Technical Report ZEP52 ZEP52 Ver.1.2 Mar.21 ZEONREX Electronic Chemicals High Resolution Positive Electron Beam Resist ZEP52 ZEON CORPORATION Specialty Materials Division Headquarters R&D Center Furukawa Sogo Bldg., 2-6-1 Marunouchi, 1-2-1 Yako, Kawakaki-ku Kawasaki-shi Chiyoda-ku, Tokyo 1-8323, JAPAN Kanagawa-ken 21-957, JAPAN Phone : 81-3-3216-59 Phone : 81-44- 276-3741 Fax : 81-3-3216-1827 Fax : 81-44- 276-3957 http://www.zeon.co.jp/
CONTENTS 1. Characteristics 2. Properties 3. Thinner 4. Developer 5. Rinse 6. Remover 7. Spin Curve 8. Dependence on Pre-bake Temperature 9. Dependence on Development Temperature & Time 1. Application Examples 11. Dry Etching Resistance 12. Example of 13. Handling Precaution 14. Appendix Any process conditions and data are examples. Those will not guarantee the same data in customers process. - 1 -
1. Characteristics ZEP52 series are high performance positive EB resists which show high resolution, high sensitivity and high dry etch resistance. They are suitable for various EB processes. (1) Resolution Show high resolution and rectangle pattern profile (2) Resistance to dry etching Show high dry etch resistance and are almost equivalent to that of positive photoresists generally used (3) Sensitivity Show high sensitivity 2. Properties Item Mw Viscosity (mpa s) Solvent Form ZEP52-12 12 o-dichlorobenzene 1QT bottle ZEP52 57, 22 or ZEP52A-7 7 Anisole 1ml bottle ZEP52A 11 3. Thinner Item Composition Remarks Form ZEP-S o-dichlorobenzene ZEP52-12 ZEP52 1QT bottle ZEP-A Anisole ZEP52A-7 ZEP52A 4. Developer Item Composition Remarks Form ZEP-RD Xylene (o-,m-,p- mixed) standard ZEP-N5 n-amyl acetate high resolution 1GL bottle ZED-WN o-xylene high resolution ZEP-SD 2-Butanone 4% Methyl isobutyl ketone 6% high sensitivity - 2 -
5. Rinse Item Composition Remarks Form ZMD-B Methyl isobutyl ketone 89% Isopropyl alcohol 11% 1GL bottle 6. Remover Item Composition Remarks Form ZDMAC Dimethylacetamide 1GL bottle 7. Spin Curve ZEP52 Spin Curve Thickness (Å) 6 5 4 3 2 1 ZEP52 ZEP52/Dilution Rate=2.5 ZEP52-12 ZEP52-12/Dilution Rate=2. ZEP52-12/Dilution Rate=2.5 Substrate : 4 inch Si wafer Spin Time : 6sec. PB time : 2min. (Oven) 1 3 5 7 Spin Speed (r.p.m.) ZEP52A Spin Curve Thickness (Å) 6 5 4 3 2 ZEP52A ZEP52A-7 Substrate : 4 inch Si wafer Spin Time : 6sec. PB time : 2min. (Oven) 1 1 3 5 7 Spin Speed (r.p.m.) - 3 -
8. Dependence on Pre-bake Temperature Dose to Clear (uc/cm 2 ) 45 4 35 3 25 2 15 1 5 12 14 16 18 2 22 Prebake Temperature o C 1min. Dev. 3min. Dev. Substrate : Si wafer PB time : 3min. Exposure : ELS33, 2kV Developer : ZED-N5 Dev. temp. : 23 o C Dev. time : 1, 3min. Rinse : ZMD-B, 23 o C, 1sec. Normalyzed Residual Thickness (%) 11 1 9 8 12 14 16 18 2 22 Prebake Temperature ( o C) 1min. Dev. 3min. Dev. Substrate : Si wafer PB time : 3min. Exposure : ELS33, 2kV Developer : ZED-N5 Dev. temp. : 23 o C Dev. time : 1, 3min. Rinse : ZMD-B, 23 o C, 1sec. - 4 -
9. Dependence on Development Temperature Dose to Clear (uc/cm 2 ) 45 4 35 3 25 2 15 1 5 15 2 25 3 Development Temperature ( o C) ZEP-RD ZED-WN ZED-N5 ZEP-SD Substrate : Si wafer PB time : 3min. Exposure : ELS33, 2kV Dev. time : 1min. Rinse : ZMD-B, 23 o C, 1sec. Normalyzed Residual Thickness (%) 11 1 9 8 15 2 25 3 Development Temperature ( o C) ZEP-RD ZED-WN ZED-N5 ZEP-SD Substrate : Si wafer PB time : 3min. Exposure : ELS33, 2kV Dev. time : 1min. Rinse : ZMD-B, 23 o C, 1sec. - 5 -
