Clevios™ Etch – Technical Guide for Clevios™ SET S3

Heraeus Deutschland GmbH & Co. KG

Guntermann | HNB-DS | Jan 2015 Seite 1

Patterning by Clevios™ SET S3

Clevios™ Print Clevios™ Clevios™ SET S3

Coated Film Clevios™ SET S3 Etch Removal

Printed by Screen** Etch 60-120 seconds in 1. Remove with selected solvents(1)

printing 10% Clevios Etch Rinse for approx 60 sec @ 20°C -25°C
Use a wet layer thickness solution*) @ 27°C or
of 6-10µm 2. Remove with 1.25% ammonia solution(2)
Rinse with DI-water
Dry for 1-2 min @ 80°C Rinse for 2 min @ 25°C or 30-60 sec @40°C
Wash with rinsing DI-water and dry for 2min@100 °C

* Etching time based on Clevios™ F ET coating. Etching time for other formulations can be different .
** 355 mesh/inch; 31 µm Polyester yellow

(1) MEK-Ethanol 25:75 – 20:80 or Acetone

(2) For improved stripping results we recommend to add a small amount of e.g Triton X-100 ( 1% by weight on Ammonia sol.)

Guntermann | HNB-DS | Jan 2015 Page 2

CLEVIOS ETCH

CLEVIOS SET S3 – GNU 1676

Solid Content :ca 25 %

Viscosity : ca 2-3 Pa.s

Dilution : MMB (3-Methoxy-3-methyl-1-butanol) B.P 174°C

Printing conditions : 355 mesh/inch

For Finelines > 400 mesh/inch
Drying : 1-2 minutes @ 80°C

Screen Cleaning : with Acetone

Guntermann | HNB-DS | Jan 2015 Page 3

ROTO VISCO RV1 – CONE / PLATE

Viscosity
Clevios SET S3
3,00

2,50

2,00
η in Pas

1,50
GNU 1676

1,00

0,50

0,00
0,00 200,00 400,00 600,00 800,00 1000,00 1200,00 1400,00 1600,00 1800,00 2000,00
1/s

Guntermann | HNB-DS | Jan 2015 Seite 4

CLEVIOS SET S 3

Troubleshooting Bubbles

How to avoid/reduce bubbles

Flash-off time before drying 2 minutes – don´t dry immediately after printing

Clevios SET S3 can be diluted with MMB (3-Methoxy-3-methyl-1-butanol)

reducing the viscosity will decrease the bubble formation

Don´t Re-use Clevios SET S3.

Using a trampolin screen (metal mesh) similar to fineline screen

Guntermann | HNB-DS | Jan 2015 Seite 5

PRINTING

Typical Printing Parameter

Heraeus

Mesh 355 mesh/inch

Or higher e.g VA400
Thread Diameter 31µm

Material Polyester

Squeegee durometer 70-75

Squeegee angle 10° = 80° Trampoline VA400

Flood bar angle 0°

Print speed 86 mm/sec

Snap off 5 mm

Flash off time 60-120“

Drying 80°C/1-2min

Screen Cleaning Acetone

Guntermann | HNB-DS | Jan 2015 Seite 6

PRINTING

Lineprofiles (Trampoline VA400 )

# Dektak 150
# ZS3 on PET, silk-screen print
L/S 300 / 100 200 / 100 100 / 100 200 / 80 100 / 80
Position Line Separation Line Separation Line Separation Line Separation Line Separation
Width (µm) Width (µm) Width (µm) Width (µm) Width (µm)
297 106 190 112 110 94 208 83 121 70
282 111 198 100 111 96 200 69 112 64
284 117 196 99 108 90 211 66 107 71

Guntermann | HNB-DS | Jan 2015 Page 7

 Preparation of an etching solution

Dissolve Clevios™ Etch at room temperature in water

After stirring for 30 minutes, remove residues by filtration, filter type 5-10 µm
polypropylene or Whatman filter paper Grade 595 or 602

Use etching solution within 48 h

NEVER STORE THE ETCHING SOLUTION IN A CLOSED BOTTLE !!
If stored for more than 48 h, storage temperature should be lower than 23°C
Used solution should be disposed within short time.
See also additional Information

Guntermann | HNB-DS | Jan 2015 Page 8

Clevios™ Etching Process
Contact angle
 Best results are obtained if the contact angle (water) of the coating is in a range of
40°-60°. Otherwise longer etching time maybe needed. Use test samples to determine
etching time.
Resolution
 In case of using Clevios™ SET S the maximum resolution is approximately 50µm
 Finer lines may also be possible, but may need longer etching time

Crosslinking
 Highly solvent resistant coatings may need longer etching time. Use test samples to find
the right balance.

Temperature of the Etching bath

 For etching the temperature should be in range of 25-30°C.
 After etching the solution should be cooled below 23°C.
Guntermann | HNB-DS | Jan 2015 Page 9
 Etching process (detailed description)
Products needed : Clevios ™ F ET, Clevios™ SET S3 and Clevios™ Etch

Film preparation

 Coat Clevios™ F ET and dry at 120°C for 5 min.

