Organic Semiconductor Single Crystals Research Articles

Topology-Mediated Molecule Nucleation Anchoring Enables Inkjet Printing of Organic Semiconducting Single Crystals for High-Performance Printed Electronics.

Printable organic semiconducting single crystals (OSSCs) offer tantalizing opportunities for next-generation wearable electronics, but their development has been plagued by a long-standing yet inherent problem─spatially uncontrolled and stochastic nucleation events─which usually causes the formation of polycrystalline films and hence limited performance. Here, we report a convenient approach to precisely manipulate the elusive molecule nucleation process for high-throughput inkjet printing of OSSCs with record-high mobility. By engineering curvature of the contact line with a teardrop-shaped micropattern, molecule nucleation is elegantly anchored at the vertex of the topological structure, enabling formation of a single nucleus for the subsequent growth of OSSCs. Using this approach, we achieve patterned growth of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene single crystals, yielding a breakthrough for an organic field-effect transistor array with a high average mobility of 12.5 cm2 V-1 s-1. These findings not only provide keen insights into controlling molecule nucleation kinetics but also offer opportunities for high-performance printed electronics.

Wafer-Scale Epitaxial Growth of Two-dimensional Organic Semiconductor Single Crystals toward High-Performance Transistors.

The success of state-of-the-art electronics and optoelectronics relies heavily on the capability to fabricate semiconductor single-crystal wafers. However, the conventional epitaxial growth strategy for inorganic wafers is invalid for growing organic semiconductor single crystals due to the lack of lattice-matched epitaxial substrates and intricate nucleation behaviors, severely impeding the advancement of organic single-crystal electronics. Here, an anchored crystal-seed epitaxial growth method for wafer-scale growth of 2D organic semiconductor single crystals is developed for the first time. The crystal seed is firmly anchored on the viscous liquid surface, ensuring the steady epitaxial growth of organic single crystals from the crystal seed. The atomically flat liquid surface effectively eliminates the disturbance from substrate defects and greatly enhances the 2D growth of organic crystals. Using this approach, a wafer-scale few-layer bis(triethylsilythynyl)-anthradithphene (Dif-TES-ADT) single crystal is formed, yielding a breakthrough for organic field-effect transistors with a high reliable mobility up to 8.6 cm2 V-1 s-1 and an ultralow mobility variable coefficient of 8.9%. This work opens a new avenue to fabricate organic single-crystal wafers for high-performance organic electronics.

General Spatial Confinement Recrystallization Method for Rapid Preparation of Thickness-Controllable and Uniform Organic Semiconductor Single Crystals.

Organic semiconductor single crystals (OSSCs) are ideal materials for studying the intrinsic properties of organic semiconductors (OSCs) and constructing high-performance organic field-effect transistors (OFETs). However, there is no general method to rapidly prepare thickness-controllable and uniform single crystals for various OSCs. Here, inspired by the recrystallization (a spontaneous morphological instability phenomenon) of polycrystalline films, a spatial confinement recrystallization (SCR) method is developed to rapidly (even at several second timescales) grow thickness-controllable and uniform OSSCs in a well-controlled way by applying longitudinal pressure to tailor the growth direction of grains in OSCs polycrystalline films. The relationship between growth parameters including the growth time, temperature, longitudinal pressure, and thickness is comprehensively investigated. Remarkably, this method is applicable for various OSCs including insoluble and soluble small molecules and polymers, and can realize the high-quality crystal array growth. The corresponding 50 dinaphtho[2,3-b:2″,3″-f]thieno[3,2-b]thiophene (DNTT) single crystals coplanar OFETs prepared by the same batch have the mobility of 4.1 ± 0.4 cm2 V-1 s-1 , showing excellent uniformity. The overall performance of the method is superior to the reported methods in term of growth rate, generality, thickness controllability, and uniformity, indicating its broad application prospects in organic electronic and optoelectronic devices.

