Chemically induced transformation of chemical vapour deposition grown bilayer graphene into fluorinated single-layer diamond

Bakharev, Pavel V.; Huang, Ming; Saxena, Manav; Lee, Suk Woo; Joo, Se Hun; Park, Sung O; Dong, Jichen; Camacho-Mojica, Dulce C.; Jin, Sunghwan; Kwon, Youngwoo; Biswal, Mandakini; Ding, Feng; Kwak, Sang Kyu; Lee, Zonghoon; Ruoff, Rodney S.

doi:10.1038/s41565-019-0582-z

Cited by 222 publications

(226 citation statements)

References 38 publications

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“…This path however has not been explored even in theory, in spite of motivating progress in experimental evidence of feasibility of such sp 2 –sp 3 transformation into extremely thin, nano‐films of diamane. [ 32–37 ]…”

Section: Figurementioning

confidence: 99%

Nano‐Thermodynamics of Chemically Induced Graphene–Diamond Transformation

Erohin

Ruan

Сорокин

et al. 2020

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GPa. Moreover, there is also a large kinetic barrier for diamond-graphite changes, in either direction. Even downhill spontaneous transformation from diamond to thermodynamically favored graphite (δg ≈ 20 meV/atom lower) is inhibited by a large barrier and would take geological times; good cause for a saying "diamonds are forever." [4] Nevertheless, at the nanoscale, such diamond graphitization [5,6] does occur through the outer atomic layers. This process can be suppressed by saturation of dangling sp 3 surface bonds with adatoms or covalent functional groups, for example, by hydrogenation, which "seals" the carbon in its energetically upper state, diamond. One could speculate that, conversely to graphitization, functionalizing the graphite surface can transform it to sp 3 state of diamond, to some depth; this however, is hindered by the energy taxing sp 3-sp 2 interface, created underneath. Moreover, although the 2D-surface can affect many properties of 3D bulk material, obviously the surface state (reconstruction or chemical passivation) cannot change the thermodynamics of phase preference across the entire macroscopic volume. High pressure, assisted by temperature, remains a prerequisite for getting 3D-diamonds from graphite. With the advent of 2D materials and particularly graphene (Gr), including its bilayer (BLG [7]) and few-layer (FLG [8]) varieties, this paradigm may change. In contrast to 3D bulk, if the sample is of very small, nanometer scale thickness, then its surface chemistry can switch the lattice organization (phase state) throughout. To appreciate the ease of such "phase conversion" by chemistry, one recalls best studied monolayer graphene hydrogenated on both sides into CH composition. It was theoretically proposed [9] and christened "graphane" in its detailed study. [10] Basic notable features distinguishing graphane are the sp 3-hybridizaton of all C-atoms (instead of sp 2 in graphene) and its wide band gap (5.4 eV in the graphane chair conformation, [11] instead of zero in semimetal graphene), which justify considering it as the ultimate, thinnest diamond slab [12] (especially since the bulk diamond surface is also typically H-passivated). The contrast in electronics of graphene and graphane invites possibilities of direct chemical patterning of functional circuitry. [13,14] The choice of active atoms is not limited to H, but can also be fluorine (interesting due to high chemical activity in its attachment to the graphene [13,15]), or chlorine. [16] The kinetics of such transformation was first analyzed in the context of hydrogen storage [17] and spillover [18] media, showing Nearly 2D diamond, or diamane, is coveted as an ultrathin sp 3-carbon film with unique mechanics and electro-optics. The very thinness (≈h) makes it possible for the surface chemistry, for example, adsorbed atoms, to shift the bulk phase thermodynamics in favor of diamond, from multilayer graphene. Thermodynamic theory coupled with atomistic first principles computations predicts not only the reduction of required pres...

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Section: Figurementioning

confidence: 99%

Nano‐Thermodynamics of Chemically Induced Graphene–Diamond Transformation

Erohin

Ruan

Сорокин

et al. 2020

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“…In the past decades, numerous investigations on the properties of diamane were performed and its potential applications were found in the fields of nano-photonics [21,22] and ultrasensitive resonator-based sensors [23]. Recently, it is exciting that the fully fluorinated AB-stacked diamane [24] and pristine diamane with (2 -110) orientation [25] were synthesized successfully in experiments. It should be noted that in previous literatures, different names, such as diamane [20,[24][25][26], diamondol [27], diamondene [28], or diamene [29], was adopted for diamane, due to the diversity of surface functional groups on the diamond film surface.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, it is exciting that the fully fluorinated AB-stacked diamane [24] and pristine diamane with (2 -110) orientation [25] were synthesized successfully in experiments. It should be noted that in previous literatures, different names, such as diamane [20,[24][25][26], diamondol [27], diamondene [28], or diamene [29], was adopted for diamane, due to the diversity of surface functional groups on the diamond film surface. Here, for the convenience of discussion, we call them collectively as diamane.…”

Section: Introductionmentioning

confidence: 99%

Diamane: design, synthesis, properties, and challenges

Qin

Gou

2021

Functional Diamond

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Diamane, the two-dimensional counterpart of diamond, is achieved from bi-layer graphene (BlG) or few-layer graphene (FlG) through surface chemical adsorption or high-pressure technology. Diamane with interlayer sp 3 bonding is found to have excellent heat transfer, ultralow friction, high natural frequency, and tunable band gap, which shows the potential technological and industrial applications in nano-photonics, ultrasensitive resonator-based sensors, and improved wear resistance. in this review, we summarize the structure character, synthesis strategies, and physical properties of different diamanes, including hydrogenated diamane (hD), fluorinated diamane (FD), and pristine diamane (PD). in addition, we discuss the effect of functional groups, element doping, and stacking order on the physical properties of diamane. Finally, the remaining challenges and future opportunities for the further development of diamane are addressed.

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“…Several works have theoretically studied on the stability of diamane that is passivated by other atoms and molecules and also its band gap and thermal conductivity, depending on passivating molecules [15,16]. The diamane can be synthesized by exposing a bilayer graphene in order to chemically react with H or F atoms [17][18][19][20].…”

Section: Introductionmentioning

confidence: 99%

Modifying Electronic and Elastic Properties of 2-Dimensional [110] Diamond by Nitrogen Substitution

Pakornchote

Ektarawong

Pinsook

et al. 2021

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One type of two-dimensional diamonds that are derived from [111] direction, so-called diamane, has been previously shown to be stabilized by N-substitution, where the passivation of dangling bonds is no longer needed. In the present work, we theoretically demonstrated that another type of two-dimensional diamonds derived from [110] direction exhibiting a washboard conformation can also be stabilized by N-substitution. Three structural models of washboard-like carbon nitrides with compositions of C6N2, C5N3, and C4N4 are studied together with the fully hydrogenated washboard-like diamane (C8H4). The result shows that the band gap of this type structure is only open the dangling bonds that are entirely diminished through N-substitution. By increasing the N content, the C11 and C22 are softer and the C33 is stiffer where their bulk modulus are in the same order, which is approximately 550 GPa. When comparing with the hydrogenated phase, the N-substituted phases have higher elastic constants and bulk modulus, suggesting that they are possibly harder than the fully hydrogenated diamane.

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Chemically induced transformation of chemical vapour deposition grown bilayer graphene into fluorinated single-layer diamond

Cited by 222 publications

References 38 publications

Nano‐Thermodynamics of Chemically Induced Graphene–Diamond Transformation

Nano‐Thermodynamics of Chemically Induced Graphene–Diamond Transformation

Diamane: design, synthesis, properties, and challenges

Modifying Electronic and Elastic Properties of 2-Dimensional [110] Diamond by Nitrogen Substitution

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