Deep Ultraviolet Photodetectors Based On Carbon-Doped Two-Dimensional Hexagonal Boron Nitride

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Functional Inorganic Materials and Devices

Deep Ultraviolet Photodetectors Based on Carbon-
Doped Two-Dimensional Hexagonal Boron Nitride
Ye Wang, Junhua Meng, Yan Tian, Yanan Chen, Gaokai Wang,
Zhigang Yin, Peng Jin, Jingbi You, Jinliang Wu, and Xingwang Zhang
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.0c05850 • Publication Date (Web): 25 May 2020
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Page 1 of 23 ACS Applied Materials & Interfaces
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Deep Ultraviolet Photodetectors Based on Carbon-
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12 Doped Two-Dimensional Hexagonal Boron Nitride
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17 Ye Wang,†,‡ Junhua Meng,*,§ Yan Tian,†,‡ Yanan Chen,†,‡ Gaokai Wang,†,‡ Zhigang Yin,†,‡ Peng
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19 Jin,†,‡ Jingbi You,†,‡ Jinliang Wu† and Xingwang Zhang*,†,‡
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22 † Key Lab of Semiconductor Materials Science, Institute of Semiconductors, Chinese Academy
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of Sciences, Beijing 100083, China
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27 ‡ Center
28 of Materials Science and Optoelectronics Engineering, University of Chinese Academy
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30 of Sciences, Beijing 100049, China
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33 § College of Applied Sciences, Beijing University of Technology, Beijing 100124, China
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 Corresponding author. E-mail: [email protected], [email protected]
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45 KEYWORDS: Two dimensional materials, hexagonal boron nitride (h-BN), ion beam sputtering
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47 deposition (IBSD), deep ultraviolet (DUV) photodetectors, hexagonal boron-carbon-nitrogen (h-
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50 BCN), doping
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ACS Applied Materials & Interfaces Page 2 of 23
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4 ABSTRACT
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Recently, the deep ultraviolet (DUV) photodetectors fabricated from two-dimensional (2D)
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10 hexagonal boron nitride (h-BN) layers have emerged as a hot research topic. However, the
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12 existing studies show that the h-BN-based photodetectors have relatively poor performance. In
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this work, C-doping is utilized to modulate the properties of h-BN and improve the performance
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17 of the h-BN-based photodetectors. We synthesized the h-BN atomic layers with various C
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19 concentrations varying from 0 to 10.2 at.% by ion beam sputtering deposition through controlling
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21 the sputtering atmosphere. The h-BN phase remains stable when a small amount of C is
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24 incorporated into h-BN, whereas the introduction of a large amount of C impurities leads to the
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26 rapidly deteriorated crystallinity of h-BN. Furthermore, the DUV photodetectors based on C-
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28 doped h-BN layers were fabricated, and the h-BN-based photodetector with 7.5 at% C exhibits
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the best performance with a responsivity of 9.2 mA·W-1, which are significantly higher than those
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33 of the intrinsic h-BN device. This work demonstrates that the C-doping is a feasible and effective
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35 method for improving performance of h-BN photodetectors.
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42 INTRODUCTION
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44 Recent investigations have demonstrated that two-dimensional (2D) hexagonal boron nitride
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47 (h-BN) is an ideal substrate and gate dielectric layer for electronic/photonic devices based on
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49 other 2D materials, due to its atomically flat and inert surface.1,2 Moreover, h-BN has also be
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51 proven to be a promising candidate for fabricating deep ultraviolet (DUV) photodetectors without
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the need for solar rejection filters because of its wide band gap and long-term stability under UV
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4 light radiation.3 Various approaches have been developed to tailor properties of h-BN and to
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6 fabricate high-performance h-BN photodetectors.4-10 In general, chemical doping is regarded as
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8 the most effective and feasible approach for tailoring the properties of semiconductor. Carbon is
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11 a very suitable dopant for h-BN since the similarities in geometry between h-BN and graphene
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13 ensure a perfect match in the lattice and bond length.