Vapor-Induced Coating Method for Well-Aligned and Uniform Organic Semiconductor Single Crystals

Vapor-Induced Coating Method for Well-Aligned and Uniform Organic Semiconductor Single Crystals

Organic Semiconductor Single Crystal Arrays: Preparation and Applications

The study of organic semiconductor single crystal (OSSC) arrays has recently attracted considerable interest given their potential applications in flexible displays, smart wearable devices, biochemical sensors, etc. Patterning of OSSCs is the prerequisite for the realization of organic integrated circuits. Patterned OSSCs can not only decrease the crosstalk between adjacent organic field-effect transistors (OFETs), but also can be conveniently integrated with other device elements which facilitate circuits application. Tremendous efforts have been devoted in the controllable preparation of OSSC arrays, and great progress has been achieved. In this review, the general strategies for patterning OSSCs are summarized, along with the discussion of the advantages and limitations of different patterning methods. Given the identical thickness of monolayer molecular crystals (MMCs) which is beneficial to achieve super uniformity of OSSC arrays and devices, patterning of MMCs is also emphasized. Then, OFET performance is summarized with comparison of the mobility and coefficient of variation based on the OSSC arrays prepared by different methods. Furthermore, advances of OSSC array-based circuits and flexible devices of different functions are highlighted. Finally, the challenges that need to be tackled in the future are presented.

High-speed hybrid complementary ring oscillators based on solution-processed organic and amorphous metal oxide semiconductors

Solution-processed single-crystal organic semiconductors (OSCs) and amorphous metal oxide semiconductors (MOSs) are promising for high-mobility p- and n-channel thin-film transistors (TFTs), respectively. Organic−inorganic hybrid complementary circuits hence have great potential to satisfy practical requirements. However, some chemical incompatibilities between OSCs and MOSs, such as heat and chemical resistance, make it difficult to rationally integrate TFTs based on solution-processed OSC and MOS onto the same substrates. Here, we report a rational integration method based on the solution-processed semiconductors by carefully managing the device configuration and the deposition and patterning techniques from a materials point of view. The balanced high performances as well as the uniform fabrication of the TFTs led to densely integrated five-stage ring oscillators with a short propagation delay of 1.3 µs per stage.

Controlling Polymorphic Transitions in n-Type Organic Semiconductor Single Crystals by Alkyl Chain Engineering

Control of polymorphic behavior is crucial for designing functional organic semiconductor devices as even a slight structural difference may translate to dramatically different electronic properties. One route to controlling structure is through stimulus-induced polymorph transitions, which allows for switching those electronic properties. However, despite advances in predicting crystal structures, the molecular design characteristics governing the polymorphic transition mechanism remains unknown. Here, we systematically investigate a series of n-type organic semiconductor molecules based on 2-dimensional quinoidal terthiophene with varying alkyl side chain lengths to modulate two distinct polymorph transitions, one cooperative martensitic transition and the other non-cooperative nucleation and growth transition. In the three molecular systems, we observe that shortening the alkyl chain past a critical length suppresses the cooperative polymorph transition by limiting the alkyl chain conformation change. On the other hand, the nucleation and growth transition temperature increases as the side chain length decreases, possibly driven by the increase in the melting point of the alkyl chains. We also found that tuning the alkyl chain length modulates the associated quinoidal to aromatic biradical switching that drives the nucleation and growth transition, suggesting a synergy between the crystal structure and electronic structure. Ultimately depending on the exact mechanism of the polymorph transition, adjusting the alkyl chain length may lead to tuning of the polymorph transition temperature or suppression of the transition altogether. This offers a potential molecular design rule to target a particular transition mechanism based on the desired behavior for the system.

Individual and synergetic charge transport properties at the solid and electrolyte interfaces of a single ultrathin single crystal of organic semiconductors.

The chemical structures and morphologies of organic semiconductors (OSCs) and gate dielectrics have been widely investigated to improve the electrical performances of organic thin-film transistors (OTFTs) because the charge transport therein is a phenomenon at the semiconductor-dielectric interfaces. Here, solid and ionic gel gate dielectrics were adopted on the lower and upper surfaces, respectively, of a single, two molecule-thick single crystals of p-type OSCs to study the charge transport properties at individual interfaces between the morphologically compatible OSC surface and different gate dielectrics. Using the four-probe method, the solid and ionic gel interfaces were found to exhibit hole mobilities of 9.3 and 2.2 cm2 V-1 s-1, respectively, which revealed the crucial impact of the gate dielectric materials on the interfacial charge transport. Interestingly, when gate biases are applied through both dielectrics, i.e., under the solid/ionic gel dual-gate transistor operation, the hole mobility at the solid gate interface is improved up to 14.7 cm2 V-1 s-1, which is 1.5 times greater than that assessed without the ionic gel gate. This improvement can be attributed to the electric double layer formed at the ionic gel/uniform crystal surface, which provides a close-to-ideal charge transport interface through dramatic trap-filling. Therefore, the present dual-gate transistor technique will be promising for investigating the intrinsic charge-transport capabilities of OSCs.

