Black Phosphorus (BP) Powder and Crystals
Low price, high purity black phosphorus powder and crystals
For the development of next-generation electronics, optoelectronics, and nanotechnology
Black phosphorus (BP) is an allotrope of phosphorus consisting of multiple layers with two-dimensional structures, weakly bonded to one another by van der Waals forces. When separated, the resulting monolayer (or few-layer) material is known as phosphorene. Due to its unique characteristics and significant potential in electronics and optoelectronics, this material is currently of great interest to the scientific community.
We supply low price black phosphorus in several different forms for a range of applications.
Black Phosphorus Powder
Can be used for preparation of black phosphorus quantum dots, nano-platelets and thin films
Available in quantities of
250 mg, 500 mg, or 1 g
Small Crystals by Weight
Can be used to produce single or few-layer phosphorene via mechanical or liquid exfoliation
Available in quantities of
250 mg, 500 mg, or 1 g
Individual Crystals by Size
Can be used to produce single or few-layer phosphorene sheets via mechanical or liquid exfoliation
Suitable for study using atomic force microscopy or transmission electron microscopy
Small (≥10 mm2) or medium (≥25 mm2) crystals available*
*Typical representative size, areas/dimensions may vary
Bulk single crystals are most commonly used as sources from which single or few-layer phosphorene sheets can be obtained via either mechanical or liquid exfoliation. In addition, the properties of single crystals can be explored using a range of microscopy techniques including atomic force microscopy (AFM) and transmission electron microscopy (TEM).
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Black phosphorus powder is generally used to prepare black phosphorus quantum-dots (BPQDs) and nano-platelets by liquid-exfoliation (assisted by sonication). As a result of its high purity, the powdered form can also be used in chemical vapour deposition to create high-quality, atomically thin films.
What is Black Phosphorus?
Black phosphorus was first synthesised in 1914 by Percy W Bridgman by heating white phosphorus at high pressures. It is the most stable known allotrope of phosphorus and consists of 2-dimensional layers of phosphorus (termed ‘phosphorene’) in the same way that graphite is made up of many layers of graphene.
Despite being largely overlooked for 100 years, the current boom in 2D materials research has led to black phosphorus being given a second look. The individual phosphorene monolayers were first separated and studied in 2014, and research into the black phosphorus’ unique properties and wide range of potential applications has been ongoing since.
What is Phosphorene?
Phosphorene is the name given to a monolayer of black phosphorus. The term is also often used to describe several stacked monolayers, alternatively known as ‘few-layer phosphorene’ or ‘few-layer black phosphorus’.
Since the discovery of graphene, interest in 2D semiconducting materials has increased substantially. Particular attention is being given to phosphorene due to its unique in-plane layered structure and thickness-dependent electronic band gap. Black phosphorus bridges the properties of graphene-like materials and transition metal dichalcogenides (TMDCs) and is set to be the next big thing in 2D optoelectronics.
Like graphene and TMDCs, black phosphorus is semiconducting in nature and has a two-dimensional layered structure consisting of individual layers stacked together through weak van der Waals forces. These layers can be separated with familiar techniques such as mechanical scotch-tape exfoliation or sonication of bulk-layered crystals.
The structure of black phosphorus arises from the electronic configuration of phosphorous (3s2 3p3). Here, sp3 hybridisation allows phosphorus to form three bonds to adjacent atoms, leaving a lone pair of electrons. Unlike graphene and TMDCs, the sp3 bonding in black phosphorus results in layers with a puckered honeycomb structure.
This structure is what gives phosphorene a number of fascinating properties which are not found in other 2D materials. Most notably, phosphorene is an intrinsic p-type semiconductor that possesses a finite and direct thickness dependant band gap. Substantial anisotropy in transport behaviour in few-layer phosphorene has been observed along different directions of the 2D crystal lattice, and this behaviour can be tuned by applying strain across the lattice.
Applications of Black Phosphorus
Due to its unique properties, exfoliated monolayer and few-layer black phosphorus has potential for a wide range of applications in electronics and optoelectronics. Applications that have been suggested (or are currently being investigated) include in LEDs, photodetectors, supercapacitors, superconductors and memory devices.