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15 Theoretical investigations have shown that B, N and C can be mixed together to form 2D
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hexagonal boron-carbon-nitrogen (h-BCN) semiconducting.11-13 Many experimental efforts have
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20 been made to achieve a homogeneous 2D h-BCN atomic layer by employing different synthetic
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22 approaches and various precursors.14-22 However, there is a strong tendency of the B-C-N ternary
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system towards segregation of h-BN and graphene domains. Ci et al.14 have synthesized h-BCN
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27 layers composed of hybridized domains of graphene and h-BN via a chemical vapor deposition
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29 (CVD) technique, and the resultant h-BCN layers exhibited typical semiconductor characteristics.
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31 Gong et al.16 developed a high-temperature topochemical conversion technique for synthesizing
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34 the semiconducting ternary h-BNC layers. Recently, we demonstrated a novel approach to prepare
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36 2D h-BCN atomic layers with a full range of compositions through ion beam sputtering deposition
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38 (IBSD) by introducing CH4 into the sputtering atmosphere.22 Nevertheless, all of these structures
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should be regarded as ternary compounds or in-plane heterostructures rather than C-doped h-BN.
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43 So far only relatively few experimental results are available for the preparation of C-doped 2D h-
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45 BN atomic layers.
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The 2D h-BN-based DUV photodetector has recently emerged as a hot research topic.
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50 However, all the h-BN photodetectors reported previously were based on intrinsic h-BN films or
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52 nanosheets. Probably limited by the insulating features and material quality, most h-BN
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54 photodetectors exhibit relatively poor performance with a low responsivity.6-10 As mentioned
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4 above, chemical doping with C is a widely used approach to modulate the electrical properties of
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6 h-BN, and may address the major challenges facing the h-BN photodetectors. In this work, we
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8 synthesized C-doped h-BN atomic layers by finely tuning the sputtering atmosphere within an
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11 IBSD system. The effects of C incorporation on the composition, structure and optical properties
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13 of the h-BN atomic layers were investigated. The results suggest that the h-BN phase remains
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15 stable on the whole with the incorporation of C up to a concentration of 7.5 at.%, and the further
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increasing C concentration leads to the deteriorated crystallinity of h-BN, and finally the
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20 formation of h-BCN alloys. Furthermore, the DUV photodetectors based on C-doped h-BN layers
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22 with various C concentrations were fabricated, and the h-BN-based photodetector with 7.5 at.%
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25 C exhibits the best performance with a photoresponsivity of 9.2 mA·W−1. Our work
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28 demonstrates that the C-doped h-BN is a promising candidate for fabricating DUV photodetectors.
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RESULT AND DISCUSSION
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36 The intrinsic and C-doped h-BN atomic layers were grown on Cu foils by IBSD technique
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38 under a mixed Ar/CH4 atmosphere. The C concentration in the h-BN layers were controlled by
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varying the CH4 flow rate at 0, 1, 2, 4 and 6 sccm, and the corresponding h-BN layers are referred
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43 as sample A, B, C, D and E, respectively. The synthesis process of h-BN is presented in detail in
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45 Experimental Section. X-ray photoelectron spectroscopy (XPS) measurements were performed to
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47 evaluate the C concentration within the h-BN atomic layers. The C 1s, B 1s, and N 1s core-level
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50 spectra of C-doped h-BN layers prepared with various CH4 flow rates are shown in Figure 1a-c,
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52 respectively. It can be seen from Figure 1a that the intensity of the C 1s peak gradually increases
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31 Figure 1. XPS core level spectra of (a) C 1s, (b) B 1s, and (c) N 1s for the C-doped h-BN layers
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synthesized with CH4 flow rates of 0, 1, 2, 4 and 6 sccm. Typical XPS spectra of (d) C 1s, (e) B
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36 1s, and (f) N 1s core level (empty circles) with multipeak fits (dashed lines) for the h-BN layer
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38 with 10.2 at.% C (sample E).