 Print the Clevios™ SET S3 material with approx. 6-10µm wet film thickness

 Flash off time before drying – 2 minutes

 Dry at 80°C for 1-2 minutes

Etching

 Dip the film in a 10% solution of Clevios™ Etch (pH 5.7-7 @20°C) for 1-2 minutes @ 27°C with circulation

 Wash the film under rinsing water and dry @ 100°C for 2 minutes

Removal

 Dip the film in a 1.25% ammonia solution (pH 9-11 @20°C) for 2 minutes at RT or for 30-60 sec @ 40°C

 Additional washing in 1% sulfuric acid recovers the conductivity

 Alternative solution: remove the Clevios™ SET S3 with rinsing MEK-Ethanol or Acetone for 30-60 Seconds

 Wash with water again and dry the film for 2 minutes @ 100°C

Guntermann | HNB-DS | Jan 2015 Page 10

Clevios Etch
Clevios Etch releases: OCl- D ClO3- D HOCl D Cl2
First studies suggest:
- HOCl / Cl2 may be active species
- a halogenated intermediate may be involved
PEDOT oxidation – possible intermediates

O O O O O O O O O O O O
O O Cl
O
S S S H S Cl S S
O H H H
S S S S S S
Cl
O O O O O O O O O O O O
n

Other possible deactivation mechanisms / effects

- disruption/rearrangement of conductivity pathways (e.g. via reaction with binder/PSS)
- Macroscopic effects: outer layer of gel particles may be partially deactivated

Guntermann | HNB-DS | Jan 2015 Page 11

Etching Results of Clevios™ Etch
10% Solution

Guntermann | HNB-DS | Jan 2015 Page 12

CLEVIOS ETCH

Etching time @ 20°C – of Clevios™ F ET (12µm wet)

1,00E+09

1,00E+08

1,00E+07

1,00E+06
30 sec
60 sec
Ohm/sq.

1,00E+05
90 sec
1,00E+04 120 sec
150 sec
1,00E+03
180 sec
210 sec
1,00E+02

1,00E+01

1,00E+00
0 after 24h after 48h
Storage time of 10% Solution

Guntermann | HNB-DS | Jan 2015 Page 13

CLEVIOS ETCH

Etching time @ 22.5°C – of Clevios™ F ET (12µm wet)

1,00E+09

1,00E+08

1,00E+07

1,00E+06
30 sec
60 sec
Ohm/sq.

1,00E+05
90 sec
1,00E+04 120 sec
150 sec
1,00E+03
180 sec
210 sec
1,00E+02

1,00E+01

1,00E+00
0 after 24h after 48h
Storage time of 10% Solution

Guntermann | HNB-DS | Jan 2015 Page 14

CLEVIOS ETCH

Etching time @ 26.5°C – of Clevios™ F ET (12µm wet)

1,00E+09

1,00E+08

1,00E+07

1,00E+06
30 sec
60 sec
Ohm/sq.

1,00E+05
90 sec
1,00E+04 120 sec
150 sec
1,00E+03
180 sec
210 sec
1,00E+02

1,00E+01

1,00E+00
0 after 24h after 48h
Storage time of 10% Solution

Guntermann | HNB-DS | Jan 2015 Page 15

Chlorine Formation

Guntermann | HNB-DS | Jan 2015 Page 16

CLEVIOS ETCH

Chlorine formation during storage

of 1000 ml Clevios™ Etch (concentration in water: 10%)

0,9

0,8

0,7
Storage temperature: < 23°C
0,6
dm³

0,5

0,4

0,3

0,2

0,1

0
0 10 20 30 40 50 60 70 80
hours

Guntermann | HNB-DS | Jan 2015 Page 17

 Chlorine formation during storage
of 1000 ml Clevios™ Etch (concentration in water: 10%)
1,8

1,6

1,4

1,2

1
Storage temperature: 27 °C
dm³

0,8

0,6

0,4

0,2

0
0 2 3 4 5 6 7 8 25 26 27 28 32 48 72 96 168
hours

Guntermann | HNB-DS | Jan 2015 Page 18

 Disposal
Sodiumthiosulfate deactivates the active ingredients of Clevios Etch and is oxidized
to sulfate.

Disposal of Etching Solution

4 NaClO + Na2S2O3 + 2 NaOH → 4 NaCl + 2 Na2SO4 + H2O

For 100g of a 10% etching solution

• Prepare a solution of 3.94g of Na2S2O3 (sodium thiosulfate) in 100g water

• Add the thiosulfate solution to the etching solution slowly under stirring (temp.
control) exothermic reaction !
• The pH of the solution will change from 6.5 to 0.12.
• Slowly add a 26% solution of sodium hydroxide (NaOH) until the pH exceeds a
value of 11.
• No further smell of chlorine should be observed.

Dispose the obtained solution in accordance with local laws.

Guntermann | HNB-DS | Jan 2015 Page 19