Sulfur-Doped Black Phosphorus Field-Effect Transistors with

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Sulfur-doped black phosphorus field-effect transistors with enhanced stability Weiming Lv, Bingchao Yang, Bochong Wang, Wenhui Wan, Yanfeng Ge, Ruilong Yang, Chunxue Hao, Jianyong Xiang, Baoshun Zhang, Zhongming Zeng, and Zhongyuan Liu ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b19169 • Publication Date (Web): 26 Feb 2018 Downloaded from http://pubs.acs.org on February 27, 2018

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ACS Applied Materials & Interfaces

Sulfur-doped black phosphorus field-effect transistors with enhanced stability Weiming Lv,† Bingchao Yang,‡ Bochong Wang,* # Wenhui Wan,# Yanfeng Ge,# Ruilong Yang,‡ Chunxue Hao,‡ Jianyong Xiang,‡ Baoshun Zhang,† Zhongming Zeng,*,† Zhongyuan Liu*‡ †

Key Laboratory of Nanodevices and Applications, Suzhou Institute of Nano-tech and Nano-

bionics, Chinese Academy of Sciences, Suzhou 215123, China ‡

State Key Laboratory of Metastable Materials Science and Technology, Yanshan University,

Qinhuangdao 066004, China #

Key Laboratory for Microstructural Material Physics of Hebei Province, School of Science,

Yanshan University, Qinhuangdao 066004, China

ACS Paragon Plus Environment

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ABSTRACT: Black phosphorus (BP) has drawn great attention owing to its tunable band gap depending on thickness, high mobility and large on/off ratio, which makes BP attractive for using in future two-dimensional electronic and optoelectronic devices. However, its instability under ambient conditions poses challenge to the research and limits its practical applications. In this work, we present a feasible approach to suppress the degradation of BP by sulfur (S) doping. The fabricated S-doped BP few layer field-effect transistors (FETs) show more stable transistors performance under ambient conditions. After exposing to air for 21 days, the charge-carrier mobility of a representative S-doped BP FETs device decreases from 607 to 470 cm2V-1s-1 (remained as high as 77.4%) in ambient and a large Ion/Ioff ratio of ~103 is still retained. The AFM analysis, including surface morphology, thickness and roughness, also indicates the slower degradation rate of S-doped BP compared with BP. First-principle calculations show that the dopant S atom energetically prefers to chemisorb on the BP surface in a dangling form and the enhanced stability of S-doped BP can be ascribed to the shift-down of the conduction band minimum (CBM) of BP below the redox potential of O2/O2-. Our work suggests that S doping is an effective way to enhance the stability of black phosphorus. KEYWORDS: Black phosphorus, field-effect transistors, stability, doping, first-principle calculation


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1. INTRODUCTION Recently, the physical dimension of silicon-based field-effect transistors (FETs) is approaching its scaling limitation. In the semiconductor industry, it is much urgent to find novel materials with sub-miniature structure and exceptional performance in order to encounter the challenges and achieve the development of related productions. Two-dimensional (2D) nanomaterials are attracting dramatically increasing interest for electronic and optoelectronic applications owing to their thickness scalability down to a monolayer with layered structure and special physical properties.1-4 As one of the newest member of 2D nanomaterials, black phosphorus (BP) has a puckered layered structure with a tunable direct band gap ranging from ~0.3 eV for bulk to ~2 eV for monolayer.5 The tunable direct bandgap on thickness gives BP an advantage over graphene that has zero band gap, and transition metal dichalcogenides (TMDs) such as MoS2 and WS2 which show relatively low mobility in transistors applications.6-9 A series of works have demonstrated that BP exhibits excellent field-effect transistor performance, with high mobility up to ~1000 cm2V-1s-1 and on/off ratio of ~102-105.5, 10-12 In addition, BP shows promising applications in extensive field such as energy storage areas (lithium/sodium ion battery, thermoelectric devices and supercapacitors),13-15 gas sensor,16-17 humidity sensor,18 biomedicine field19 and memory devices, etc.20-23 In spite of the board research and application prospects of BP, the environmental instability is a fundamental obstacle limiting its development. Previous studies have confirmed that BP is reactive to water and oxygen under ambient conditions.24-26 BP has a puckered honeycomb structure, in which one phosphorus atom is covalently bonded to three neighboring atoms by using three single outermost orbital electrons. The left two electrons forming a lone pair of electrons are exposed, which can readily react with oxygen to form PxOy.27 Then the reaction