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41 with increasing CH4 flow rate, while its binding energy remains approximately 284.8 eV for all
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43 the samples. The C concentrations are calculated from the corresponding XPS spectra together
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46 with the sensitivity factors. As listed in Table 1, the C concentration in the h-BN layers increases
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48 from 2.4 to 10.2 at.%, when the CH4 flow rate varies from 1 to 6 sccm. Unlike the C 1s spectra,
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50 the intensities of B 1s and N 1s peaks gradually decrease with the increase of C concentration, as
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shown in Figure 1b and 1c. To analyze their chemical states, the XPS spectra of C 1s, B 1s, and
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55 N 1s core-level are deconvoluted for sample E with 10.2 at.% C (Figure 1d-f). The main peak of
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4 C 1s is located at 284.8 eV (Figure 1d), which is attributed to C-C sp2 bonds.18,23 The shoulder at
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6 the lower binding energy side originates from C-B bonds, while the other one at the higher binding
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8 energy can be assigned to C-N bonding.18,24 The fraction of C–C bonds is calculated to be about
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11 55% according to the area ratio of each component, implying quite a few C atoms are aggregated
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13 and form graphene domains. Furthermore, the C-N bonding is more favorable than C-B bonding
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15 because the bond energy of C–N bond (2.83 eV) is higher than that of C–B bond (2.59 eV).25 In
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contrast, the B 1s spectrum is resolved into two peaks located at 190.5 and 189.5 eV (Figure 1e),
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20 whereas the N 1s spectrum gives two peaks centered at 399.2 and 398.0 eV (Figure 1f). The main
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22 peaks of the B 1s (190.5 eV) and N 1s (398.0 eV) spectra are consistent with those of the intrinsic
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h-BN (i.e., sample A, Figure S1), while two shoulders centered at 189.5 eV and 399.2 eV suggest
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27 that some B and N atoms bond with C atoms.15,18,26 The bonding characteristics of the elements
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29 reveal that B, C, and N atoms bond with each other and there is a tendency of C segregation in h-
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31 BN with higher C concentrations.
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34 Figure 2a-e displays the scanning electron microscopy (SEM) images of the intrinsic and C-
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36 doped h-BN atomic layers. All the h-BN layers grow into near-fully covered and continuous layers
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38 with a large number of merged h-BN grain boundaries. As illustrated in the inset of Figure 2e, the
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grain boundaries are consisted of many small triangular h-BN domains came from the secondary
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43 nucleation. In addition, with the increase of C concentration, the more grain boundaries are
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45 observed. Obviously, the incorporation of C atoms leads to the increased secondary nucleation at
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grain boundaries, indicating that the C impurity and C-related defects probably serve as nucleation
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50 seeds of h-BN. Unlike the SEM images, the optical microscope image of the transferred h-BN
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52 layer (sample D) on a SiO2/Si substrate indicates that the C-doped h-BN layer is substantially
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54 continuous and uniform over a large area (Figure 2f and Figure S2). A high-resolution
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4 transmission electron microscopy (HRTEM) image together with the corresponding selected-area
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6 electron diffraction (SAED) pattern of h-BN with 7.5 at.% C shows the characteristic h-BN lattice
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8 constant of 0.25 nm (Figure S3), however, one cannot distinguish B, C and N atoms in the lattice
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11 due to their very close atomic sizes.
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Figure 2. SEM images of (a) the intrinsic h-BN (sample A) and the doped h-BN layers with C
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36 concentrations of (b) 2.4 at.% (sample B), (c) 4.5 at.% (sample C), (d) 7.5 at.% (sample D) and
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38 (e) 10.2 at.% (sample E). The inset in (e) shows a zoom-in view of grain boundaries. (f) Optical
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40 microscopy image of the transferred h-BN layer with 7.5 at% C (sample D) on a SiO2/Si substrate.
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43 To study the effects of the C incorporation on the microstructure of h-BN layers, the Raman
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spectra of the intrinsic and C-doped h-BN transferred onto SiO2/Si substrates were collected, as
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48 displayed in Figure 3a. The Raman peak at ~1450 cm-1, which are observed from all the samples,
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50 is attributed to the 3rd order silicon long wavelength transverse optical phonon (Si, 3TO)
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52 originating from the substrate. The intrinsic h-BN layer (sample A) exhibits a unique Raman peak
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55 ascribed to the B-N vibrational E2g mode (h-BN, E2g) at 1364 cm−1. It has a small blue shift of
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17 Figure 3. (a) Raman spectra of the intrinsic h-BN (sample A) and the doped h-BN with various
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19 C concentrations. (b) Tauc plots of absorption coefficients and (c) The sub-band gap absorption
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tails for the intrinsic and doped h-BN layers with various C concentrations. The lines in (c) present
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24 the fits of the absorption tails to the Urbach equation.