Black phosphorus powder can be used to synthesis black phosphorus quantum dots (BPQDs). The properties of BPQDs make them well suited for the development of thermoelectric devices, sensors, LEDs, OPVs, and energy storage systems.
Field-effect transistors for electronic devices
Field-effect transistors (FETs) are the most studied of phosphorene’s potential applications, with many theoretical and experimental studies carried out over the last 5 years. The attractive FET characteristics of relatively high on/off ratio and good charge carrier mobility along with a high conductivity should ensure fast switching with high efficiency and error-free logic.
Photodetectors in communication networks
Phosphorene’s direct bandgap is tunable (between 0.3 eV to 1.88 eV) by changing the number of stacked layers. This makes it optically active in the red to NIR spectrum and has allowed the fabrication of visible to NIR photodetectors , , . This region of the spectrum is important for optical fibre networks and suggests that phosphorene could play a role in future communication networks.
Photovoltaics and solar cells
The photovoltaic effect has been observed in few-layer black phosphorus . With thicker samples having a bandgap smaller than that of silicon, it could be used to harvest the NIR-IR region of the solar spectrum that silicon cannot access. While the observed external quantum efficiencies observed so far are small (<1%), it has been predicted that a modified phosphorene structure could reach efficiencies of 20% .
Phosphorene is an interesting prospect for chemical sensing due to its large surface-to-volume ratio and the presence of a lone electron pair on each atom. A NO2 sensor has been demonstrated with a sensitivity of 20 parts per billion in air . A theoretical study has suggested that single molecule sensing may be possible with such sensors .
Phosphorene combines low thermal and high electrical conductivity, making it suitable for thermoelectric applications.
Flexible memory devices
Black phosphorus quantum dots have the potential to be used as the active layer in flexible memory devices. They have exhibited a non-volatile, re-writable memory effect with high on/off current ratios (more than 6.0 × 104).
Energy storage and battery electrodes
Phosphorene combines significant, reversible charge-storage capacity with small volume change and good electrical conductivity. This combination of properties makes it good candidate for energy storage applications. Phosphorene has therefore been proposed as an anode material for Li-ion batteries, with lithium diffusion expected to be orders of magnitude faster than in other 2D materials . Structural engineering, incorporation into heterostructures with other 2D materials, and addition of defect states is expected to improve lithium diffusion rates and binding energies.
Next generation batteries
Few-layer black phosphorus may also find application in future sodium ion batteries (the expected replacement for lithium ion) . The large interlayer spacing allows for the diffusion of the large sodium ions, in contrast to current graphite anodes.
Black Phosphorus Structure
When individual layers of black phosphorus are separated from the bulk crystal through mechanical exfoliation or sonication, the resulting 2D layers of phosphorene have atoms arranged in a puckered honeycomb structure. It is this structure which gives the material its fascinating properties.
The puckered honeycomb structure of phosphorene means that charge carriers experience a very different topology depending on which direction they are travelling in the phosphorene plane (the 2 principle in-plane axes being termed ‘armchair’ (AC) perpendicular to the ridges and ‘zig-zag’ (ZZ) parallel to the ridges). This results in a strong anisotropy in many of its properties, such as carrier mobility (and effective mass), thermal conductivity, and mechanical characteristics (including Young’s modulus).
2D Black Phosphorus Properties
Like other van der Waals 2-dimensional materials such as MoS2, the optical, electronic, and mechanical properties of phosphorene differ from that of the bulk state due to combinations of factors. These include:
- High surface-to-volume ratio
- Out-of-plane charge carrier confinement
- No interlayer interactions
- Increased Coulomb interaction between charge carriers (reduced dielectric screening)
A hole mobility up to ~1000 cm2V-1s-1 has been measured in few-layer phosphorene in a FET structure . The anisotropy of carrier mobility travelling along the AC and ZZ directions has also been demonstrated .