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between PxOy and water results in the formation of phosphoric acid that will lead to compositional and physical change and finally etch the material away after long-term exposure in air.6, 12, 24, 28-29 Many efforts have been made to improve the stability of BP in air, including a passivation treatment by covering cap layer such as Al2O3,28, 30-31 SiO2,32 and graphene, etc.12 and coordination or functionalization process by chemical modification such as via aryl diazonium,29 titanium sulfonate ligand33 and metal ions, etc.34 Recent works have demonstrated that doping is an effective way to modify the physical and chemical properties of BP.35-40 In our previous work, tellurium (Te) doping BP FETs shown high carrier mobility and enhanced stability.41 Our theoretical calculation shows that the doped Te atoms cause the conduction band minimum (CBM) shifting close to or even below the redox potential of O2/O2-, which reduce the possibility of generation of light-induced O2- and suppress the oxidation process of BP.27, 42 As the elements of S and Te belong to the same main group and the radius of S atom is similar to the P atom, the S atom doping can enhance the stability of BP and the effect may be more efficient than Te. In this work, we synthesized the S-doped BP using the method of high-pressure and hightemperature. The stability of S-doped BP FETs were investigated by continuously measuring the FETs performances and characterizing the morphology change using atomic force microscope (AFM) under ambient conditions for 21 days. The FETs performances and AFM results suggested that the S-doping could enhance the stability of BP effectively, consistent with the first-principle calculations. 2. EXPERIMENTAL SECTION 2.1 Synthesis of BP and S-doped BP. BP crystal was synthesized from the red phosphorus (99.999%, Alfa Aesar) under high temperature of 1000 °C and high pressure of 2 GPa for 10 min in the six-anvil cubic apparatus (Six WC anvils, China). S-doped BP


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crystal was synthesized under the same conditions mixed with 1wt% sulfur (99.99%, Alfa Aesar). 2.2 Fabrication of S-doped BP FETs. The mechanically exfoliated S-doped BP flakes were transferred to a 300 nm SiO2 covered p++Si substrate. The metal contacts of Au (70 nm)/Ni (10 nm) were fabricated using electron-beam lithography and electron-beam evaporator. The samples were stored at ultra-clean chamber with constant humidity of 45%-50% and steady temperature of 25 °C for aging study. 2.3 Characterization. X-ray diffraction (XRD) was characterized on a Rigaku Smartlab diffractometer using Cu Kα radiation (40 V, 200 mA). Raman spectra were measured on Renishaw inVia microRaman spectroscopy with a laser radiation of 514 nm. Si powder was used to calibrate the peak positions for XRD and Raman measurements. Fracture surfaces and elemental analysis were checked on a SEM (Quanta FEG 250) equipped with EDS. Electrical measurement was performed on a Keithley 4200 parameter analyzer under ambient conditions. The morphology characterization was investigated on an Atomic Force Microscopy (Veeco Dimension 3000) using normal tapping mode under ambient conditions. The XPS measurements were performed on an Axis Ultra spectrometer (ESCALAB 250Xi, Thermo Fisher). 2.4 First-Principle Calculations. The first-principle calculations were carried out within the frame of density functional theory (DFT), as implemented in the Vienna ab-initio simulation package (VASP). The exchange-correlation interactions were treated within the generalized gradient approximation of the Perdew-Burke-Ernzerhof type. The computational details can be found in the Supporting Information.


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3. RESULTS AND DISCUSSION

Figure 1. (a) XRD patterns and (b) Raman spectra of BP and S-doped BP. Insert in Figure 1a is the enlarged region of reflection peaks of (040) and (111). Si powder is used for calibration of peak positions. (c) SEM images of S-doped BP crystals. The scale bar is 5 µm. Element mapping of (d) P and (e) S in a selected area marked in Figure 1c. Figure 1 illustrates the structure characterization of BP and S-doped BP powder. In Figure 1a, the XRD pattern of S-doped BP is similar to the undoped BP with obvious reflection peaks of (020), (040) and (060), implying high quality of the as-prepared Sdoped BP.43 The insert figure in Figure 1a shows a slight shift of reflection peaks (040) and (111) to lower angle in S-doped BP, which is caused by S doping. The Raman spectra for both BP and S-doped BP sample exhibit characteristic vibration modes of A , B and A .41, 43 Similarly, the vibration modes of S-doped BP shift to lower wavenumber. The induced S atoms change the layer thickness and spacing, which lead to the shift of


