Band structure engineering in organic semiconductors

Schwarze, Martin; Tress, Wolfgang; Beyer, Beatrice; Gao, Feng; Scholz, Reinhard; Poelking, Carl; Ortstein, Katrin; Günther, Alrun A.; Kasemann, Daniel; Andrienko, Denis; Leo, Karl

doi:10.1126/science.aaf0590

Cited by 253 publications

(310 citation statements)

References 51 publications

(45 reference statements)

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“…[25] However, only F x ZnPcs (x = 0, 4, 8, 16) were studied in their work. [25] However, only F x ZnPcs (x = 0, 4, 8, 16) were studied in their work.…”

Section: Doi: 101002/adma201605053mentioning

confidence: 99%

“…[25] However, only F x ZnPcs (x = 0, 4, 8, 16) were studied in their work. [25] In addition, it is found from our calculated values that quadruple moments are not significantly affected by a different central metal ion in the F x MePcs (Me = Cu, Zn; x = 0, 4, 8, 16) studied, which indicates the p-type to n-type transition observed in our systems is mainly derived from the fluorination of metal phthalocyanines that leads to the polarization change. The eigenvalues of quadruple tensors of all system studied at ω B97XD/6-311G level are given in Table S1 (Supporting Information), with similar trends observed in both systems if compared to Table S1 (Supporting Information) of recent work.…”

Section: Doi: 101002/adma201605053mentioning

confidence: 99%

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Molecular Crystal Engineering: Tuning Organic Semiconductor from p‐type to n‐type by Adjusting Their Substitutional Symmetry

Jiang

et al. 2017

Advanced Materials

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Focusing on the bottleneck of molecularly engineered organic semiconductors, a breakthrough is made to tune the electronic properties of organic semiconductors from p-type to n-type by using fluorinated metal phthalocyanines as examples. The experimentally observed p-type to n-type transition characteristics of single-crystal field-effect devices result from a combination of extrinsic and intrinsic properties of materials with different fluoridation substitution.

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“…[25] However, only F x ZnPcs (x = 0, 4, 8, 16) were studied in their work. [25] However, only F x ZnPcs (x = 0, 4, 8, 16) were studied in their work.…”

Section: Doi: 101002/adma201605053mentioning

confidence: 99%

Section: Doi: 101002/adma201605053mentioning

confidence: 99%

Molecular Crystal Engineering: Tuning Organic Semiconductor from p‐type to n‐type by Adjusting Their Substitutional Symmetry

Jiang

et al. 2017

Advanced Materials

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“…This type of band gap engineering has recently been realised in some organic semiconductors, despite the stronger localization of their electronic states. 65 It is therefore interesting to see whether we can obtain an intermediate value of the band gap from mixing the wide-gap and narrow-gap PMOF materials.…”

Section: 64mentioning

confidence: 99%

Porphyrin-based metal-organic frameworks for solar fuel synthesis photocatalysis: band gap tuning via iron substitutions

et al. 2017

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Photocatalysts based on metal-organic frameworks (MOFs) are very promising due to a combination of high tuneability and convenient porous structure. Introducing porphyrin units within MOFs is a potential route to engineer these natural photosynthesis molecular catalysts into artificial photosynthesis heterogeneous catalysts. Using computer simulations based on density functional theory, we explore how to modify the electronic structure of porphyrin-based MOFs to make them suitable for the photocatalysis of solar fuel synthesis via water splitting or carbon dioxide reduction. In particular, we have investigated the effect that Fe substitutions have on the electronic properties of porphyrin-based metal organic frameworks. By aligning the electron levels with a vacuum reference, we show that Fe at the porphyrin metal centre has the effect of slightly raising the position of the valence band edge, whereas Fe at the octahedral metal node has the ability to significantly lower the position of the conduction band edge on the absolute scale. Iron is therefore a very useful dopant to engineer the band structure and alignment of these MOFs. We find that the porphyrin-based structure with Al in the octahedral sites and Zn in the porphyrin centres has a band gap that is slightly too wide to take advantage of visible-light solar radiation, while the structure with Fe in the octahedral sites has bandgaps that are too narrow for water splitting photocatalysis. We then show that the optimal composition is achieved by partial substitution of Al by Fe at the octahedral sites, while keeping Zn at the porphyrin centres. Our study demonstrates that porphyrinbased MOFs can be engineered to display intrinsic photocatalytic activity in solar fuel synthesis reactions.

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“…Specifically, the additional functional control, which may be achieved through the formation of heterostructures realized by placing one supramolecular layer on another and resulting in growth into the third dimension perpendicular to the substrate, has not been widely explored for these materials. Such additional control of material properties is well established for semiconductors, both organic [25][26][27][28][29][30] and inorganic 31 , and, more recently, layered materials 32 , providing a strong motivation to explore analogue materials derived from stacked supramolecular networks. Here we describe the successful formation of heterostructures formed by the sequential growth of distinct one-and two-dimensional arrays.…”

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confidence: 99%

Supramolecular heterostructures formed by sequential epitaxial deposition of two-dimensional hydrogen-bonded arrays

et al. 2017

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Two-dimensional supramolecular arrays provide a route to the spatial control of the chemical functionality of a surface, but their deposition is in almost all cases limited to a monolayer termination. Here we investigate the sequential deposition of one 2D array on another to form a supramolecular heterostructure and realise growth, normal to the underlying substrate, of distinct ordered layers, each of which is stabilised by in-plane hydrogen bonding. For heterostructures formed by depositing terephthalic acid (TPA) or trimesic acid (TMA) on cyanuric acid/melamine (CA.M) we determine, using atomic force microscopy under ambient conditions, a clear epitaxial arrangement despite the intrinsically distinct symmetries and/or lattice constants of each layer. Structures calculated using classical molecular dynamics are in excellent agreement with the orientation, registry and dimensions of the epitaxial layers. Calculations confirm that van der Waals interactions provide the dominant contribution to the adsorption energy and registry of the layers.

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Band structure engineering in organic semiconductors

Cited by 253 publications

References 51 publications

Molecular Crystal Engineering: Tuning Organic Semiconductor from p‐type to n‐type by Adjusting Their Substitutional Symmetry

Molecular Crystal Engineering: Tuning Organic Semiconductor from p‐type to n‐type by Adjusting Their Substitutional Symmetry

Porphyrin-based metal-organic frameworks for solar fuel synthesis photocatalysis: band gap tuning via iron substitutions

Supramolecular heterostructures formed by sequential epitaxial deposition of two-dimensional hydrogen-bonded arrays

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