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27 5 cm-1 compared to the previous result, probably due to the increasing layer-number of h-BN.27
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29 The E2g peak located at ~1366 cm-1 were also observed in all the other samples studied, which
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confirms the formation of h-BN. It is noted that the h-BN Raman peak shows an obvious
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34 asymmetric broadening at the lower wavenumber side for both sample D and sample E, which
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36 can be attributed to the contribution of the D band from C clusters or graphene (Gr, D) at ~1345
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38 cm-1 (Figure S4), as reported previously.16,28 Simultaneously, a broad and weak band at
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41 approximately 1590 cm-1 appears in the Raman spectrum of sample C, and its intensity increases
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43 with further increasing C concentration. The band at 1590 cm-1 is ascribed to the in-plane
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45 stretching vibration of sp2 C-C bonds.28 The presence of the G band, along with an asymmetric
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48 broadening of h-BN Raman peak, again suggests the segregation of the C cluster. Furthermore,
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50 the full width at half-maximum (FWHM) of the h-BN Raman peak remarkably increases from 16
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52 cm-1 for sample A (intrinsic h-BN) to 33 cm-1 for sample E with 10.2 at.% C. Besides the
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4 contribution from the D band of graphene, the slightly degraded crystalline quality of h-BN is
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6 also responsible for the broadening of Raman peaks.
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8 The UV-vis absorption spectra of C-doped h-BN were measured to investigate their optical
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11 properties, which were transferred onto the transparent quartz substrates in advance. As shown in
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13 Figure S5, all the spectra exhibit a similar feature that a sharp absorption peak at around 200 nm
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15 is observed in the UV region with nearly no absorbance in the entire visible range. This
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characteristic absorption spectrum of 2D h-BN is different from the results reported by Ci et al.14,
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20 in which two absorption edges were observed from the absorption curves of h-BNC films. As an
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22 indirect band gap material,29 the band gap of h-BN layer can be determined from Tauc formula.
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As shown in Figure 3b, the band gap is deduced from the intercept of the linear part of Tauc plot,
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27 and the obtained band gap are given in Table 1. As can be seen from Table 1, the band gap of the
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29 h-BN layers decreases from 5.82 eV for the intrinsic sample A to 5.78 eV for the h-BN layers
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31 with 2.4 at.% C (Sample B) and 5.58 eV for sample E with 10.2 at.% C, respectively. In addition
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34 to the band gap narrowing, the C doping has also an effect on the sub-band gap absorption. It is
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36 well known that the disordered structure of semiconductors or insulators leads to the broadening
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38 of the absorption edge and forms an exponential absorption tail. This sub-band gap absorption tail
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41 can be expressed by the so-called Urbach equation30 =0 exp(h/E0), where 0 is a constant and
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43 E0 is the Urbach energy. In Figure 3c, the absorbance  is plotted as a function of incident photon
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energy h, and the dashed lines show the fits of the absorption tails to the Urbach equation. The
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48 Urbach energies E0 extracted from these fits are also listed Table 1. It can be seen from Table 1
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50 that the Urbach energy E0 rises with increasing C concentration, which means that the
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incorporation of more C atoms causes the greater the topological, structural, and compositional
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55 disorder. The Urbach energies listed in Table 1 are significantly larger than the values (<100 meV)
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4 in most semiconductors, however, these values are consistent with other reports on BN.31,32 We
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6 speculate that the larger band gap and the deeper defect level may be responsible for the larger
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8 Urbach energy of h-BN. All these characterization results suggest that a little amount of C doping
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11 in h-BN results in a slight reduction of band gap and the degraded crystallinity.
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15 Table 1. The C concentration, position and width of Raman E2g peak, Urbach energy E0 and band
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17 gap of the h-BN layers grown with different CH4 flow rates.