9. Dependence on Development Time Å Dose to Clear (uc/cm 2 ) 45 4 35 3 25 2 15 1 5 ZEP- RD ZED- WN ZED- N5 ZEP- SD 2 4 6 8 1 Development time (min.) Substrate : Si wafer PB time : 3min. Exposure : ELS33, 2kV Dev. temp. : 23 o C Rinse : ZMD-B, 23 o C, 1sec. Normalyzed residual thickness (%) 11 1 9 8 ZEP- RD ZED- WN ZED- N5 ZEP- SD 2 4 6 8 1 Development time (min.) Proce s s Conditions Subs trate : Si wafer Res is t : ZEP52 Film thicknes s : 5Å PB time : 3min. Expos ure : ELS33, 2k Dev. temp. : 23 o C Rins e : ZMD-B, 23 o C, 1-6 -
1. Application Examples.15µm Isolated Space PB time : 2min. Exposure : 3kV, 5 1-11 A, 1 line exp. 5 1-5 µc/cm Dev. temp. : ZED-WN, 23 o C, 3sec. Rinse : IPA, 23 o C, 2sec..1µm Isolated Line PB time : 2min. Exposure area : 1µm (2 2dot) Exposure : 3kV, 5 1-11 A, 1 line exp..7µsec./dot Dev. temp. : ZED-WN, 23 o C, 6sec. Rinse : IPA, 23 o C, 2sec..5µm Isolated Space Film thickness : 15Å Exposure : 75kV These data were presented by ELIONIX INC. - 7 -
11. Dry Etching Resistance (1) CF 4 Dry Etching Rate CF 4 Dry Etching Conditions.15torr, 7sqcm, 2W 35 3 Etching Rate (Å/min.) 25 2 15 1 5 ZEP series Competitor E Novolak Resist O (2) Cl 2 +O 2 Dry Etching Rate Cl 2 +O 2 Dry Etching Conditions Cl 2 /O 2 =4/1, 5min. Etching Rate (Å/min.) 5 45 4 35 3 25 2 15 1 5 ZEP52 Novolak Resist - 8 -
12. Example of (1) Coating (2) Pre-bake (3) Exposure (4) Development (5) Rinse (6) Post bake (7) De-scum (8) Etching ZEP52/52A 2rpm 6sec 5Å ZEP52-12/52A-7 2rpm 6sec 3Å 17-2 o C 2-3min. (Oven) 17-2 o C 2-5min. (Hot Plate) 2-5µC/ 2 cm at 2kV 2-25 o C 6-36sec. (Dipping) ZEP-RD, ZED-N5, ZED-WN 2-25 o C 1-6sec. (Dipping) ZMD-B In case of wet etching 1-14 o C 2-3min. (Oven) 1-14 2-3min. (Hot Plate) O 2 -plasma Dry process and wet process can be used. Wet Etching solution for Cr Ammonium cerium (IV) nitrate (NH 4 ) 2 Ce(NO 3 ) 6 Perchloric acid HClO 4 3-8wt% Pure water H 2 O 77-84wt% 13-18wt% (9) Resist Removing < deep-uv + organic solvent > 1 st step: 185nm+254nm,1mW/cm 2,3min.-irradiation 2 nd step: Dimethylacetamide (DMAC) or 1-Methyl-2-pyrrolidinone (NMP), 23 o C 1min. *As the polymer of ZEP52 is decomposed by deep-uv irradiation, it can be easily removed. <organic solvent > N-methyl-2-pyroridone (3-35 o C) <hot H 2 SO 4 -H 2 O 2 > hot H 2 SO 4 -H 2 O 2 (9-1 o C) - 9 -
13. Handling Precautions (1) Flammable Liquid (2) Harmful by inhalation (3) Avoid contact with skin and eyes CAUTION: Open carefully. Use in well ventilated area. In case of contact with skin and eyes, rinse immediately with plenty of water for 15 minutes and get medical attention. In case of fire use Alcohol form CO 2 or dry chemical, never use water. STORAGE: Keep capped and away from oxidants, sparks and open flame. Store at cool [32 o F ( o C) - 77 o F (25 o C)], dark place. Use in clean room. - 1 -
14. Appendix (1) Refractive Index of ZEP52 Film Cauchy Coefficient n = n + n 1 /λ 2 + n 2 /λ 4 n = 1.54193 n 1 = 4.1132 1 5 n 2 = 4.7357 1 12 Absorption coefficient = Unit of λ : Å Measured by UV-125/SE (KLA Tencor) (2) Glass Transition Temperature of ZEP52 Polymer Tg : 15 o C Measured by DSC < U.S.A > Zeon Chemicals L.P. (ZCLP) 4111 Bells Lane, Louisville, Kentucky 4211 (TEL) +1-52-775-236 (FAX) +1-52-775-225 < Europe > Zeon Europe GmbH Am Seestern 18 4547 Dusseldorf Germany (TEL ) +49-211-5267-113 (FAX) +49-211-5267-16 - 11 -