'Molecular Beam Epitaxy' on Organic Semiconductor Single Crystals: Characterization of Well-Defined Molecular Interfaces by Synchrotron Radiation X-ray Diffraction Techniques.

Epitaxial growth, often termed “epitaxy”, is one of the most essential techniques underpinning semiconductor electronics, because crystallinities of the materials seriously dominate operation efficiencies of the electronic devices such as power gain/consumption, response speed, heat loss, and so on. In contrast to already well-established epitaxial growth methodologies for inorganic (covalent or ionic) semiconductors, studies on inter-molecular (van der Waals) epitaxy for organic semiconductors is still in the initial stage. In the present review paper, we briefly summarize recent works on the epitaxial inter-molecular junctions built on organic semiconductor single-crystal surfaces, particularly on single crystals of pentacene and rubrene. Experimental methodologies applicable for the determination of crystal structures of such organic single-crystal-based molecular junctions are also illustrated.

Organic Semiconductor Single‐Crystal Light‐Emitting Transistors

AbstractOrganic semiconductor single crystals, with the unique advantages of high carrier transport properties, high optical quality, and low defect density, are ideal candidates for constructing high‐performance organic light‐emitting transistors (OLETs) and advancing their related potential applications, including smart displays, micro‐nano light sources, organic electrically pumped lasers, and integrated photonic circuits. Recently, significant progress has been made in organic semiconductor single‐crystal light‐emitting transistors (OSSCLETs), particularly high‐mobility emissive organic semiconductor single crystals, high‐performance light‐emitting transistors, and color‐tunable organic semiconductor single crystals and OLETs. In this review, the exciting advances in OSSCLETs are summarized in terms of advanced organic semiconductor materials, high‐quality organic semiconductor single crystals, advanced device technologies, and high‐performance light‐emitting transistors. Finally, the challenges and prospects of OSSCLETs as well as promising research directions in this field are briefly summarized.

(Invited) Organic Thin Films Transistors: From Mechanical to Biochemical Sensors

Interest in organic electronic materials, and in particular their potential for low-cost fabrication over large areas, led to the development of organic field-effect transistors (OFETs). The potential of OFETs has been demonstrated in a variety of applications, including pixel drivers for displays, bionic skin, wearable electronics and sensitive chemical sensors that can operate in aqueous environments. OFETs use conjugated, semiconducting small molecules and polymers and offer an alternative to inorganic devices for applications in which facile processing on different substrates and tunable electronic properties are required. The flexibility requirement implies either performance stability towards deformation, or conversely, detectable response to the deformation itself. The knowledge of the electromechanical response of organic semiconductors to external stresses is therefore not only interesting from a fundamental point of view, but also necessary for the development of real world applications. To this end, this presentation highlights the importance of the choice of functional materials (organic semiconductors and dielectrics) as well as the relationship structure/properties in transistors based sensors. Organic semiconductors (OSCs) are promising transducer materials when applied in OFETs taking advantage of their electrical properties that highly depend on the morphology of the semiconducting film. The effects of a high-performance p-type organic semiconductor, namely dinaphtho [2,3-b:2,3-f] thieno [3,2–b] thiophene (DNTT) thickness on its piezoresistive sensitivity are presented. A critical thickness corresponding to the appearance of charge carriers percolation paths in the material can tune the gauge factors (GFs) by a factor 10. In addition, single crystal OSC are regarded as promising electroactive materials for strain sensing application. Herein this talk, we will present how strain induces simultaneous mobility changes along all three axes, and that in some cases the response is higher along directions orthogonal to the mechanical deformation. These variations cannot be explained by the modulation of intermolecular distances, but only by a more complex molecular reorganisation, which is particularly enhanced, in terms of response, by p-stacking and herringbone stacking. This microscopic knowledge of the relation between structural and mobility variations is essential for the interpretation of electromechanical measurements for crystalline organic semiconductors, and for the rational design of electronic devices. Alternatively, this talk will highlight how the use of an active gate dielectric layer such as poly(vinylidenefluoride/trifluoroethylene) (P(VDF-TrFE)) piezoelectric polymer can lead to highly efficient electro-mechanical sensitivity. In such case, the sensing mechanism of the electro-mechanical transducer originates from the piezoelectric material itself, which affects the electrical behavior of the transistor as signature of a mechanical event. The second part of this talk will focus on another kind of TFT based sensor, namely the organic electrochemical transistors (OECTs) which have found recently applications in chemical and biological sensing and interfacing and neuromorphic computing. OECT rely on ions that are injected from the electrolyte into polymer-based mixed conductors, thereby changing its doping state and hence its conductivity. While great progress has been achieved, organic mixed conductors frequently experience significant volumetric changes during ion uptake/rejection, i.e., during doping/ de-doping and charging/discharging. Although ion dynamics may be enhanced in expanded networks, these volumetric changes can have undesirable consequences, e.g., negatively affecting hole/electron conduction and severely shortening device lifetime. New materials able to transport ions and electrons/holes and that exhibits low swelling will be presented, expanding the materials-design toolbox for the creation of low-swelling soft mixed conductors with tailored properties and applications in bioelectronics and beyond.

