Synthesis and Phase Relations of Single‐Phase Fibrous Phosphorus

Eckstein, Nadine; Hohmann, Andrea; Weihrich, Richard; Nilges, Tom; Schmidt, Peer

doi:10.1002/zaac.201300327

Cited by 65 publications

(69 citation statements)

References 20 publications

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“…Ruck et al synthesized 1D red phosphorus nanowires in 2005 by heating red phosphorus in an evacuated ampoule at around 590 8 8Cf or several days. [11] Violet phosphorus,w hich also falls into the category of red phosphorus and first prepared by Hittorf in 1865, forms red-to-violet colored platelets and displays acomplex tubular Phosphorus is an onmetal with several allotropes,from the highly reactive white phosphorus to the thermodynamically stable black phosphorus (BP) with apuckered orthorhombic layered structure. In 1969, Thurn and Krebs postulated the structure of this crystalline form of red phosphorus.…”

Section: Introductionmentioning

confidence: 99%

“…[6] Thestructure of this type of red phosphorus is considered to be apolymeric network of different building units,w hich are well-known from various compounds containing amorphous polymeric phosphorus structures (see Scheme 1f or the structures of selected phosphorus allotropes). Red phosphorus has been found to exist in avariety of crystalline forms (types I-V), [3,[7][8][9][10][11][12] all of which exhibit ar eddish color. Ruck et al synthesized 1D red phosphorus nanowires in 2005 by heating red phosphorus in an evacuated ampoule at around 590 8 8Cf or several days.…”

Section: Introductionmentioning

confidence: 99%

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Black Phosphorus Rediscovered: From Bulk Material to Monolayers

2017

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Phosphorus is a nonmetal with several allotropes, from the highly reactive white phosphorus to the thermodynamically stable black phosphorus (BP) with a puckered orthorhombic layered structure. The bulk form of BP was first synthesized in 1914, but received little attention until it was rediscovered in 2014 as a member of the new wave of 2D layered nanomaterials. BP can be exfoliated to a single sheet that acts as a semiconductor with a tunable direct band gap, a high carrier mobility at room temperature, and an in-plane anisotropy. The development of BP applications is hampered by surface degradation, thus efforts to achieve effective BP passivation are ongoing, such as its integration in van der Waals heterostructures. BP has been tested as a novel nanomaterial in batteries, transistors, sensors, and photonics. This Review begins with the origin of the BP story, following the path from a bulk material to modern few/single layers. The physical and chemical properties are summarized, and the state-of-the-art of BP applications highlighted.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Black Phosphorus Rediscovered: From Bulk Material to Monolayers

2017

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“…Current reports include the catalytic activity of red P [17], black P as photo-detector [18], or the highly topical discovery of single-layer phosphorenes [19,20]. Especially in the field of solid-state chemistry, finding novel ways of preparation [21,22] and exploration of existing and new allotropes is still a challenging task. This applies for experimentalists [9,10,15] as much as for theoreticians [23][24][25][26][27][28].…”

Section: Introductionmentioning

confidence: 99%

Van der Waals interactions in selected allotropes of phosphorus

Bachhuber

Appen

Dronskowski

et al. 2014

Zeitschrift Für Kristallographie - Crystalline Materials

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Selected allotropes of phosphorus are investigated by different levels of density functional theory (DFT) calculations to evaluate the relative stability orders with a special focus on the role of van der Waals interactions. Phosphorus is an excellent reference system with a large number of allotropes. Starting from low-dimensional molecular (0D, white P) and polymer structures (1D, P nanorods) to layered (2D, black P) and tubular structures (2D and 3D, crystalline forms of red P), covalent structure motifs are interconnected by van der Waals interactions. They are a key factor for the correct energetic description of all P allotropes. A comparative study is carried out within the local density approximation (LDA) and the generalized gradient approximation (GGA), with and without implementation of a dispersion correction by Grimme (GGA-D2). Our intention is to achieve a reasonable agreement of our calculations with experimental data, the plausibility of energy values, and the treatment of long-range interactions. The effect of van der Waals interactions is exemplified for the interlayer distances of black phosphorous and its electronic structure.

