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1 Electronic Supplementry Mteril (ESI) for Journl of Mterils Chemistry C. This journl is The Royl Society of Chemistry 2018 Electronic supplementry informtion ovel Dendritic Lrge Molecules s Solution-Processble Thermlly Activted Delyed Fluorescent Emitters for Simple Structured on-doped Orgnic Light Emitting Diodes Mlleshm Goduml, Sun Choi, Hyung Jong Kim, Chiho Lee, Sungnm Prk, Ji Su Moon, b Si Woo Kim, b Jng Hyuk Kwon, b Min Ju Cho nd Dong Hoon Choi* Deprtment of Chemistry, Reserch Institute for turl Sciences, Kore University, 145 Anm-ro, Seongbuk-gu, Seoul, 02841, Republic of Kore. b Deprtment of Informtion Disply, Kyung Hee University, 26, Kyungheede-ro, Dongdemun-gu, Seoul, 02447, Republic of Kore *Emil: dhchoi8803@kore.c.kr Fx: , Tel: Figures TBCZ TB7CZ Fig. S1 Chemicl structures of crbzole-bsed dendrons nd emissive core used in this study. 1

2 TB2CZ- TB14CZ- Het flow Temperture ( o C) Fig. S2 DSC thermogrms of the TB2CZ- nd TB14CZ-. () ormlized bsorbnce (.u.) Toluene Film Wvelength (nm) ormlized PL Intensity (.u.) ormlized bsorbnce (.u.) Toluene Film Wvelength (nm) ormlized PL Intensity (.u.) Fig. S3 UV-Vis bsorption nd PL spectr of () TB7CZ, nd in toluene nd film sttes. 2

3 () ormlized bsorbnce (.u.) (c) ormlized bsorbnce (.u.) hexne toluene chloroform EA Wvelength (nm) hexne toluene chloroform EA Wvelength (nm) ormlized PL Intensity (.u.) (d) ormlized PL Intensity (.u.) Wvelength (nm) Wvelength (nm) Fig. S4 UV-Vis bsorption nd PL spectr of TB2CZ- ( nd b) nd TB14CZ- (c nd d) in different polr solvents. 3

4 () ormlized Intensity (.u.) Fluorescence Phoshorescence Wvelength (nm) ormlized Intensity (.u.) Fluorescence Phoshorescence Wvelength (nm) Fig. S5 Low temperture fluorescence nd phosphorescence spectr mesured t 77K in film sttes. () TB2CZ- nd TB14CZ- () 100 K 200 K 300 K ormlized Intensity (.u.) Time ( s) ormlized Intensity (.u.) K 200 K 300 K Time ( s) Fig. S6 Temperture-dependent trnsient PL decy of () TB2CZ- nd TB14CZ- in film sttes. 4

5 () EL Intensity (.u.) (c) EQE (%) Wvelength (nm) TB2CZ- TB14CZ- TB2CZ- TB14CZ (d) Current Efficiency (cd A -1 ) TB2CZ- TB14CZ Voltge (V) 10 2 TB2CZ- TB14CZ Luminnce (cd m -2 ) Power Efficiency (lm W -1 ) Fig. S7 Chrcteristics of TADF-OLED devices for TB2CZ- (t=120 nm) nd TB14CZ- (t=90 nm): () the normlized EL spectr (mesured t 1000 cd m -2 ), current density voltge luminnce (J V L), (c) EQE versus current density, nd (d) current efficiency nd power efficiency versus current density plots. The inset in Fig. is the device structure. () Energy xis (ev) ITO TB2CZ: TB14CZ: TPBI LiF/Al Energy xis (ev) ITO -5.2 PEDOT :PSS PVK TB2CZ: TB14CZ: TPBI LiF/Al Fig. S8 Schemtic energy level digrms of () device A, nd device B. 5

6 () EL Intensity (.u.) (c) EQE (%) TB2Cz- TB14Cz- TB2CZ- TB14CZ Wvelength (nm) (d) Current Efficiency (cd A -1 ) TB2CZ- TB14CZ Voltge (V) TB2CZ- TB14CZ Luminnce (cd m -2 ) Power Efficiency (lm W -1 ) Fig. S9 Chrcteristics of TADF-OLED devices for TB2CZ- nd TB14CZ-: () the normlized EL spectr, t 1000 cd m -2 (inset shows the device structure), current density voltge luminnce (J V L), (c) EQE versus current density nd (d) current efficiency nd power efficiency versus current density plots. 6

7 () (C) (D) Voltge (V) (C) (D) Voltge (V) Fig. S10 Current density voltge (J V) chrcteristics of hole only devices in simple (device C) nd multilyered structure (device D): () TB2CZ- nd TB14CZ-. Tbles Tble S1: Opticl, photophysicl, nd electrochemicl dt of key frgments (TB7CZ nd ). compound λ bs /b (nm) λ em /b (nm) E g c (ev) HOMO d (ev) LUMO e (ev) TB7CZ 300, 333, 349/ 299, 335, , 406/ 334, / / In toluene. b In thin film. c Clculted from bsorption threshold (film stte). d Clculted using oxidtion onset in film stte. e Obtined by dding opticl bnd gp to HOMO level. 7

8 Tble S2: UV-Vis bsorption nd PL dt of TB2CZ- nd TB14CZ- in different polr solvents. compound Hexne /b (nm) Toluene /b (nm) Chloroform /b (nm) EA /b (nm) TB2CZ- 298, 335, 347/ 389, 467, , 338, 349/ 394, , 338, 349/ 425, , 337, 348/ 400, 572 TB14CZ- 298, 335, 348/ 388, , 336, 349/ 392, , 337, 350/ 396, , 336, 348/ 390, 558 UV-Vis bsorption. b PL dt. Tble S3: TB2CZ- nd TB14CZ- dendrimers bsed TADF-OLED performnce dt (device A). Compound V on (V) Luminnce b (cd m -2 ) CE b (cd A -1 ) PE b (lm W -1 ) EQE (%) b λ mx c (nm) CIE c (x,y) TB2CZ , 0.57 TB14CZ , 2 Turn-on voltge t brightness of 1 cd m -2. b Mximum vlue. c At luminnce of 1000 cd m -2. * CE : current efficiency, PE: power efficiency, EQE: externl quntum efficiency. Thickness of TB2Cz-= 120 nm; Thickness of TB14Cz- = 90 nm Tble S4: TB2CZ- nd TB14CZ- dendrimers bsed TADF-OLED performnce dt (device B). Compound V on (V) Luminnce b (cd m -2 ) CE b (cd A -1 ) PE b (lm W -1 ) EQE (%) c t mx/100/500 cd m -2 λ mx d (nm) CIE d (x,y) TB2CZ /9.9/ , 0.57 TB14CZ /5.4/ , 2 Turn-on voltge t brightness of 1 cd m -2. b Mximum vlue. c Dt t mximum, 100 nd 1000 cd m -2. d At luminnce of 1000 cd m -2. * CE : current efficiency, PE: power efficiency, EQE: externl quntum efficiency. 8