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19 CH4 C Peak Band
20 Peak width
Sample flow concentration position E0 (eV) gap
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rate (at.%) (cm-1) (eV)
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23 A / / 1364 16 0.297 5.82
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25 B 1 2.4 1365 19 0.307 5.78
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27 C 2 4.5 1366 23 0.357 5.75
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29 D 4 7.5 1366 29 0.470 5.68
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31 E 6 10.2 1366 33 0.579 5.58
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36 The DUV photodetector prototypes were fabricated from the intrinsic and C-doped h-BN
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38 atomic layers transferred on 300-nm-thick SiO2/Si substrates. Figure 4a presents a schematic view
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40 of h-BN photodetector, and the corresponding photograph of device is given in Figure S6. Two
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43 parallel Ti/Au electrodes with a thickness of 200 nm were deposited on the surface of the
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45 transferred h-BN layers which were covered with a thin gold wire. The resulted electrode interval
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47 is about 20 m, and the optical microscopy image of Ti/Au electrodes is shown in the inset of
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50 Figure 4e. Figure 4b presents the semi-logarithmic I-V curves of photodetectors fabricated from
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52 h-BN samples A-E (referred as device A-E) plotted in the dark and under the 212 nm laser
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54 illumination (15.9 mW·cm-2), respectively. As can be seen, the photocurrents of all the devices
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4 are about four orders of magnitude higher than their dark currents at 20 V, which means a high
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6 on/off ratio of approximately 104 for all the devices. To investigate the effect of C concentration
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8 on the detector performance, the photocurrents and dark currents of at 20 V as a function of the C
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11 concentration are extracted and plotted in Figure 4c. It can be seen that the photocurrent rises from
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13 6.1 nA for device A, to a maximum of 43.9 nA for device D, then decreases to 33.0 nA for device
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15 E. Contrarily, the dark current exhibits a monotonous increase with the C concentration. The
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increase of photocurrent after C introducing is partly attributed to an increase of absorption
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20 because of the reduced band gap (Figure S5a). As a result, the on/off ratio exhibits a similar C-
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22 concentration dependence as the photocurrent (Figure S7), and device D with 7.5 at.% C shows a
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maximum on/off ratio of 5.3104.
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27 The photoresponsivity R and specific detectivity D* are two most important parameters for a
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29 photodetector. The responsivity R quantifies the sensitivity of photodetector to the incident light,
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and it can be given by R=Jph/Llight, where Llight is the incident light intensity and Jph is the
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34 photocurrent density. The detectivity D* characterizes the normalized signal-to-noise
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36 performance of photodetector. When the dark current is dominated by the shot noise, D* can be
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38 given as D*=RS1/2/(2qId)1/2, where S is the area of photodetectors, q is the unit charge, and Id is
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41 the dark current. Both R and D* calculated at 20 V are plotted as a function of the C concentration
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43 in Figure 4d. One can see that the responsivity rises from 1.28 mA·W−1 for device A (intrinsic h-
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45 BN) to a maximum of 9.2 mA·W−1 for device D with 7.5 at.% C. Then it decreases to 6.9 mA/W,
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48 when the C concentration further increases to 10.2 at.% (device E). It is noticed that the D* and
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50 R clearly show a closely similar dependence on the C concentration, and the highest D* value of
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52 3.09×1011 Jones (Jones=cm Hz1/2W−1) is obtained for device D. Both responsivity (9.2 mA·W−1)
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and D* (3.09×1011Jones) are significantly higher than not only those of the reference device A
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26 Figure 4. (a) Schematic diagram of h-BN-based photodetector. (b) Semilogarithmic I-V curves
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28 of the photodetectors based on h-BN layers with different C concentrations in the dark and under
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the 15.9 mW cm-2 laser irradiation. (c) The photocurrent and dark current of at 20 V as a function
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33 of the C concentration. (d) Responsivity R and specific detectivity D* calculated at 20 V as a
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35 function of the C concentration. (e) Dependence of normalized responsivity for device D at 20 V
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37 on the incident laser wavelength. The inset shows the optical microscopy image of Ti/Au
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40 electrode. (f) The transient response characteristics of device D for obtaining the response times.
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(R=1.28 mA·W−1, D*=4.81×1010 Jones), but also the values reported previously for DUV
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45 photodetectors based on h-BN and other III-V semiconductors,6-10,34 For example, specific
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47 detectivity is only 2.4×108 Jones for the h-BN metal-semiconductor-metal (MSM)
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photodetectors8 and 1.8×1010 Jones for the h-BN detector fabricated from h-BN directly grown
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52 on sapphire,10 and a detailed comparison of device performance is given in the Table 2. However,
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54 it should be noted that the 1011 Jones is an upper value of the detectivity and that the actual value
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4 will be much lower when the 1/f noise is considered. The above results suggest that the
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6 incorporation of a small amount of C leads to the formation of defects, grain boundaries, as well
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8 as the reduced band gap, which is effective to improve the photocurrent, while the dark current
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11 only slightly increases with the C concentration. In addition, the C concentration further increases
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13 to 10.2 at.%, the presence of a large amount of C impurities leads to the rapidly deteriorated
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15 crystallinity of h-BN. Consequently, the dark current of device E remarkably increases, and it
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outweighs the improved photocurrent, resulting in degradation of device performance.