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“…Figure 1shows that the peaks originating from the films grown at 500 8 8C( top spectrum) match the ones obtained for the commercially available type I a-RP powder (bottom spectrum), confirming that the films produced were composed of a-RP.T he peak marked with an (*) in the top spectrum originated from the gold-coated Si/ SiO 2 substrate used as as upport for the films in this experiment (see Figure S2). It is worth noting that despite the fact that other allotropic RP can be produced by applying at emperature treatment to a-RP powder, [21,31] the Raman peaks from the synthesized a-RP film do not match any of the peaks reported for any of the type II-V red phosphorus,f urther confirming that the deposited films are made of a-RP. [28][29][30] At this stage,e ach individual peak in the Raman spectrum cannot be assigned to any specific vibrational mode since the structural composition of a-RP has not yet been resolved.…”

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confidence: 85%

“…[28][29][30] At this stage,e ach individual peak in the Raman spectrum cannot be assigned to any specific vibrational mode since the structural composition of a-RP has not yet been resolved. It is worth noting that despite the fact that other allotropic RP can be produced by applying at emperature treatment to a-RP powder, [21,31] the Raman peaks from the synthesized a-RP film do not match any of the peaks reported for any of the type II-V red phosphorus,f urther confirming that the deposited films are made of a-RP. [21] An optical profilometer was used to measure the films thickness and surface roughness.A saseparate note,a tomic force microscope (AFM) was not suitable for the measurement in this case since some of the films have thicknesses that fall outside of the range for aconventional AFM.…”

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confidence: 92%

High Electron Mobility of Amorphous Red Phosphorus Thin Films

et al. 2019

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Blackp hosphorus (BP) has been gathering great attention for its electronic and optoelectronic applications due to its high electron mobility and high I ON/OFF current switching ratio.T he limitations of this material include its low synthetic yield and high cost. One alternative to BP is another type of phosphorus allotrope,r ed phosphorus (RP), which is much more affordable and easier to process.A lthough RP has been widely used in industry for hundreds of years and considered as an insulating material, in this study,wedemonstrate through field-effect transistors (FET) measurements that amorphous red phosphorus (a-RP) films are semiconductive with ah igh mobility of 387 cm 2 V À1 s À1 and ac urrent switching ratio of % 10 3 ,w hich is comparable to the electronic characteristics previously reported for BP.T he films were produced via at hermal evaporation method or af acile drop-casting approach onto Si/SiO 2 substrates.W ea lso report as tudy of the oxidation process of the films over time and am ethod to stabilizet he films via doping a-RP with metal oxides.T he doped films retain stability for one thousand I-V cycles,w ith no signs of degradation.Phosphorus exhibits aw ide variety of allotropes,which can be divided into three distinct groups:w hite,b lack, and red phosphorus.T hese three groups have been known for hundreds of years, [1] but their crystal structures were only described in the last century.W hite phosphorus,d efined as the standard state of phosphorus (even though it is not the most thermodynamically stable), is ac rystalline four-atoms cage arrangement of phosphorus (P 4 ), and exists in three different arrangements (a-, b-and g-P 4 ). [2,3] Black phosphorus (BP) exists in an amorphous form [4] and three known different crystalline phases (orthorhombic,c ubic and rhombohedral). [5][6][7][8] Orthorhombic BP is the most thermodynamically stable BP allotrope and its crystal structure consists of layers held by van der Waals forces,which exhibits flakiness similar to graphite. [9][10][11][12] Bulk BP has aband gap of % 0.3 eV; as the layer number is decreased, quantum confinement effects increase that value to as high as 1.5 eV for monolayer phosphorene. [13][14][15] This tunability makes BP suitable for aw ide variety of electronic and optoelectronic applications.F ew-layer BP is ap -type charge carrier with mobilities as high as 1000 cm 2 V À1 s À1 . [16] 2D BP nanomaterials used in optoelectronic devices to date are typically prepared by two methods.T he first involves manual delamination of bulk crystals and subsequent transfer to as ubstrate, [10] as was originally employed for the isolation of graphene.H owever, this is an extremely low throughput strategy and offers little hope for scalable device integration. Thesecond method involves ultrasonic delamination of abulk BP crystal to form as uspension of few-layer fragments,w ith asubsequent solution-deposition step to form athin film. [17][18][19] Thed rawbacks of this method include 1) the solvent and ultrasound can introduce defects;2 )t ...

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Synthesis and Phase Relations of Single‐Phase Fibrous Phosphorus

Cited by 65 publications

References 20 publications

Black Phosphorus Rediscovered: From Bulk Material to Monolayers

Black Phosphorus Rediscovered: From Bulk Material to Monolayers

Van der Waals interactions in selected allotropes of phosphorus

High Electron Mobility of Amorphous Red Phosphorus Thin Films

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