Color‐Saturated Green‐Emitting QD‐LEDs

Semiconductor nanocrystals (NCs) or quantum dots (QDs) show great promise for use in QD-LED (quantum dot lightemitting device) displays, owing to their unique optical properties and the continual development of new core and core–shell structures to meet specific color needs. This in combination with the recent development of more efficient and saturated QD-LEDs as well as new QD-LED fabrication techniques, suggests that QD-LEDs have the potential to become an alternative flat-panel display technology. The ideal red, green, and blue emission spectrum of an LED for a display application should have a narrow bandwidth and a wavelength such that its color coordinates on the Commission Internationale de l+Eclairage (CIE) chromaticity diagram lie outside the current National Television System Committee (NTSC) standard color triangle (see Figure 2). For a Gaussian emission spectrum with a full width at half maximum (FWHM) of 30 nm and a maximized perceived power, the optimal peak wavelength for display applications is l= 610– 620 nm for red, l= 525–530 nm for green, and l= 460– 470 nm for blue. For the red pixels, wavelengths longer than l= 620 nm become difficult for the human eye to perceive, while those shorter than l= 610 nm have coordinates that lie inside the standard NTSC color triangle. Optimization of wavelength for the blue pixels follows the same arguments as for the red pixel, but at the other extreme of the visible spectrum. For green pixels, l= 525–530 nm provides a color triangle with the largest area on the CIE chromaticity diagram (and therefore the largest number of colors accessible by a display). Wavelengths longer than l= 530 nm make some of the blue/green area of the triangle inaccessible. Wavelengths shorter than l= 525 nm compromise the yellow display emissions. To date, efficient red-emitting QD-LEDs with a peak emission wavelength optimized for display applications have been realized using (CdSe)ZnS core–shell NCs, while blue QD-LEDs with a peak wavelength of emission optimized for display applications have been realized with a (CdS)ZnS core–shell material. To date, although efficient green-emitting core–shell semiconductor NCs that emit at l= 525 nm have been synthesized, they have not been successfully incorporated into a QD-LED suitable for display applications. Previous work using (CdSe)ZnS core–shell NCs gave QD-LEDs that emit at wavelengths no shorter than l= 540–560 nm. 14] Using (CdSe)ZnS core–shell NCs to achieve l= 525 nm emission requires making small CdSe cores ( 2.5 nm in diameter). 16] Such small CdSe semiconductor NCs can be difficult to synthesize with narrow size distributions and high quantum efficiencies, and are also more difficult to process and overcoat with a higher-band-gap inorganic semiconductor, which is necessary for incorporation into solid-state structures. A core–shell composite, rather than an organically passivated NC, is desirable in a solid-state QD-LED device owing to the enhanced photoluminescence and electroluminescence (EL) quantum efficiencies of core– shell NCs and their greater tolerance to the processing conditions necessary for device fabrication. Larger NCs are also more desirable for use in QD-LEDs because the absorption cross section of NCs scales with size. Larger NCs with larger absorption cross sections lead to an increase in the efficiency of F?rster energy transfer from electroluminescing organic molecules to NCs in a working QD-LED, which in turn leads to more efficient devices. Herein, we report the synthesis of a CdxZn1 xSe alloy core on which we then grew a CdyZn1 yS shell to create a core– shell NC material with the ideal spectral characteristics for green emission in a QD-LED display and with a size large enough for fabricating a working QD-LED. Our CdxZn1 xSe core synthesis was based on work recently published, in which Cd and Se precursors were slowly introduced into a growth solution of ZnSe NCs. A three-step synthetic route was employed to prepare the (CdxZn1 xSe)CdyZn1 yS core–shell NCs. In the first step, ZnSe NCs were prepared by rapidly injecting 0.7 mmol of diethylzinc (Strem) and 1 mL of tri-noctylphosphine selenide (TOPSe; 1m) dispersed in 5 mL of tri-n-octylphosphine (TOP; 97% Strem) into a round-bottom flask containing 7 grams of degassed hexadecylamine (distilled from 90% Sigma–Aldrich) at 310 8C and by then growing the NCs at 270 8C for 90 min. The second step consisted of transferring 8 mL of the above ZnSe NC growth solution, at 160 8C, into a degassed solution of 16 grams of trin-octylphosphine oxide (TOPO; distilled from 90% Sigma– Aldrich) and 4 mmol of hexylphosphonic acid (HPA; Alfa Aesar), also at 160 8C. A solution of 1.1 mmol of dimethylcadmium (Strem) and 1.2 mL of TOPSe (1m) dispersed in 8 mL of TOP (97% Strem) was then introduced dropwise [*] Dr. J. S. Steckel, Dr. P. Snee, Dr. J. P. Zimmer, J. E. Halpert, Prof. M. G. Bawendi Massachusetts Institute of Technology Department of Chemistry Center for Materials Science and Engineering and The Institute for Soldier Nanotechnologies 77 Massachusetts Avenue, Room 6-221 Cambridge, MA 02139 (USA) Fax: (+1)617-253-7030 E-mail: mgb@mit.edu Dr. S. Coe-Sullivan, P. Anikeeva, L.-A. Kim, Prof. V. Bulovic Massachusetts Institute of Technology Laboratory of Organic Optics and Electronics Department of Electrical Engineering and Computer Science Cambridge, MA 02139 (USA) [] These authors contributed equally to this work.