(Invited, Digital Presentation) Epitaxial Organic Molecular Interfaces As Well-Ordered Model Systems for Molecular Semiconductor p-n Junctions for Optoelectronic Applications

Donor-acceptor molecular interfaces are nothing but p-n junctions for organic optoelectronic devices such as organic light emitting diodes and organic solar cells where an exciton forms or dissociates. Understanding about dominating factors determining the intermolecular assembly and charge carrier exchange processes are highly anticipated for the establishment of smart design strategies of practically efficient devices. Molecular heterojunctions built on single crystal organic semiconductors provide well-ordered model systems disentangling complex intermolecular contacts in real devices. Moreover, the p-n junctions of highly ordered molecular assembly lead to the enhancement of the mobility of charge carriers and excitons through the inter-molecular delocalization of the electronic states, which potentially opens a new route for efficient optoelectronic applications of molecular semiconductors. In this contribution, crystallographic and electronic structures of well-ordered molecular semiconductor homo- and hetero-epitaxial junctions are overviewed.One representative system is a “complementary” p-n junction of perfluoropentacene (C22F14) crystalline ad-layers formed on the single crystal pentacene (C22H14) [1]. Grazing-incidence X-ray diffraction (GIXD) analyses revealed hetero-epitaxial growth of perfluoropentacene in a uniform crystallographic orientation with respect to the surface lattice of the single crystal pentacene. The energy-momentum dispersions of inter-molecular electronic bands were successfully demonstrated by angle-resolved photoelectron spectroscopy (ARPES) for the hetero-epitaxial perfluoropentacene as well as for the single crystal pentacene, which strongly suggests realization of the delocalization of electrons and holes across this well-ordered molecular p-n junction.To further improve the crystallinity of the epitaxial molecular heterojunctions, the authors’ group proposed a new concept of “quasi-homoepitaxial organic semiconductor junctions”, at which a molecular species with nearly identical in-plane lattice constants to those of the substrate molecular single crystal surface is stacked [2]. Actually, quasi-homoepitaxial crystallites of bis(trifluoromethyl)dimethylrubrene was revealed to form highly-ordered interface of much improved mean crystallite size on the single crystal surface of (unsubstituted) rubrene by means of high-resolution GIXD. The electronic structures exhibiting spontaneous electron transfer at this inter-molecular contact and possible opto-electronic applications of this quasi-homoepitaxial junction are also discussed in this presentation.This contribution is supported by Grant-in Aids for Transformative Research Areas (A) “Dynamic Exciton: Emerging Science and Innovation” (JSPS-KAKENHI Grant Number JP21H05405).[1] Y. Nakayama, et al., J. Phys. Chem. Lett. 10 (2019) 1312.[2] K. Takahashi, et al., J. Phys. Chem. Lett. 12 (2021) 11430.

Intrinsic Linear Dichroism of Organic Single Crystals toward High‐Performance Polarization‐Sensitive Photodetectors (Adv. Mater. 22/2022)

Polarization-Sensitive Photodetectors High-performance polarization-sensitive organic photodetectors with a linear dichroic ratio as high as 1.9 are successfully developed by Huanli Dong, Zhongming Wei, Liqiang Li, Wenping Hu, and co-workers, as described in article number 2105665, utilizing the intrinsic anisotropic nature of organic semiconductor single crystals. These devices show new opportunities for using organic semiconductors to develop highly compact polarization-sensitive photodetectors in diverse applications, and open up a new area for the study of organic semiconductors.

A Direct Writing Approach for Organic Semiconductor Single-Crystal Patterns with Unique Orientation.