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20 Table 2. Performance comparison of DUV photodetectors fabricated from h-BN layers and other
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22 III-V semiconductors.
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24 Material Morphology Wavelength Responsivity (R) Rise/Decay time Ref.
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26 250−276
AlGaN nanorods 115 mA·W-1@3 V — 33
27 nm
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29 170–200 4.5~6.8 mA·W-1
30 AlN film — 34
nm @±30 V
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33 AlN micro/nanowire < 200 nm 0.39 A·W-1@50 V <0.1s/<0.2s 35
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GaN film 365 nm 50 mA·W-1@5 V — 36
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36 h-BN nanosheets 250 nm 9 μA·W-1@0 V — 7
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38 h-BN atomic layers ＜225 nm 0.1 mA·W-1@20 V 0.32 s/0.63 s 8
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40 h-BN atomic layers ＜225 nm 1.33 mA·W-1@25 V 1.04 ms/1.08 ms 10
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42 h-BN nanosheets 254 nm 1.5 mA·W-1@-5 V — 6
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44 this
45 h-BN atomic layers ＜226 nm 9.2 mA·W-1@20 V < 0.5 ms
work
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50 To check the DUV selectivity of the h-BN photodetector, a spectral response test was
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52 performed by using the laser with wavelengths of 212, 218, 243, 284 and 450 nm. The normalized
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54 spectral response curve of device D is presented in Figure 4e. According to the spectral response
55
56
57
58 13
59
1
2
3
4 curve fitted by an exponential decay function, the cut-off wavelength is estimated to be around
5
6 226 nm (5.49 eV), which is slightly lower than its band gap of 5.68 eV determined from the
7
8 aforementioned Tauc plot. To obtain the response time for the photodetector, the transient
9
10
11 response characteristics were recorded under 212 nm laser irradiation by using an oscilloscope.
12
13 As shown in Figure 4f, the response time is determined to be about 0.5 ms, which is close to the
14
15 limit of the setup (Figure S8). Hence, the actual response time should be less than 0.5 ms, and it
16
17
18
is much faster compared to the h-BN-based photodetectors reported previously.5-10,35 In addition,
19
20 the on/off switching behavior can be well maintained over multiple cycles, implying the
21
22 outstanding switching capability and reproducibility (Figure S9). The combination of the high
23
24
on/off ratio, responsivity, specific detectivity and the fast response time makes C-doped h-BN a
25
26
27 promising material for fabricating DUV photodetectors.
28
29
30
31
32 CONCLUSION
33
34
35 In summary, the h-BN atomic layers with various C concentrations varying from 0 to 10.2
36
37 at.% were prepared by the IBSD method through controlling the sputtering atmosphere. The h-
38
39 BN phase remains stable on the whole with the incorporation of C up to 7.5 at.%, while the
40
41
42
crystalline quality of h-BN layer is degraded with simultaneous replacement by a h-BCN alloy
43
44 for the higher C concentrations. Moreover, the photodetectors were fabricated based on C-doped
45
46 h-BN atomic layers with different C concentrations. It is found the performance of h-BN
47
48
photodetectors is firstly improved with increasing C concentration, but the further increase of C
49
50
51 concentration causes the degradation of device performance. The photodetector fabricated from
52
53 h-BN with 7.5 at.% C exhibits the best performance with a photoresponsivity of 9.2 mA·W−1,
54
55 which are about an order of magnitude higher than those of the intrinsic h-BN device. This work
56
57
58 14
59
1
2
3
4 demonstrates that the C-doping is a very promising way for improving performance of h-BN-
5
6 based DUV photodetectors.
