Recently, the Sn-doped In₂O₃ (indium tin oxide (ITO)) material as a transparent conducting oxides is widely used on many technological applications, such as solar cell 1 and flat panel display 2 3 . Especially in nanoscale region, the Sn-doped In₂O₃ (ITO) nanowires have exhibited some superior properties such as good thermal stability, higher metallic conductivity, and excellent oxidation resistance, which make ITO nanowires (NWs) being suitable as a promising candidate not only as a transparent electrode but also as an emitter 4 5 6 7 . Up to now, several research groups have reported the growth of ITO nanowires, nanorods, and nanowhisker with different synthetic methods, such as thermal evaporation 8 9 10 11 , electron beam evaporation 12 , sputtering 13 , and pulse laser deposition 14 . These nanostructures were found to exhibit a good performance at field emission as an electron emitter due to their high aspect ratio at the nanoscale region and unique extrinsic properties. In the previous report, Wan et al. has reported the epitaxial growth of vertically aligned ITO NWs on the (100) yttrium-stabilized zirconia substrate and showed a superior field emission property 6 .

For a good field emission performance from nanowires, it highly depends on the shape of the nanowire 15 , circus radius of the nanowire at the tip region 16 , work function 17 , and packing density of the nanowire 15 . Thus, to obtain the high-density emission sites, one of the most important factors, the screen effect, due to the disturbance of electric field resulting from the interference of emission at different spacings between nanowires must be minimized 18 . Therefore, the selective area growth of nanowires was required. However, how electrical field emission properties of ITO NWs influenced by the screen effect in the differently grown situations is still interesting 19 . Several selective growth methods had been used, such as nanosphere lithography 20 , electron-beam lithography 21 22 , and conventional photolithography 19 .

In this regard, we present a selective area growth of single crystalline Sn-doped ITO NWs to improve the field emission properties owing to the reduction of the screen effect. In our previous study, the conductive properties of ITO NWs have been investigated, which is compatible with that of the high quality ITO thin films 23 24 . A periodically arrayed Au film prepared via a copper grid mask is used to control the growth area of ITO NWs in order to investigate the screen effect. Importantly, the length of ITO NWs was found to significantly influence the field emission properties. As a result, the reduced turn-on fields from 9.3 to 6.6 V μm⁻¹ and improved β values from 1,621 to 1,857 could be found after the selective area growth of Sn-doped ITO NWs at 3 h.

Figure 1 shows the growth of ITO NWs catalyzed by a selected-area gold film. According to the vapor–liquid–solid (VLS) growth mechanism 25 26 27 , the possible reaction routes can be assumed as follows:

2 I n g + 1 2 O 2 g → I n 2 O g

S n g + 1 2 O 2 g → I n 2 O g

I n 2 O g + H 2 g → 2 In Au + H 2 O g

Sn O 2 g + 2 H 2 g → Sn Au + 2 H 2 O g

2 In Au + 3 H 2 O g → I n 2 O 3 s + 3 H 2 g

Sn Au + 2 H 2 O g → Sn O 2 s + 2 H 2 g

The reaction of the VLS method is at a high-temperature environment. As the temperature increases to 600°C, the Au drops could be formed, and the low melting point of the source powder (In and Sn) is evaporated to combine with oxygen gas to form metal oxide gases (In₂O₃, SnO₂) through the chemical reactions of Equations 1 and 2. Subsequently, the metal oxide gases could be reduced by hydrogen to form the metal atoms and then enter to the liquid gold drops to form eutectic alloy through Equations 3 and 4. Furthermore, hydrogen and oxygen could combine to form H₂O. Finally, the eutectic alloy drops would be oxidized to form the Sn-doped In₂O₃ NWs by H₂O, namely, Equations 5 and 6. When the temperature increased to 600°C, the oxygen would be introduced into the alumina tube, resulting in the oxidization of In and Sn vapors, with which the growth time would be conducted at 600°C for 3 and 10 h.

To decrease the screening effect on the arbitrarily grown ITO NWs, the Sn-doped ITO NWs were alternatively grown on the Au film with the selective area of patterned 50-μm square with a distance of 10 μm for each square pattern. Figure 2a reveals a SEM image of Sn-doped ITO nanowires after the selective area growth. Clearly, the center of the patterned area shows the arbitrary growth of ITO NWs (Figure 2b), and the inset shows ITO nanowires with catalytic Au nanoparticles, confirming the VLS method of Sn-doped ITO NWs. In addition, the dispersion of ITO nanowire diameter ranges from 40 to approximately 200 nm with an average diameter of 110 nm.

To illuminate the detailed structure and components of the ITO NWs, the as-prepared nanowires were characterized by XRD, TEM, and XPS. Figure 3a shows the X-ray spectra of ITO NWs. All the peaks are indexed being the In₂O₃ cubic structure, while a small peak shows Au₉In₄ phase, which comes from the catalytic gold nanoparticles on the top of ITO nanowires. Furthermore, the high-resolution TEM image and the corresponding selected area electron diffraction (SAED) pattern with zone axis of [001] are shown in Figure 3b and the inset, respectively. The symmetric spots in the SAED pattern exhibit a single crystalline phase with the growth direction of [100]. The lattice spacing of 0.506 nm corresponding to (200) plane was indexed, which is consistent with In₂O₃ cubic phase. The XPS analysis is used to confirm the chemical compositions of ITO NWs. Figure 3c shows the XPS spectra of O 1s, In 3d, and Sn 3d core levels in the ITO NWs. The binding energy of Sn 3d _5/2 and Sn 3d _3/2 at 495.1 ± 0.1 eV and 486.6 ± 0.1 eV, correspond to the Sn⁴⁺ ion, respectively, which are relative to the electrical conduction of the nanowires 28 . The O 1s peak is deconvoluted by a Gaussian function into three positions. The lower binding energy component at 530 ± 0.1 eV is due to the O²⁻ ions whose neighboring indium atoms are surrounded by the six nearest O²⁻ ions. The medium binding energy at 531.3 ± 0.1 eV corresponds to the oxygen deficiency regions, which are called oxygen vacancies 28 29 . The higher binding energy at 532.6 ± 0.1 eV is associated with the oxygen of free hydroxyl group, which is possibly due to the water molecules absorbed on the surface 30 . All XPS results show that Sn atoms are doped into the In₂O₃ NWs with the existence of oxygen vacancies. Consequently, the oxygen vacancies and Sn ions contribute the electron concentration to the NWs, resulting in an n-type semiconducting behavior.