Specifically, after exfoliation of black phosphorus crystals or powder, black phosphorus typically has the following properties:
- Orthorhombic C puckered honeycomb structure
- 0.3 eV ~ 1.5 eV thickness-dependent bandgap
- High charge carrier mobility ~1000 cm2V-1s-1
- Thermal conductivity of 86 (34) Wm-1K-1 in ZZ (AC) direction (few-layer)
- On/off ratio of 105
Black phosphorus powder can be combined with liquid-phase exfoliation or further chemical modification to control the physical and electronic properties of the resultant semiconductor material. Liquid-phase exfoliation is often used to create black phosphorus quantum dots. Black phosphorus quantum dots have an average size of 4.9 nm and a thickness of 1.9 nm.
Band Gap of Phosphorene
Black phosphorene has a thickness-dependent direct band gap, ranging from 1.88 eV (for a single monolayer) to 0.3 eV (for the bulk material).
A comparison between the band gaps of several 2-dimensional materials is shown below, along with those of conventional bulk semiconductors. The wide tunability of the phosphorene bandgap by changing the sample thickness makes it attractive for a number of applications.
Processing Black Phosphorus
Phosphorene monolayers and multilayers can be produced from bulk black phosphorus through either mechanical (scotch-tape method) or liquid exfoliation. CVD growth has recently been reported for few-layer thicknesses with areas of a few square microns .
Black phosphorus degrades under ambient conditions. Studies show that water alone does not result in its degradation. However, oxygen plays an important role in its degradation by inducing changes in its electronic structure.
Black phosphorus powder is often used in the preparation of black phosphorus quantum dots, normally via liquid-phase exfoliation.
Literature and Reviews
- The renaissance of black phosphorus, X. Ling et al., PANS, 112 (15), 4523-4530 (2015); DOI: 10.1073/pnas.1416581112.
- Isolation and characterization of few-layer black phosphorus, A. Castellanos-Gomez et al., 2D Mater. 1(2) 025001 (2014); doi:10.1088/2053-1583/1/2/025001.
- High-mobility transport anisotropy and linear dichroism in few-layer black phosphorus, J. Qiao et al., Nat. Commun., 5:4475 (2014); DOI: 10.1038/ncomms5475.
- Black Phosphorus: Narrow Gap, Wide Applications, A. Castellanos-Gomez, J. Phys. Chem. Lett., 6, 4280−4291 (2015); DOI: 10.1021/acs.jpclett.5b01686.
- Strain Engineering for Phosphorene: The Potential Application as a Photocatalyst, B.Sa et al., J. Phys. Chem. C, 118 (46), 26560–26568 (2014); DOI: 10.1021/jp508618t.
- Phosphorene: Fabrication, Properties, and Applications, L. Kou etal., J. Phys. Chem. Lett., 2015, 6 (14), 2794–2805 (2015); DOI: 10.1021/acs.jpclett.5b01094
- Strain-Engineering the Anisotropic Electrical Conductance of Few-Layer Black Phosphorus, R. Fei et al., Nano Lett., 14 (5), 2884–2889 (2014); DOI: 10.1021/nl500935z.
- Layer-dependent Band Alignment and Work Function of Few-Layer Phosphorene, Y. Cai et al., Sci. Rep., 4 : 6677 (2014); DOI: 10.1038/srep06677.
- Visualizing Optical Phase Anisotropy in Black Phosphorus, S. Lan et al., ACS Photonics, 3 (7), 1176–1181 (2016); DOI: 10.1021/acsphotonics.6b00320.
- Recent advances in synthesis, properties, and applications of phosphorene, M. Akhtar et al., NPJ 2D Mater. Appl., 1, 5 (2017).
- Semiconducting Black Phosphorus, A. Morita, Appl. Phys. A 39, 227-242 (1986)
- Black Phosphorus Gas Sensors, A. Abbas et al., ACS Nano, 9 (5), 5618–5624 (2015)
- Semiconducting black phosphorus: synthesis, transport properties and electronic applications, H. Liu et al., Chem. Soc. Rev., 44, 2732 (2015)
- From Black Phosphorus to Phosphorene: Basic Solvent Exfoliation, Evolution of Raman Scattering, and Applications to Ultrafast Photonics, Z. Guo et al., Adv. Funct. Mater., 25, 6996–7002 (2015)
- High-quality sandwiched black phosphorus heterostructure and its quantum oscillations, X. Chen et al., Nat. Commun., 6, 7315 (2015)
- Anisotropic in-plane thermal conductivity observed in few-layer black phosphorus, Z. Luo et al., Nat. Commun., 6, 8572 (2015)
- Phosphorene: An Unexplored 2D Semiconductor with a High Hole Mobility, H. Liu et al., ACS Nano, 8 (4), 4033–4041 (2014)
- Black Phosphorus-Monolayer MoS2 van der Waals Heterojunction p-n Diode, Y. Deng et al., ACS Nano, 8 (8), 8292–8299 (2014)
- Two-dimensional crystals: Phosphorus joins the family, Nat. Nanotech., 9 (5), 330 (2014)
- Black Phosphorus Quantum Dots with Tunable Memory Properties and Multilevel Resistive Switching Characteristics, S. Han et al., Adv. Sci., 4, 1600435 (2017); DOI: 10.1002/advs.201600435.
