Organic single crystals have a great potential in the field of organic optoelectronics because of their advantages of high carrier mobility and high thermal stability. However, the application of the organic single crystals in light‐emitting devices (OLEDs) has been limited by single‐layered structure with unbalanced carrier injection and transport. Here, fabrication of a multilayered‐structure crystal‐based OLED constitutes a major step toward balanced carrier injection and transport by introducing an anodic buffer layer and electron transport layer into the device structure. Three primary color single‐crystal‐based OLEDs based on the multilayered structure and molecular doping exhibit a maximum luminance and current efficiency of 820 cd cm−2 and 0.9 cd A−1, respectively, which are the highest performance to date for organic single‐crystal‐based OLEDs. This work paves the way toward high‐performance organic optoelectronic devices based on the organic single crystals.

Organic single-crystalline semiconductors with long-range periodic order have attracted much attention for potential applications in electronic and optoelectronic devices due to their high carrier mobility, highly thermal stability, and low impurity content. Molecular doping has been proposed as a valuable strategy for improving the performance of organic semiconductors and semiconductor-based devices. However, a fundamental understanding of the inherent doping mechanism is still a key challenge impeding its practical application. In this study, solid evidence for the "perfect" substitutional doping mechanism of the stacking mode between the guest and host molecules in organic single-crystalline semiconductors using polarized photoluminescence spectrum measurements and first-principles calculations is provided. The molecular host-guest doping is further exploited for efficient color-tunable and even white organic single-crystal-based light-emitting devices by controlling the doping concentration. The clarification of the molecular doping mechanism in organic single-crystalline semiconductor host-guest system paves the way for their practical application in high-performance electronic and optoelectronic devices.

Organic single crystals with much higher carrier mobility and stability compared to the amorphous organic materials have shown great potential in electronic and optoelectronic devices. However, their applications in white organic light‐emitting devices (WOLEDs), especially the three‐color‐strategy WOLEDs, have been hindered by the difficulties in fabricating complicated device structures. Here, double‐doped white‐emission organic single crystals are used as the active layers for the first time in the three‐color‐strategy WOLEDs by co‐doping the red and green dopants into blue host crystals. Precise control of the dopant concentration in the double‐doped crystals results in moderately partial energy transfer from the blue donor to the green and red dopants, and thereafter, simultaneous RGB emissions with balanced emission intensity. The highest color‐rendering index (CRI) and efficiency, to the best of the authors' knowledge, are obtained for the crystal‐based WOLEDs. The CRI of the WOLEDs varies between 80 and 89 with the increase of the driving current, and the luminance and current efficiency reach up to 793 cd m−2 and 0.89 cd A−1, respectively. The demonstration of the present three‐color organic single‐crystal‐based WOLED promotes the development of the single crystals in optoelectronics.