Figure 4a shows field emission properties of the ITO NWs grown on Au film and patterned Au film with growth time of 3 and 10 h, respectively. The turn-on field (E _on) is defined as the electric field required for generating a current density of 0.01 mA/cm², and 0.1 mA/cm² is sufficient for operating display panel devices. It is found that the turn-on field decreases from 9.3 to 6.6 V μm⁻¹ after the selective area growth of ITO NWs at the growth time of 3 h. Insets in Figure 4b reveal a linear relationship, so-called ln(J/E ²)-(1/E) plot, indicating that the field-emission behavior follows Fowler-Nordheim relationship, i.e., electrons tunneling through a potential barrier, which can be expressed as follows 31 32 33 :

J = A β 2 E 2 ϕ exp − B ϕ 3 2 βE ,

where J is the emission current density; E, the applied field; ϕ, the work function of emitter material; β, the enhancement factor; A, constant (1.56 × 10⁻¹⁰ A V⁻² eV); and B, constant (6.8 ×10³ eV^−3/2 V μm⁻¹) The field enhancement factor, β, reflects the degree of the field emission enhancement of the tip shape on a planar surface, which is also dependent on the geometry of the nanowire, the crystal structure, and the density at the emitting points. It can be determined by the slope of the ln(J/E ²)-(1/E) plot with a work function value of 4.3 eV 6 . Consequently, the turn-on fields and the β values of the ITO NWs with and without selective area growth at different growth times are listed in Table 1. Obviously, the field enhancement factors (β) from 1,621 to 1,857 can be achieved after the selective area growth at 3 h. Moreover, we find that the screen effect also highly depends on the length of nanowires on the field emission performance. As a result, the turn-on fields increase from 6.6 to 13.6 V μm⁻¹, and β values decrease from 1,857 to 699 after 10-h growth. Compared to the β values of other materials, such as Si nanowires (β = 1,000) 34 , NiSi₂ nanorods (β = 630) 35 , NiSi₂ nanowires (β = 501) 36 , SnO₂ (β = 1402.9) 37 , AlN (β = 950) 38 , and ZnO (β = 1,464) 39 , the Sn-doped ITO NWs are promising emitters. The findings indicate that the less stacking density via the selective area growth and the reduction of the NW length could decrease the screen effect, resulting in the increase of the enhancement factor.

The cross-sectional SEM images for the growth of Sn-doped ITO NWs at 10 and 3 h are shown in Figure 5a,b to confirm the reduction of the screen effect, respectively. Obviously, ITO NWs are tangled together due to the longer length (10-h growth), while the quasi-vertical growth could be achieved at the shorter time (3-h growth). According to the screening effect, the electrical field around ITO NWs with longer length and random growth would interfere together to result in screen effect, thereby a poor field emission 40 41 . The corresponding potential distribution of the ITO NWs for Sn-doped ITO NWs grown at 10 and 3 h related to the electrical field are shown in Figure 5c,d, respectively. Notably, Figure 5c (10-h growth) reveals that the NWs significantly tangled together, resulting in lower current emission because of the lesser equipotential lines owing to the server screen effect. Therefore, only the higher NWs would emit current. On the contrary, Figure 5d (3-h growth) reveals that the shorter NWs could decrease the screen effect due to the much larger dispersive equipotential lines around the NWs, triggering a higher current emission. This is why the shorter grown time of ITO NWs shows the much better FE property. The findings provide an effective way of improving the field emission properties for nanodevice application.

We present a selective area growth of single crystalline Sn-doped In₂O₃ (ITO) nanowires synthesized via VLS method at 600°C in order to improve the field emission behavior by the reduction of screen effect. The enhanced field emission performance reveals the reduction of turn-on fields from 9.3 to 6.6 V μm⁻¹ with increase of field enhancement factors (β) from 1,621 to 1857 after the selective area growth at 3 h. Moreover, we find that the screen effect also highly depends on the length of nanowires on the field emission performance. The turn-on fields increase from 6.6 to 13.6 V μm⁻¹, and β values decrease from 1,857 to 699 after the 10-h growth. The screen effect is predominated after the length of nanowires increases, namely the longer growth time, thereby degrading the field emission performance. Consequently, the turn-on fields and β values change from 13.6 V μm⁻¹ and 699 to 6.6 V μm⁻¹ and 1,857, respectively, as the growth time of Sn-doped ITO NWs decreases into 3 h. The detailed screen effect in terms of electrical potential and NW density was investigated in details. The findings provide an effective way of improving the field emission properties for nano-emitter application.

The authors declare that they have no competing interests.

WCC operated the SEM instrument and measured the FE property. PJL deposited the gold film of Si sample. CCJ operated the TEM instrument. CHK carried out the XPS characterization. SJL and YLC support the information and organized the final version of the paper. All authors read and approved the final manuscript.