7
8
9
10
11
12 EXPERIMENTAL SECTION
13
14 Synthesis and characterizations of h-BN layers: The intrinsic and C-doped h-BN atomic
15
16 layers on Cu foils were prepared by the IBSD technique, in which a sintered h-BN target was
17
18
19
sputtered with a 1 keV Ar+ ion beam, as described previously.37,38 The mixed CH4/Ar gas was
20
21 introduced into the sputtering chamber, in which CH4 was used as the C source. To control the C
22
23 concentration within the h-BN layers, the CH4 flow rate was varied from 1~6 sccm, while the Ar
24
25
flow rate kept a constant. During the growth of h-BN, the vacuum level of sputtering chamber
26
27
28 was 3~3.510-2 Pa, and the substrates were held at 1050 °C. All the samples were grown for 40
29
30 minutes, resulting in a 4∼5 nm thick h-BN layer.8
31
32
33
The morphologies of h-BN atomic layers were characterized by using a FEI Nova NanoSEM
34
35 650 field emission scanning electron microscope and an Olympus BX51M reflected light optical
36
37 microscope. The XPS spectra were recorded with a Thermo Scientific ESCALAB 250Xi
38
39
spectrometer, and a monochromated Al Kα was used as X-ray source. The UV-vis absorption
40
41
42 spectra were collected by a Varian Cary 5000 spectrometer in a double-beam mode. The Raman
43
44 spectra were measured with a HORIBA iHR550 spectrometer equipped with a 532 nm solid laser
45
46 as the excitation source.
47
48
49 Device fabrication and Characterization: For device fabrication, the IBSD-grown h-BN
50
51 layers on Cu foils were firstly transferred on a 300 nm SiO2/Si substrate by the wet-transfer
52
53 method using rosin as a support layer. In short, the thin rosin support layer was prepared on the
54
55
56
h-BN layer by spin coating a rosin solution. After complete etching of the underlying Cu foil, the
57
58 15
59
1
2
3
4 rosin/h-BN layer was transferred on a SiO2/Si substrate. Then, the rosin support layer was
5
6 sequentially dissolved by acetone and banana oil solutions. Finally, the 20 nm Ti/180 nm Au
7
8 electrodes were deposited via electron beam evaporation on the surface of h-BN layer covered
9
10
11 with a thin gold wire. The electrode interval is about 20 m, and the length is 1.5 mm. The I-V
12
13 curves were measured with a Keithley 4200-SCS source measurement unit under ambient
14
15 conditions. We used a frequency-quadrupled Ti sapphire laser as the light source for detector test,
16
17
18 and its wavelength and light intensity can be easily adjusted. An oscilloscope and a chopper with
19
20 an operating frequency of 100 Hz were utilized to measure the photoresponse time.
21
22
23
24
25
ASSOCIATED CONTENT
26
27
28 Supporting Information.
29
30
31 B 1s and N 1s core-level XPS spectra of the intrinsic h-BN layer; Optical microscope image of
32
33
34 the transferred h-BN layer; HRTEM image and the SAED pattern of h-BN with 7.5 at.% C;
35
36 Deconvolution of Raman spectrum for h-BN with 10.2 at.%; UV-vis absorption spectra of h-BN
37
38 samples and a typical transmittance spectra of h-BN; The photograph of typical DUV
39
40
41
photodetector; The on/off ratio measured at 20 V under the dark and the laser illumination; The
42
43 transient response characteristics of a Si photodiode; The photo-switching behavior for the
44
45 photodetector based on h-BN with 7.5 at. % C.
46
47
48
49
50
51
AUTHOR INFORMATION
52
53
54 Corresponding Author
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56
57
58 16
59
1
2
3
4 *E-mail: [email protected], [email protected]
5
6
7
Notes
8
9 The authors declare no competing financial interests.
10
11
12
13
14
15 ACKNOWLEDGMENT
16
17
18 This work is partially supported by the National Key R&D Program of China
19
20 (2018YFB0406500), the National Natural Science Foundation of China (61674137, 61874106,
21
22 61904174), the Beijing Municipal Science and Technology Project (Z181100004418007), and the
23
24
25
Strategic Priority Research Program of Chinese Academy of Sciences (XDB43000000).
26
27
28
29
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Deep Ultraviolet Photodetectors Based On Carbon-Doped Two-Dimensional Hexagonal Boron Nitride

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