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A and A . The SEM image of S-doped BP powders demonstrates a well-layered structure (Figure 1c). As shown in Figure 1d and 1e, the EDS results from the flake confirm the coexistence of phosphorus and S elements, and the S element is uniformly distributed. The weight percent of S is calculated to be 0.88% which is consistent with the experimental design. High-resolution X-ray photoelectron spectroscopy (HR-XPS) was performed to examine the binding energy of P and S in BP. The P 2p3/2 and P 2p1/2 peaks of undoped BP are located at 130.5 eV and 130.9 eV (Figure S1a), while for the S-doped BP, the binding energy of P 2p3/2 and P 2p1/2 increase about ~0.3 eV. The peaks of S 2p3/2 at 164.8 eV and S 2p1/2 at 163.5 eV in S-doped BP are about 0.4 eV less than that of bare S (Figure S1b), confirming the successful doping of S into BP crystal. The shift of S peaks is similar to that of Ag+ in the Ag+-modified BP.34 The synchronous shift of both P peaks and S peaks indicates that there is an electronic interaction between P and S in the S-doped BP and the formation of S-P bond. For evaluating the electronic properties, S-doped BP nanoflakes with thickness about ~10 nm were mechanically exfoliated onto p++ silicon substrates covering 300 nm SiO2 to fabricate the back-gated FETs. Figure 2a shows a schematic of the FETs device and the measurement circuit. Ni/Au electrodes were used as source and drain electrodes by using electron beam lithography. Figure 2b shows the AFM image and height profile of one representative S-doped BP FET device, which indicates a thickness of ~9.5 nm. The channel length and channel width are ~1.3 µm and ~0.9 µm, respectively. Figure 2c shows the output curves of S-doped BP FETs devices by sweeping drain-source current versus drain-source voltage (Ids-Vds) at backgate voltage (Vg) ranging from -80 V to 80 V with a step of 10 V. The excellent linearity implies good Ohmic contact characteristics of the S-doped BP flakes with Au/Ni electrodes. Figure 2d shows


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the transfer curves of S-doped BP FETs by sweeping Ids versus Vg ranging from -80 V to 80 V at fixed Vds of 0.01 V. The monotonically decreased Ids values with increased Vg indicate the P-type semiconducting behavior of S-doped BP FETs.5

Figure 2. (a) Schematic of device structure of few-layer S-doped BP FETs. (b) Height profile and AFM image of S-doped BP FETs. The scale bars is 1 µm. (c) The output characteristics of newly prepared S-doped BP FETs by sweeping drain-source current (Ids) under backgate voltage (Vg ) ranging from -80 V to 80 V with a step of 10 V. (d) The transfer curves of S-doped BP FETs at fixed Vds of 0.01 V. Two parameters including carrier mobility and current Ion/Ioff ratio are extracted from the transfer curves to characterize the electrical performance of S-doped BP FETs devices. The mobility can be calculated using the following equations:

µFE =

dIds

L

dVg WCi Vds

(1)


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where L and W are the length and width of the channel, respectively, Ci=εε0/d is the capacitance per unit area, ε0=8.854×10-12 F/m is the permittivity of vacuum, ε=3.9 is the relative dielectric constant of SiO2, d=300 nm is the thickness of the SiO2 dielectric layer, dIds/dVg is the maximum slope of liner scale of the transfer curve.44 The carrier mobility of the S-doped BP FETs is calculated to be 607 cm2V-1s-1 and the Ion/Ioff ratio is estimated to be ~103. The mobility and Ion/Ioff ratio are counted and the distributions from 15 S-doped FETs with thickness of ~10 nm are shown in Figure 3. Around 26.7% of the devices possess a mobility more than 600 cm2V-1s-1, while 80% devices have an Ion/Ioff ratio larger than 103. The values of mobility and Ion/Ioff ratio are both comparable to those published BP devices indicating the S-doped BP FETs devices here are at a high-performance level.5, 11, 45

Figure 3. Statistics of (a, b) mobility and (c, d) Ion/Ioff ratio for 15 S-doped BP FETs devices.


