FREE shipping to on qualifying orders when you spend or more. All prices ex. VAT.

Black Phosphorus (BP) Powder and Crystals


Product Code M2106C1
Price $286.00 ex. VAT

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

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

≥99.995% purity

From £260

Black phosphorus crystal by weight

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

≥99.999% purity

From £440

Black phosphorus crystal by size

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*

≥99.999% purity

From £480

*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).

Platinum FET Test Chips for 2D Materials

Test chips optimized for 2D materials
  • Affordable
  • World-Wide Shipping
  • Dual Channel Electrodes

Buy Online £180

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 [20], [21], [22]. 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 [23]. 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% [24].

Gas sensors

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 [25]. A theoretical study has suggested that single molecule sensing may be possible with such sensors [26].

Thermoelectric applications

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 [27]. 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) [28]. 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.

Phosphorene structure
Top and side view of single-layer phosphorene structure showing armchair (AC) and zigzag (ZZ) directions

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 [4]. The anisotropy of carrier mobility travelling along the AC and ZZ directions has also been demonstrated [8].

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).

Black phosphorus monolayer and bulk band structure
Electronic band structure of bulk (left) and monolayer (right) black phosphorus. Note that the band gap of the monolayer has been underestimated by the DFT calculation.

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.

2D and conventional bulk semiconductor bandgap chart
Bandgap energies of 2D materials and conventional bulk semiconductors

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 [29].

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.
  1. Red Phosphorus: An Elemental Photocatalyst for Hydrogen Formation from Water, F. Wang et al., Appl. Catal., 111, 409-414 (2012)
  2. Single-Layered Hittorf’s Phosphorus: A Wide-Bandgap High Mobility 2D Material, Schusteritsch et al., Nano Lett., 16 (5), 2975-2980 (2016)
  3. 2D Nanoelectronics: Physics and Devices of Atomically Thin Materials, M. Dragoman and D. Dragoman, Springer International Publishing (2017)
  4. Thermal conductivity determination of suspended mono- and bilayer WS2 by Raman spectroscopy, Peimyoo et al., Nano Research, 8 (4), 1210–1221 (2015)
  5. Thermal Conductivity of Monolayer Molybdenum Disulfide Obtained from Temperature-Dependent Raman Spectroscopy, R. Yan et al., ACS Nano, 8 (1), 986–993 (2014)
  6. Black phosphorus field-effect transistors, Li et al, Nature Nanotechnology, 9, 372–377 (2014)
  7. Anisotropic Thermal Conductivity of Exfoliated Black Phosphorus, H. Jang et al., Advanced materials, 27 (48), 8017-8022 (2015)
  8. Rediscovering black phosphorus as an anisotropic layered material for optoelectronics and electronics, Xia et al., Nature Communications, 5, 4458 (2014)
  9. 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)
  10. 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)
  11. 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)
  12. Optical tuning of exciton and trion emissions in monolayer phosphorene, J. Yang et al., Light: Science & Applications, 4, 312 (2015)
  13. Tin Disulfide-An Emerging Layered Metal Dichalcogenide Semiconductor: Materials Properties and Device Characteristics, Y. Huang et al., ACS Nano, 8 (10), 10743–10755 (2014)
  14. 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)
  15. 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)
  16. Tuning magnetotransport in a compensated semimetal at the atomic scale, L. Wang et al., Nature Communications, 6, 8892 (2015)
  17. Tungsten ditelluride: a layered semimetal, C. Lee, Scientific Reports, 5, 10013 (2015)
  18. Indirect-to-Direct Band Gap Crossover in Few-Layer MoTe2, I. Lezama, Nano Lett., 15 (4), 2336-2342 (2015)
  19. Optical Properties and Band Gap of Single- and Few-Layer MoTe2 Crystals, C. Ruppert et al., Nano Lett., 14 (11), 6231-6236 (2014)
  20. Black Phosphorus Photodetector for Multispectral, High-Resolution Imaging, M. Engel et al., Nano Lett, 14 (11), 6414–6417 (2014)
  21. Waveguide-integrated black phosphorus photodetector with high responsivity and low dark current, N. Youngblood et al., Nature Photonics, 9, 247–252 (2015)
  22. Fast and Broadband Photoresponse of Few-Layer Black Phosphorus Field-Effect Transistors, M. Buscema et al., Nano Lett., 14 (6), 3347–3352 (2015)
  23. Photovoltaic effect in few-layer black phosphorus PN junctions defined by local electrostatic gating, M. Buscema et al., Nature Communications, 5, 4651 (2014)
  24. Edge-Modified Phosphorene Nanoflake Heterojunctions as Highly Efficient Solar Cells, W. Hu et al., Nano Lett., 16 (3), 1675–1682 (2016)
  25. Ultrahigh sensitivity and layer-dependent sensing performance of phosphorene-based gas sensors, S. Cui et al., Nature Communications, 6, 8632 (2015)
  26. Large Electronic Anisotropy and Enhanced Chemical Activity of Highly Rippled Phosphorene, A. Kistanov et al., Phys. Chem. C, 120 (12), 6876–6884 (2016)
  27. 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)
  28. 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)
  29. Growth of 2D black phosphorus film from chemical vapor deposition, J. Smith et al., Nanotechnology, 27 (21), 215602 (2016)

Technical Data

CAS Number 7723-14-0
Chemical Formula P
Molecular Weight 30.97 g/mol
Bandgap 0.3 eV ~ 1.5 eV
Synthesis Synthetic, by chemical vapour transport (CVT)
Structure Orthorhombic C
Electronic Properties 2D semiconductor
Melting Point 416 °C
Colour Black
Form Purity
Black phosphorus powder ≥99.995%
Small crystals by weight ≥99.999%
Individual crystals by size ≥99.999%

MSDS Documents

Black phosphorus powder MSDSBlack phosphorus powder

Black phosphorus small crystals MSDSSmall crystals

Black phosphorus cyrstal MSDSIndividual crystals

Pricing Table

Product Code Form Size/Weight Price
M2106C1 Powder 250 mg £260
M2106C1 Powder 500 mg £440
M2106C1 Powder 1 g £740
M2106B1 Small crystals 250 mg £440
M2106B1 Small crystals 500 mg £760
M2106B1 Small crystals 1 g £1200
M2106A10 Crystal Small (≥10 mm2) £480 ea.
M2106A25 Crystal Medium (≥25 mm2) £640 ea.

Shipping is free for qualifying orders.

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.

General

Applications


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. All products are for laboratory and research and development use only, and may not be used for any other purpose including health care, pharmaceuticals, cosmetics, food or commercial applications.

Return to the top