- Quantum dots derived from two-dimensional materials and their applications for catalysis and energy, X, Wang et al., Chem. Soc. Rev., 45, 2239 (2016); DOI: 10.1039/c5cs00811e.
- Electronic properties of bilayer phosphorene quantum dots in the presence of perpendicular electric and magnetic fields, L. Li et al., Phys. Rev. B 96, 155425 (2017); DOI: 10.1103/PhysRevB.96.155425.
- Black Phosphorus Quantum Dots, X. Zhang et al., Angew. Chem. Int. Ed., 54, 3653 –3657 (2015); DOI: 10.1002/anie.201409400.
- Ultrasmall Black Phosphorus Quantum Dots: Synthesis and Use as Photothermal Agents, Z. Sun et al., Angew. Chem., 127,11688 –11692 (2015); DOI:10.1002/ange.201506154.
- Red Phosphorus: An Elemental Photocatalyst for Hydrogen Formation from Water, F. Wang et al., Appl. Catal., 111, 409-414 (2012)
- Single-Layered Hittorf’s Phosphorus: A Wide-Bandgap High Mobility 2D Material, Schusteritsch et al., Nano Lett., 16 (5), 2975-2980 (2016)
- 2D Nanoelectronics: Physics and Devices of Atomically Thin Materials, M. Dragoman and D. Dragoman, Springer International Publishing (2017)
- Thermal conductivity determination of suspended mono- and bilayer WS2 by Raman spectroscopy, Peimyoo et al., Nano Research, 8 (4), 1210–1221 (2015)
- Thermal Conductivity of Monolayer Molybdenum Disulfide Obtained from Temperature-Dependent Raman Spectroscopy, R. Yan et al., ACS Nano, 8 (1), 986–993 (2014)
- Black phosphorus field-effect transistors, Li et al, Nature Nanotechnology, 9, 372–377 (2014)
- Anisotropic Thermal Conductivity of Exfoliated Black Phosphorus, H. Jang et al., Advanced materials, 27 (48), 8017-8022 (2015)
- Rediscovering black phosphorus as an anisotropic layered material for optoelectronics and electronics, Xia et al., Nature Communications, 5, 4458 (2014)
- Graphene Field-Effect Transistors with High On/Off Current Ratio and Large Transport Band Gap at Room Temperature, F. Xia et al., Nano Lett., 10 (2), 715–718 (2010)
- High-mobility and air-stable single-layer WS2 field-effect transistors sandwiched between chemical vapor deposition-grown hexagonal BN films, M. Iqbal et al., Scientific Reports, 5, 10699 (2015)
- Low voltage and high ON/OFF ratio field-effect transistors based on CVD MoS2 and ultra high-k gate dielectric PZT, C. Zhou et al., Nanoscale, 7, 8695-8700 (2015)
- Optical tuning of exciton and trion emissions in monolayer phosphorene, J. Yang et al., Light: Science & Applications, 4, 312 (2015)
- Tin Disulfide-An Emerging Layered Metal Dichalcogenide Semiconductor: Materials Properties and Device Characteristics, Y. Huang et al., ACS Nano, 8 (10), 10743–10755 (2014)
- SnS-based thin film solar cells: perspectives over the last 25 years, Journal of Materials Science: Materials in Electronics, J. Andrade-Arvizu et al., 26 (7), 4541–4556 (2015)
- Tin(II) Sulfide (SnS) Nanosheets by Liquid-Phase Exfoliation of Herzenbergite: IV−VI Main Group Two-Dimensional Atomic Crystals, J. Brent et al., J. Soc., 137, 12689 (2015)
- Tuning magnetotransport in a compensated semimetal at the atomic scale, L. Wang et al., Nature Communications, 6, 8892 (2015)
- Tungsten ditelluride: a layered semimetal, C. Lee, Scientific Reports, 5, 10013 (2015)
- Indirect-to-Direct Band Gap Crossover in Few-Layer MoTe2, I. Lezama, Nano Lett., 15 (4), 2336-2342 (2015)