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Figure 4. Aging characterizations of S-doped BP FETs under ambient environment. (a) The transfer curves of the S-doped BP FETs at fixed drain-source voltage (Vds) of 0.01V after an exposure time of 0, 1, 3, 7, 10, 14, 17, and 21 days. (b) Normalized carrier mobility and (c) Normalized Ion/Ioff ratio aging characterization for BP and S-doped BP FETs. The error bars represent the maximum and minimum values of three devices. (d) Attenuation rate of mobility and Ion/Ioff comparison for BP and S-doped BP FETs for 21 days. The stability under ambient environment is an important property for a semiconductor material in constructing devices. In order to study the stability of S-doped BP FETs, the transfer curves were tested at increased exposure time in ambient conditions with relative steady humidity of 45%-50% and constant temperature of 25 °C as shown in Figure 4a. Compared with the undoped BP FETs (refer to our previous work in Ref 41), the drain-source current Ids decrease much slower owing to the gradually increase of resistance caused by the degradation. The mobility decreases from 607 to 490 cm2V-1s-1 for a S-doped FETs device in ambient for 21 days. Also, we


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have counted the detailed changes of normalized mobility and normalized Ion/Ioff ratio as shown in Figure 4b and 4c for BP and S-doped BP FETs, respectively. The average values of three devices are also displayed. With the increase of exposure time, the undoped BP FETs devices show a fast drop of mobility and Ion/Ioff ratio. While for the S-doped BP FETs, the degradation of mobility is quite slow and a high Ion/Ioff ratio of ~103 is still retained. The comparisons of mobility and Ion/Ioff residual ratio for BP and S-doped BP FETs in ambient for 21 days are shown in Figure 4d which imply enhanced stability of the S-doped BP FETs intuitively.

Figure 5. AFM images of (a) BP flake after exposure time of 0, 3, 5, 9, 16, and 20 days and (b) S-doped BP flake after exposure time of 0, 1, 5, 8, 15, and 21 days. The BP and S-doped BP flakes were stored in ambient conditions with relative steady humidity of 45-50% and constant temperature of 25 °C. The scale bars are 1 µm.


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AFM measurement is used to analyses on the morphology features of BP and S-doped BP during the exposure time. Figure 5 shows the surface morphology variation of mechanically exfoliated BP (Figure 5a) and S-doped BP (Figure 5b) flakes stored at ultra-clean chamber with constant humidity of 45%-50% and steady temperature of 25 °C. The initially exfoliated BP and S-doped BP flakes present smooth surface with only a small amount of “bubbles”, which comes from the one-hour-delay for selecting the proper few-layer flakes under a microscope after exfoliation. The “bubbles” are ascribed to the reaction of BP with adsorbed oxygen and water on the sample surface. As described in the introduction part, one phosphorus atom has an exposed lone pair of outermost orbital electrons and these electrons can easily react with oxygen and H2O to form phosphoric acid which will etch the material away.24, 29 As the exposure time increases, more “bubbles” appear on the surface and the “bubbles” joint each other and become bigger leading to the destruction of the crystal structure. This process is more obvious for undoped BP flake. After exposure for 16 days, the degradation etched most part of the material away for undoped BP, while for the S-doped BP (after 15 days), the “bubbles” are small and still uniformly distributed on the flake surface indicating the degradation is effectively suppressed. We also extract the thickness and roughness information for both BP and S-doped BP samples as a function of exposure time (as shown in Figure 6) from the AFM analyses. In Figure 6a, the thickness represents the effective result eliminating the errors caused by the “bubbles” on the flake surface and the height profiles are obtained along the dash line in AFM images as shown in Figure 5. For undoped BP sample, the thickness decreases quickly from ~9.3 nm to ~1.5 nm with a thickness reduction of 83.9% after exposure in ambient for 20 days. While for Sdoped BP, the thickness decreases only from ~11.5 nm to ~9.4 nm with a thickness reduction of 18.3% after exposure in ambient for 28 days. The much slower decrement of thickness also


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confirms the enhanced stability of S-doped BP. The growth of “bubbles” causes the increase of the surface roughness. The S-doped BP flakes experiences a much slower increase in roughness as shown in Figure 6b, compared to undoped BP. It's worth noting that for the undoped BP flake, as the “bubbles” evolve into large size and are nonuniformly distributed on surface, it’s hardly to extract the roughness correctly after exposing in ambient for 10 days.

Figure 6. (a) Variation of thickness with exposure time. The height profile was extracted from the position of dash line in Figure 5 (b) Variation of surface roughness (Ra) with exposure time. In order to better understand the effect of the S-dopant on the BP, we performed firstprinciples calculations on the S-doped few-layer BP by considering the situations of substitution and adatom. As shown in Figure S2, we consider four potential structures with that one and two P atoms replaced by one S atom in monolayer BP, the S atom are intercalated into bilayer BP and the S atom adsorbs on the surface of bilayer BP in the dangling form. The calculated formation energies (see Table S1) of the four potential structures are -1.63 eV, -0.72 eV, -1.57 eV and -2.53 eV, respectively. The calculated results revel that the dopant S atom energetically prefers to chemisorb on the BP surface in a dangling form. The direct band structure of S-doped BP is still kept and the partial density of S presented in the valence band does not affect the valence band maximum (VBM) or conduction band minimum (CBM) of BP (Figure 7b and 7c).


