Calibration Curve ABS Absorbance vs. S Content % Ingredient S Content (%) Page 7 of 12

8 CIRCUPOSIT TM 71 T Electroless Copper CIRCUPOSIT TM 71 T Electroless Copper Control Procedure The CIRCUPOSIT 71 T Electroless Copper concentration should be between %. To raise the T content by 10%, add 2.0 ml/l of CIRCUPOSIT 71 T. CIRCUPOSIT 71 T concentration can be determined following the control procedure below. I. Equipment a) Two-100 ml volumetric flasks b) 10 ml graduated pipette c) 5 ml transfer pipette d) Hot plate e) UV spectrophotometer II. Reagents a) 0.5% Sulfuric Acid b) Ammonium molybdate; dissolve 70g of ammonium molybdate 4H 2O in D.I. water; dilute to one liter c) Reference solution; pipette 5 ml plating solution and dilute to approximately 50 ml with D.I. water; bring to ph with 5% III. sulfuric acid; bring to 100 ml in a volumetric flask Procedure a) Accurately pipette a 5 ml sample of CIRCUPOSIT 71 Electroless Copper bath into a volumetric flask. b) Dilute to 50 ml with D.I. water. c) Adjust ph to with 5% sulfuric acid solution. d) Add 10 ml of ammonium molybdate (70 g/l) solution. e) Boil for minutes. f) After cooling, bring to 100 ml in a volumetric flask. g) Measure absorbance; ABS (390 nm; reference solution as reference). h) Obtain the concentration from the calibration curve. IV. Calculation Formula for linear portion of Dow Electronic Materials calibration curve from 0 to 200%. CIRCUPOSIT 71 T % = 191(ABS) V. Calibration Curve ABS Absorbance vs. T Content % Ingredient T Content (%) Page 8 of 12

9 Replenishment Dilute CIRCUPOSIT 71 A Electroless Copper to 25% strength, CUPOSIT TM Y and CUPOSIT Z Additives to 50% strength. Replenishment of copper bath requires a continuous flow of replenishers. The exact flow of replenishers primarily depends on the bath loading and copper deposition rate. As a starting point, set the pump for a loading of 1.0 dm2/l (0.4 ft 2 / gal.) to replenish as follows: Replenishment Schedule 100 liter (26 gal.) bath 100 liter bath (ml/min.) CIRCUPOSIT 71 A Electroless Copper 8.8* CIRCUPOSIT 71 E 3.3 CIRCUPOSIT 71 S 0.11 CIRCUPOSIT 71 T 0.44 CIRCUPOSIT 71 U 0.55 CUPOSIT TM Y Additive 10.0* CUPOSIT Z 8.0* Adjust pump to maintain at level CIRCUPOSIT 71 A Cu content 3.05 g/l (0.41 oz./gal.) CIRCUPOSIT 71 E EDTA content ~43 g/l (5.7 oz./gal.) CIRCUPOSIT 71 U U content ~100% CIRCUPOSIT 71 T T content ~110% CIRCUPOSIT 71 S S content ~75% CUPOSIT Y Plating rate CUPOSIT Z ph = *After dilution Bailout And Water Addition Typical Consumption For 378 Liter (100 Gallon) Bath The normal bailout rate is 15% of bath volume per cycle. Bath Volume: 100 liters (26 gallons) Bath Loading: 1.0 dm 2 /L (0.4 ft 2 /gallon) Plating Rate: 2.5 µm/hour (100 µin/hour) Bailout Rate: Should be 1.1 liter per hour (0.29 gal./hour) The hourly bailout volume is proportional to the plating rate and bath loading. Larger bailout will be needed to keep the specific gravity of the bath below The volume of the bath should be maintained by manual or automatic level control. Typical total consumption for make-up and replenishment to run 4 cycles, based on 15% bailout rate, is as follows: Page 9 of 12