- Optical Properties and Band Gap of Single- and Few-Layer MoTe2 Crystals, C. Ruppert et al., Nano Lett., 14 (11), 6231-6236 (2014)
- Black Phosphorus Photodetector for Multispectral, High-Resolution Imaging, M. Engel et al., Nano Lett, 14 (11), 6414–6417 (2014)
- Waveguide-integrated black phosphorus photodetector with high responsivity and low dark current, N. Youngblood et al., Nature Photonics, 9, 247–252 (2015)
- Fast and Broadband Photoresponse of Few-Layer Black Phosphorus Field-Effect Transistors, M. Buscema et al., Nano Lett., 14 (6), 3347–3352 (2015)
- Photovoltaic effect in few-layer black phosphorus PN junctions defined by local electrostatic gating, M. Buscema et al., Nature Communications, 5, 4651 (2014)
- Edge-Modified Phosphorene Nanoflake Heterojunctions as Highly Efficient Solar Cells, W. Hu et al., Nano Lett., 16 (3), 1675–1682 (2016)
- Ultrahigh sensitivity and layer-dependent sensing performance of phosphorene-based gas sensors, S. Cui et al., Nature Communications, 6, 8632 (2015)
- Large Electronic Anisotropy and Enhanced Chemical Activity of Highly Rippled Phosphorene, A. Kistanov et al., Phys. Chem. C, 120 (12), 6876–6884 (2016)
- Ultrafast and Directional Diffusion of Lithium in Phosphorene for High-Performance Lithium-Ion Battery, W. Li et al., Nano Lett., 15 (3), 1691–1697 (2015)
- Phosphorene as an anode material for Na-ion batteries: a first-principles study, V. Kulish et al., Phys. Chem. Chem. Phys., 17, 13921-13928 (2015)
- Growth of 2D black phosphorus film from chemical vapor deposition, J. Smith et al., Nanotechnology, 27 (21), 215602 (2016)
|Molecular Weight||30.97 g/mol|
|Bandgap||0.3 eV ~ 1.5 eV|
|Synthesis||Synthetic, by chemical vapour transport (CVT)|
|Electronic Properties||2D semiconductor|
|Melting Point||416 °C|
|Black phosphorus powder||≥99.995%|
|Small crystals by weight||≥99.999%|
|Individual crystals by size||≥99.999%|
|M2106B1-250mg||Small crystals||250 mg||£480|
|M2106B1-500mg||Small crystals||500 mg||£850|
|M2106B1-1g||Small crystals||1 g||£1300|
|M2106A10||Crystal||Small (≥10 mm2)||£520 ea.|
|M2106A25||Crystal||Medium (≥25 mm2)||£700 ea.|
We get asked a lot of questions about the materials we stock. You can find the answers to the most frequently asked questions about black phosphorus and phosphorene below. Please contact us for all other enquries.
Depending on environmental conditions and how it is processed, elemental phosphorus can take several forms (allotropes). These allotropes are generally referred to by their physical appearance; white (or yellow) phosphorus, red phosphorus, violet phosphorus, and black phosphorus.
White phosphorus will auto-ignite and burn fiercely in air when heated to 30 °C, which limits its use in pure form to explosives. It is a wide bandgap insulator, and this – combined with its tendency to explode – is the reason why it has not garnered much interest from the optoelectronic industry.
Red phosphorus is a more stable allotrope (note that several different forms of red phosphorus exist, with varying degrees of crystallinity) that displays some semiconducting properties . Despite having a bandgap in the near-infrared (NIR), red phosphorus is also yet to find an application in semiconductor devices. It is, however, used on the striking surface of ‘safety’ matchboxes. Previously, ‘non-safety’ matches used white phosphorus as the ignition source.