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Based on the configuration of dangling form, we further calculated the electronic band structure of BP and S-doped BP with different layers (Figure 7b and S3). As shown in Figure 7d, CBM of one to three layers of S-doped BP with respect to vacuum energy shift below the redox potential of O2/O2-. The redox potential of O2/O2- is just located in the band gap of BP, which result in the process that the photo-generated electrons can transfer from the conduction band of BP to the O2 on its surface and generate O2-. This process acts as the trigger of the degradation process of BP.38 Hence, the S-doped BP is more difficult to produce the O2- anion and the oxidization process can be effectively suppressed, further improving the stability.

Figure 7. (a) Simulation cell configuration of trilayer S-doped BP. (b) The electronic band structure and (c) partial density of state of trilayer S-doped BP. (d) The valence band maximum (VBM) and conduction band minimum (CBM) of few-layer BP and S-doped BP with respect to vacuum energy (Ec). The dashed line represents the relative position of redox potential of O2/ O2-.


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4. CONCLUSION In summary, the S-doped BP FETs presented high transistors performance and excellent stability. The charge-carrier mobility remained ~ 77% as the initial value and a high Ion/Ioff ratio of ~103 under ambient for 21 days. The surface morphology variation confirmed that the degradation of S-doped BP was effectively suppressed. The enhanced stability could be attributing to the effective suppression of the oxidization process by S doping as indicated by the first-principles calculations. Our work indicates a feasible method to enhance the stability of BP without changing the transistor performance of BP. ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: XPS spectrum of BP and S-doped BP, the potential structures of S-doped BP with formation energy Ef, the electronic band structure of BP and S-doped BP with different layer. AUTHOR INFORMATION Corresponding Authors * E-mail: [email protected] * E-mail: [email protected] * E-mail: [email protected] Notes The authors declare no competing financial interest.


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ACKNOWLEDGMENT We gratefully acknowledge the financial support from the National Natural Science Foundation of China (Grant No.51672240, 51732010, 51761145025). REFERENCES (1) Xu, M.; Liang, T.; Shi, M.; Chen, H. Graphene-Like Two-Dimensional Materials. Chem. Rev. 2013, 113, 3766-3798. (2) Champness, N. R. Two-Dimensional Materials: Crystallized Creations in 2D. Nat. Chem. 2014, 6, 757-759. (3) Chhowalla, M.; Shin, H. S.; Eda, G.; Li, L. J.; Loh, K. P.; Zhang, H. The Chemistry of TwoDimensional Layered Transition Metal Dichalcogenide Nanosheets. Nat. Chem. 2013, 5, 263275. (4) Akinwande, D.; Petrone, N.; Hone, J. Two-Dimensional Flexible Nanoelectronics. Nat. Commun. 2014, 5, 5678. (5) Li, L.; Yu, Y.; Ye, G. J.; Ge, Q.; Ou, X.; Wu, H.; Feng, D.; Chen, X. H.; Zhang, Y. Black Phosphorus Field-Effect Transistors. Nat. Nanotechnol. 2014, 9, 372-377. (6) Buscema, M.; Groenendijk, D. J.; Blanter, S. I.; Steele, G. A.; van der Zant, H. S.; Castellanos-Gomez, A. Fast and Broadband Photoresponse of Few-Layer Black Phosphorus Field-Effect Transistors. Nano Lett. 2014, 14, 3347-3352. (7) Levi, R.; Bitton, O.; Leitus, G.; Tenne, R.; Joselevich, E. Field-Effect Transistors Based on WS2 Nanotubes with High Current-Carrying Capacity. Nano Lett. 2013, 13, 3736-3741. (8) Lopez-Sanchez, O.; Lembke, D.; Kayci, M.; Radenovic, A.; Kis, A. Ultrasensitive Photodetectors Based on Monolayer MoS2. Nat. Nanotechnol. 2013, 8, 497-501. (9) Georgiou, T.; Jalil, R.; Belle, B. D.; Britnell, L.; Gorbachev, R. V.; Morozov, S. V.; Kim, Y. J.;


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Graphic Abstract


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Sulfur-Doped Black Phosphorus Field-Effect Transistors with

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