Organic semiconductor single-crystal (OSSC) patterns with precisely controlled orientation are of great significance to the integrated fabrication of devices with high and uniform performance. However, it is still challenging to achieve purely oriented OSSC patterns due to the complex nucleation and growth process of OSSCs. Here, a general direct writing approach is presented to readily obtain high-quality OSSC patterns with unique orientation. In specific, a direct writing method is demonstrated wherein the microscale meniscus is manipulated, which makes it possible to precisely control the nucleation and growth process of the OSSC because of its comparable size to the crystal nuclei. The resulting OSSC patterns are highly crystalline and purely oriented, in which each ribbon crystal shows a deviation angle of 33° to the printing direction. The mechanism of orientation purification is revealed experimentally and theoretically, and the results show that the TCL deformation caused by the difference in wettability and adhesive force, as well as the asymmetry of fluid concentration distribution, are the key factors leading to the selective deposition and unique orientation. Moreover, organic field-effect transistors (OFETs) and polarization-sensitive photodetectors are prepared based on the OSSC patterns with unique orientation, which exhibit higher device performance compared to the non-purely oriented crystal-based OFETs.

Luminescent High‐Mobility 2D Organic Semiconductor Single Crystals

Abstract2D organic semiconductor single crystals comprising one or a few molecular layers of macroscopic lateral sizes are ideal materials for ultrathin, flexible, and transparent field‐effect devices—a platform for transistors and sensors. In recent years, these 2D materials have demonstrated high performance not inferior to their 3D counterparts. However, light emissive properties of 2D organic semiconductor single crystals have not yet been reported, and a combination of high charge‐carrier mobility and bright luminescence in one material is still a challenge for 2D organic optoelectronics. Emissive high‐mobility 2D organic semiconductor based on a [1]benzothieno[3,2‐b]benzothiophene (BTBT)‐derivative, 2,7‐bis(4‐decylphenyl)[1]benzothieno[3,2‐b][1]benzothiophene (DPBTBT), is presented here. DPBTBT molecules self‐organize in large‐area ultrathin single‐crystalline films consisting of one or a few molecular layers. These 2D single crystals perfectly suit as an active layer of organic field‐effect transistors in full accordance with Shockley's model and uniquely combine the high charge‐carrier mobility reaching 7.5 cm2 V–1 s–1 with prominent light emissive properties, which allow a demonstration of the first 2D organic light‐emitting transistor. The high charge‐carrier mobility and thermal stability of the crystalline phases, pronounced luminescence, and good shelf‐life stability suggest that emissive BTBT‐type molecules are a promising avenue for 2D organic optoelectronics.

The prospects of organic semiconductor single crystals for spintronic applications

Spintronic applications of OSSCs are discussed from the aspects of molecular structure, stacking structure, OSSC-based spintronic device fabrication, and multifunctional applications.

Crystallization from a Droplet: Single-Crystalline Arrays and Heterojunctions for Organic Electronics.

ConspectusSingle crystals of organic semiconductors (OSCs) are believed to have both high mobility and intrinsic flexibility, making them promising candidates for flexible electronic/optoelectronic applications and being consistently pursued by researchers. The van der Waals force in OSC enables low-temperature solution processing of single crystals, but the relatively weak binding energy brings challenges in forming large, uniform, and defect-free single crystals. To promote the study on OSC single crystals, a generalized method that grows high-quality crystals in an easy-to-handle, time/resource-saving, and repeatable manner is apparently necessary. In 2012, Li et al. developed a droplet-pinned crystallization (DPC) method that uses a rather simple strategy to create a steadily receding contact line for the growth of OSC single crystals. Instead of setting up expensive equipment, controlling strict deposition parameters, or waiting for days or weeks for countable crystal seeds, the DPC method offers a time- and cost-effective way to obtain OSC single crystals for further study of the tendency of crystallization, single-crystal mobility, and molecular packing information. The DPC method is primarily a powerful tool for studying the charge-transport mechanisms in OSC single crystals. In pioneering work, high-mobility single crystals of both p-type 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-PEN) and n-type C60 materials were obtained. Driven by the demands from practical applications, we then focused on the general lagging of electron mobility in OSC materials. The ambipolar property of TIPS-PEN was studied, and a strong correlation between electron mobility and polar species (polar solvent residuals and surface hydroxyl groups) was observed. The latter further guided the harvest of electron mobility in a series of OSC materials. Undoubtfully, the facile DPC method accelerated these studies by providing a time-efficient, reliable, and repeatable testing platform. Additionally, flexibility on OSC materials and solvents, where not only one-component but also binary systems were allowed, is another critical integrity of the DPC method. The m-xylene/carbon tetrachloride binary solvent was proven to be efficient for growing ribbon-like C60 single crystals rather than needle-like crystals from typical one-component solvents. Afterward, a variety of OSC materials (including p-type, n-type, and ambipolar ones) and a series of solvents (including aromatic, aliphatic, and polar ones) were studied. The crystallization of OSC single crystals was primarily found at either the top liquid-air interface or the bottom solid-liquid interface. The interactions between OSC molecules and substrate surfaces were deduced as the qualitative determining factor. By utilizing the top interface crystallization, the two-step sequential deposition of single-crystalline OSC heterojunctions was enabled. Moreover, by selecting appropriate pairs of OSC materials that crystallize at separate interfaces, the facile one-step formation of single-crystalline OSC heterojunctions was achieved. The OSC single crystals and heterojunctions (including horizontal, vertical, and bulk heterojunctions) thereof exhibit promising potentials in circuits, photovoltaics, and photodiodes and would probably provide new insights for the future development of organic electronics.