10 Typical Consumption for 378 liter (100 gallon) bath Make-up Total Consumption CIRCUPOSIT 71 E 64.3 liters (17 gal.) liters (27.4 gal.) Electroless Copper CIRCUPOSIT 71 A 5.7 liters (1.5 gal.) 31.8 liters (8.4 gal.) CIRCUPOSIT 71 U 3.8 liters (1.0 gal.) 10.2 liters (2.7 gal.) CIRCUPOSIT 71 T 7.6 liters (2.0 gal.) 13.2 liters (3.5 gal.) CIRCUPOSIT 71 S 0.76 liters (0.2 gal.) 1.9 liters (0.5 gal.) CUPOSIT TM Y Additive 3.8 liters (1.0 gal.) 63.2 liters (16.7 gal.) CUPOSIT Z 3.8 liters (1.0 gal.) 51.5 liters (13.6 gal.) Typical total consumption for each cycle after 4 cycles, based on 50% bailout rate, is as follows: Typical Consumption for 378 liter (100 gallon) bath CIRCUPOSIT 71 E Electroless Copper Per Cycle Add. Total Consumption 19.7 liters (5.2 gal.) liters (32.6 gal.) CIRCUPOSIT 71 A 7.57 liters (2.0 gal.) 39.4 liters (1.04 gal.) CIRCUPOSIT 71 U 3.4 liters (0.9 gal.) 13.6 liters (3.6 gal.) CIRCUPOSIT 71 T 3.0 liters (0.8 gal.) 16.3 liters (4.3 gal.) CIRCUPOSIT 71 S 0.38 liters (0.1 gal.) 2.3 liters (0.6 gal.) CUPOSIT TM Y 16.7 liters (4.4 gal.) 79.9 liters (21.1 gal.) CUPOSIT Z 13.6 liters (3.6 gal.) 65.1 liters (17.2 gal.) Equipment Tanks: Polypropylene, fluoropolymer or fluoropolymer-coated Heaters: Fluoropolymer or fluoropolymer-coated coils Filtration: Continuous bath circulation through 1 5 micron polypropylene filtration cartridges is mandatory; examine and replace cartridges as necessary Pump: External pump with intake from sump Process Lines: Polypropylene, Fluoropolymer-resin Air Lines: Rigid CPVC Plumbing: Rigid CPVC Product Data CIRCUPOSIT 71 E Electroless Copper Appearance: Blue ph: 12.5 Specific Gravity: 1.14 CIRCUPOSIT 71 A Appearance: Blue ph: <2.0 Specific Gravity: 1.45 CIRCUPOSIT 71 U Appearance: Blue ph: 2.0 Specific Gravity: 1.0 Page 10 of 12

11 CIRCUPOSIT TM 71 T Electroless Copper Appearance: Clear, colorless ph: 13.0 Specific Gravity: 1.05 CIRCUPOSIT 71 S Appearance: Blue ph: 10.5 Specific Gravity: 1.03 CUPOSIT TM Y Appearance: Clear, colorless ph: 6.0 Specific Gravity: 1.1 CUPOSIT Z Appearance: Clear, colorless ph: >12.0 Specific Gravity: 1.3 Page 11 of 12

12 Handling Precautions Before using this product, or the analytical reagents required for this control, consult the Material Safety Data Sheet (MSDS)/Safety Data Sheet (SDS) for details on material hazards, recommended handling precautions and product storage. CAUTION! Keep combustible and/or flammable products and their vapors away from heat, sparks, flames and other sources of ignition including static discharge. Processing or operating at temperatures near or above product flashpoint may pose a fire hazard. Use appropriate grounding and bonding techniques to manage static discharge hazards. CAUTION! Failure to maintain proper volume level when using immersion heaters can expose tank and solution to excessive heat resulting in a possible combustion hazard, particularly when plastic tanks are used. Storage Disposal Considerations Store products in tightly closed original containers at temperatures recommended on the product label. Dispose in accordance with all local, state (provincial) and federal regulations. Empty containers may contain hazardous residues. This material and its container must be disposed in a safe and legal manner. It is the user's responsibility to verify that treatment and disposal procedures comply with local, state (provincial) and federal regulations. Contact your Dow Electronic Materials Technical Representative for more information. Product Stewardship Customer Notice Dow has a fundamental concern for all who make, distribute, and use its products, and for the environment in which we live. This concern is the basis for our product stewardship philosophy by which we assess the safety, health, and environmental information on our products and then take approp riate steps to protect employee and public health and our environment. The success of our product stewardship program rests with each and every individual involved with Dow products - from the initial concept and research, to manufacture, use, sale, disposal, and recycle of each product. Dow strongly encourages its customers to review both their manufacturing processes and their applications of Dow products from the standpoint of human health and environmental quality to ensure that Dow products are not used in ways for which they are not intended or tested. Dow personnel are available to answer your questions and to provide reasonable technical support. Dow product literature, including safety data sheets, should be consulted prior to use of Dow products. Current safety data sheets are available from Dow. For Industrial Use Only. This information is based on our experience and is, to the best of our knowledge, true and accurate. However, since conditions for use and handling of products are beyond our control, we make no guarantee or warranty, expressed or implied, regarding the information, the use, handling, storage or possession of the products, or the applications of any process described herein or the results sought to be obtained. Nothing herein shall be construed as a recommendation to use any product in violation of any patent rights. Contact: North America: Japan: (+81) Asia: (+852) Europe: (+41) Notice: No freedom from infringement of any patent owned by Dow or others is to be inferred. Because use conditions and applicable laws may differ from one location to another and may change with time, Customer is responsible for determining whether products and the information in this document are appropriate for Customer's use and for ensuring that Customer's workplace and disposal practices are in compliance with applicable laws and other government enactments. The product shown in this literature may not be available for sale and/or available in all geographies where Dow is represented. The claims made may not have been approved for use in all countries. Dow assumes no obligation or liability for the information in this document. References to Dow or the Company mean the Dow legal entity selling the products to Customer unless otherwise expressly noted. NO WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCLUDED. Page 12 of 12