Violet phosphorus (or ‘Hittorf phosphorus’, after the person who first discovered it) is a stable crystalline allotrope that takes the structural form of nanotubes with a pentagonal cross-section. It is sometimes classed as a subset of red phosphorus. Despite being isolated in 1865, relatively little is known about it. Some recent theoretical work suggests that monolayers of violet phosphorus could exhibit a larger direct bandgap than black phosphorus with good charge carrier mobility . This could be a material to watch out for in the near future.
Black phosphorus differs considerably from other allotropes of phosphorus, which do not share its stability, properties, or structure.
The properties of the four common allotropes of phosphorus are summarised in the following table.
White (or yellow)
Violet (or Hittorf/ monoclinic)
Black (or phosphorene)
Appearance at room temperature
Purple solid. Large pieces appear glossy
Tetrahedron of 4 P atoms
Amorphous structure of covalently-bonded P atoms
Crystalline pentagonal nanotubes of covalently bonded P atoms
Van der Waals bonded layers of P atoms covalently bonded in a puckered honeycomb structure
Heating of phosphate rock with carbon and silica to ~1200 °C
Heating of white phosphorus to ~300 °C in an air-free environment
Heating and cooling of white phosphorus dissolved in lead, or heating of red phosphorus in a sealed tube
Heating of white phosphorus to ~200 °C at 1.2 GPa, or from red phosphorus at 8.5 GPa
Will auto-ignite when exposed to air at ~30 °C. Wide band gap insulator. Chemiluminescent (but not phosphorescent)
Will auto-ignite when exposed to air at ~300 °C. Semiconductor
More stable and more dense than red phosphorus. Monolayers may exhibit a direct band gap larger than black phosphorus
Most stable allotrope of phosphorus. Semiconductor. Thickness-dependent bandgap. High charge carrier mobility
Matches, flame retardant (when mixed with flammable plastics at low concentration)
Little is currently known about the optoelectronic properties of violet phosphorus
Potential applications in optical devices (eg. photodetectors), electronics (eg. FETs), energy storage, and many more
The structure of each allotrope of phosphorus is shown below.
Single-layer black phosphorus’ hole mobility compares favourably with Transition Metal Dichalcogenide Monolayers (TMDCs) but is orders of magnitude below that of graphene. Thermal conductivity is again below that of graphene, but competitive with TMDCs. Transistors fabricated from few-layer phosphorene display a high on/off ratio of 105 – significantly better than unmodified graphene, but falling behind TMDCs.
Phosphorene can be seen as an intermediary material, taking favourable properties of graphene and TDMCs but dispensing with their undesirable characteristics.
A comparison between some of the relevant optoelectronic properties of 2D materials is given in the table below.
2 eV (WS2)
1.9 eV (MoS2)
0.3 eV (bulk) – 1.88 eV (monolayer)
~1000 cm2V-1s-1 (WS2)
~350 cm2V-1s-1 (MoS2)
~1000 cm2V-1s-1 
32 Wm-1K-1 (WS2) 
35 Wm-1K-1 (MoS2) 
86 (34) Wm-1K-1 in ZZ (AC) direction (few-layer) 
~107 (WS2) 
~108 (MoS2) 
Few or multi-layer black phosphorus and black phosphorus quantum dots (created via the processing of black phosphorus crystals or powder) are used for a wide range of applications, including:
- Field-effect transistors
- Electronic devices
- Photovoltaics and solar cells
- Gas sensors
- Energy storage
- Battery electrodes
- Thermoelectric applications
- Flexible memory devices
Please see the applications section on the overview tab for more information.
Black phosphorus quantum dots are normally created from black phosphorus powder via liquid-phase exfoliation.
To the best of our knowledge the information provided here is accurate. However, Ossila assume no liability for the accuracy of this page. The values provided are typical at the time of manufacture and may vary over time and from batch to batch. Products may have minor cosmetic differences (e.g. to the branding) compared to the photos on our website. All products are for laboratory and research and development use only, and may not be used for any other purpose including health care, military, pharmaceuticals, cosmetics, food, or commercial applications.