Growing two-dimensional single crystals of organic semiconductors on liquid surfaces

Two-dimensional (2D) organic semiconducting single crystals (OSSCs) combine the advantages of OSSCs and 2D molecular materials, and currently, are an important and hot research topic in the field of organic optoelectronics and 2D materials. Growth of large-sized 2D OSSCs with controlled thickness is highly important for fundamental research and practical application, which is still a challenging task. Liquid surfaces can provide ideal platforms for growth of large-scale and layer-controlled 2D OSSCs because their surfaces are molecularly flat and free-defect, the “coffee-ring” effect can be effectively suppressed on liquid surfaces, and the improved spread area of organic semiconductor solutions on liquid surfaces. This perspective concentrates on recent advances in the growth of large-area and layer-controlled 2D OSSCs on liquid surfaces; the optoelectronic applications based on 2D OSSCs, as well as the challenges and outlooks in the field, are also discussed.

Modulated-photocurrent spectroscopy of single-crystal organic semiconductor rubrene with pristine and trap-dominated surfaces

High-performance, benchmark organic semiconductor rubrene is investigated by modulated-photocurrent (MPC) spectroscopy. In this technique, periodically modulated and steady-state photocarrier populations are simultaneously generated in the sample by two independent light beams, with the resultant photocurrent measured by a lock-in amplifier. The technique allows identifying a bandlike carrier motion (as opposed to incoherent hopping) as the dominant charge transport mechanism in this highly crystalline molecular semiconductor, in agreement with prior studies, yet without the need for fabrication of complex transistor devices. Moreover, MPC spectroscopy is used to determine the important parameters, such as the density of states for traps, their carrier capture coefficient, and attempt to escape frequency, as well as the quantum efficiency of photocarrier generation and the photocarrier mobility. The MPC spectroscopy is also shown to be able to discriminate charge transport at the surface of the crystal from that occurring in the bulk. The wealth of the thus obtained information is essential for our better understanding of the microscopic mechanisms governing photoconductivity in this class of materials.

Spin injection and transport in single-crystalline organic spin valves based on TIPS-pentacene

Single crystals of organic semiconductors with perfect crystal structure and minimal density of defects can exhibit high mobility and low spin scattering compared with their amorphous or polycrystalline counterparts. Therefore, these materials are promising candidates as the spin transport media to obtain long spin relaxation times and spin diffusion lengths in spintronic devices. However, the investigation of spin injection and transport properties in organic single crystals is hindered by the inability to construct devices such as single-crystalline organic spin valves (OSVs). Herein, thin and large organic single crystals of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) were grown on a liquid substrate and transferred to a target substrate carrying ferromagnetic electrodes to construct single-crystalline OSVs. The magnetoresistance (MR) responses of the single crystals were investigated to study their spin injection and transport properties. MR value as high as 17% was probed with an intermediate layer thickness of 269 nm. More importantly, spin transport was still observed in a single crystal of a thickness up to 457 nm, which was much larger than that of polycrystalline thin film. Our research provides a general methodology for constructing single-crystalline OSVs and paves the way to probe the intrinsic spin transport properties of organic semiconductors based on single crystals.