Supporting Information. Preparation and Evaluation of a Zirconia/Oligosiloxane Nanocomposite for LED Encapsulation

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1 Supporting Information Preparation and Evaluation of a Zirconia/Oligosiloxane Nanocomposite for LED Encapsulation Pao-Tang Chung, Shian-Hau Chiou, Chin-Yao Tseng, Anthony Shiaw-Tseh Chiang* Dept. Chemical & Materials Engineering, National Central University *stchiang@cc.ncu.edu.tw S-1

2 Table S1. Specifications of the LED packages employed Package Lead frame LED die Size (mil) Source Dominant (nm) Forward Current (ma) P1 NTF-010-K Epileds Co P2 NTF-010-K Epileds Co P3 NCTU Genesis photonics NTF-010-K1 (with lens) is from NANTEC. NCTU-5050 (without lens) is from NCTU Semiconductor Laser Technology Laboratory. GaN-based blue-led chip was employed in all cases. Schematic S1. Schematic drawing representing the architecture of package P1 and P2 NTF-010-K1 GaN LED Ag paste Sn solder Silicone lens Cu substrate heat sink Schematic S2. Schematic drawing representing the architecture of package P3 NCTU-5050 Sn solder Ag paste GaN LED Cu substrate heat sink S-2

3 Figure S1. 1H NMR spectrum of MPTMS (a), BA (b) and the dual-modified zirconia nanocrystal (c) from which we calculate the BA/MPS molar ratio is (a) pure MPTMS (b) (d) CH (a) H 3 (d) O H H 3 C (g) O Si (f) (c) O CH3 O (d) CDCl 3 (a) (b) O (e) CH 3 (c) (d) (e) (f) (g) (b) pure BA (h) HO O (i) (j) CH 3 (h) (i) (j) CDCl 3 (c) Dual-modified zirconia (e) CDCl 3 (a) (b) (c) (h) (f) (i) (j) (g) chemical shift (ppm) S-3

4 Figure S2. Confirmation of the estimated refractive index for modified zirconia nanoparticles by matching the predicted index of 2-Phenoxy ethyl acrylate dispersions with that measured at various particle loadings Phenox ethyl acrylate sol Extrapolate to Refractive Effective medium (Bruggeman) Vol fraction of zirconia filler Figure S3. The particle size distribution of modified zirconia nanocrystal dispersed (5wt%) in different solvents as measured by DLS analysis. Volume density Chloroform EA Toluene PGMEA THF Benzene MEK MMA styrene size (d,nm) S-4

5 Figure S4. 29 Si NMR spectra of the three oligosiloxane resins S1, S2 and S3 discussed in this study. S1 DoC = 95 % DPSD D 1 D 2 MPS T 2 T 3 Intensity S2 DoC = 80 % DMDMS D 1 D 2 DPSD D 1 D 2 MPS T 2 T 3 S3 DoC = 86 % DPSD MPS D 1 D 2 T 2 T 3 DMDMS D 1 D 2 TPS M chemical shift (ppm) The degree of condensation (DOC) for the oligosiloxane was calculated from the area occupied by different 29 Si NMR signals, according to the equation 1,2 : DOC(%) i i i im id it i 0 i 0 i i i i M 2 D 3 T i 0 i 0 i 0 In here, i M, i D and i T are the Si-species with one, two and three hydrolysable silane- compounds, respectively, with i being the number of siloxane bounds formed on the Si-atom. The denominator is the sum of all possible siloxane bounds. The nominator is the total number of siloxane bounds actual formed. S-5

6 Figure S5. Magnified pictures of the encapsulations showing the appearance of cracks and oily phase in the encapsulant S-1 and S-2, respectively. In here, P1, P2 and P3 are the type of lead frame and die listed in Table S1. R0, R1, S1, S2 and S3 are the type of resin used to encapsulate the package. P1-R1 P1-S1 P1-S2 P2-R0 P2-R1 P2-S3 P3-R0 P3-R1 P3-S3 Due to the crack and the phase separation, the light output of packages P1-S1 and P1-S2 quickly dropped after the first 60 hours under hot and humid conditions. The light intensity reduced to about 85% of the initial value after 600 hours. Comparatively, the package encapsulated by the reference resin maintained at about 95% its original output in the first 200 hours and remained above 90% after 600 hours of testing. S-6

7 Figure S6. The results of TGA analysis for zirconia/oligosiloxane composites Weight(%) S3 C-2 C-3 C-4 Filler Derivative Temperature o C S-7

8 Figure S7. The comparison of view angle between P3-R1 and P3-C2 packages Radiometric (W/m) P3-R1 P3-C View Angle (degees) References 1. Sepeur, S.; Kunze, N.; Werner, B.; Schmidt, H. UV Curable Hard Coatings on Plastics. Thin Solid Films 351[1-2], Yang, S.; Kwak, S. Y.; Jin, J.; Bae, B. S. Highly Condensed Epoxy- Oligosiloxane-Based Hybrid Material for Transparent Low-k Dielectric Coatings. ACS Appl. Mater. Interfaces 2009, 1 (7), S-8