Noriaki Toyoda

In recent years, enclosing liquid in a “liquid cell” (Fig. 1) has made it possible to analyze the chemical composition of the liquid sample and map samples in the liquid-solid interface using XPS, EDX, SEM in ultra-high vacuum (UHV). The most important part of the cell is the electron transmission window that allows electrons to input to or extract from the liquid sample. Silicon nitride (SiNx) is the most suitable material as the window, which has excellent mechanical properties. R. Endo et. al. has successfully measured the concentration of CsCl solution using a SiNx window with the film thickness of 5 nm¹. However, the transmittance of 1 keV photoelectron is about 10% with the thickness of SiNx membrane. When the membrane thickness is decreased to 2 nm, the transmittance can be improved to more than 40%, which means that even higher sensitivity can be achieved. However, the burst pressure must be 1 atm or more because the membrane needs to perform enclosing a liquid sample in UHV. In previous research, we demonstrated low damage etching of an SiNx film using gas cluster ion beam (GCIB) for thinning the window². Herein, GCIB is composed of aggregates of several thousands of atoms, and the energy of the individual atoms in the GCIB reduces to several eV/atom with an acceleration voltage of several kV. This enables irradiation on the target surface with little damage. Combining O₂-GCIB irradiation and exposure of acetylacetone (Hacac) gas enable reactive etching of SiNx². In this study, we utilized the above techniques to ultra-thin SiNx films and investigate whether the low-damage irradiation effect of GCIB is effective for SiNx films. In addition, Proof-of-principle of high sensitivity in liquid sample detection using ultra-thinning SiNx films is demonstrated using SEM/EDS. We have evaluated the burst pressure of ultra-thinned SiNx membranes of TEM window chips (SiMPore, Inc.) by reactive etching with O₂-GCIB and Hacac gas, where the thickness was originally 11 nm. The SiNx membrane was also etched in the same way using 400 eV Ar⁺ beam, and the burst pressure was evaluated. These irradiation doses were controlled so that the remaining SiNx membrane thickness was 4.5 nm. As a result, the burst pressure was 1 atm in the case of Ar⁺ beam, whereas it was 2.5 atm in the case of the GCIB etching. Therefore, it was found that low damage irradiation of GCIB was valid for thinning SiNx membrane. We sealed pure water in the liquid cell shown in Fig. 1 and performed EDS measurement. When electron beam with the energy of 5 keV was injected at the SiNx/water, generated characteristics X-ray of oxygen which photon energy is 0.52 keV could be observed. On the other hands, no O peak was observed in the SiNx/Si region. This result indicates that the O peak originated from the pure water under the SiNx membrane. Next, we carried out the measurements on a pristine SiNx membrane (t = 11 nm) and the GCIB-etched SiNx membrane (t = 4.5 nm), and compared their O peak characteristic X-ray intensities. Herein, the incident electron energies were 1.0 and 1.5 keV. The peak intensity of the GCIB-etched SiNx membrane was 1.6 times stronger than that of the pristine membrane at 1.5 keV. At 1.0 keV, the O peak was observed in GCIB-etched SiNx, but not in pristine SiNx. This is because the penetration depth of electrons in the SiNx film decreases with decreasing electron energy. From the above results, we have shown that the ultrathin SiNx membrane thinned by GCIB could be used for highly sensitive detection of pure water. Acknowledgement This work was supported by JSPS KAKENHI Grant Numbers 23K13236 and 22K04930. References [1] R. Endo, D. Watanabe, M. Shimamura et. al., Appl. Phys. Lett., 114, 173702 (2019). [2] M. Takeuchi R. Fujiwara, N. Toyoda, Jpn. J. Appl. Phys., 62, SG1051 (2023). Figure 1 <p></p>

Abstract We would like to improve detection sensitivity by making photoelectron transmission window (SiNx membrane) of liquid cell ultra-thin for liquid measurement using XPS or X-ray PEEM at UHV. In this study, thinning of the membrane using gas cluster ion beams (GCIB) was demonstrated and the burst pressure was compared with those thinned with atomic 400 eV Ar+ ions. It was shown that SiNx membranes thinned by GCIB was 2.5 times higher burst pressure than the Ar+ ions. In addition, improvement of sensitivity of characteristic X-ray from liquid-water induced by low-energy electrons was investigated. By using 4.5 nm thick SiNx membrane etched by GCIB, the X-ray intensity became 1.6 times higher than those from 11 nm thick pristine membrane at electron beam energy of 1.5 keV. This result showed good agreement with Monte Carlo simulation results of the electron-beam-induced X-ray emission from liquid-water beneath SiNx membrane.

Abstract Atomic layer etching (ALE) of silicon nitride film (SiNx) was demonstrated using oxygen gas cluster ion beam (O2-GCIB) with acetylacetone (Hacac) as adsorption gas. GCIB is a beam of aggregates of several thousand atoms, enabling low damage and high energy density irradiation. In this study, we performed the characterization of the ALE, and revealed the etching mechanism. XPS results indicated the following etching process. (i) O2-GCIB irradiation oxidizes the surface of SiNx film, (ii) the oxide layer reacts with Hacac vapor, and (iii) the reaction layer is removed by the GCIB. The ALE can be executed by sequential repetition of the processes (i)~(iii). This technique enables highly accurate control of SiNx film thickness with low irradiation damage.

Abstract Surface-activated bonding (SAB) of Cu by gas cluster ion beam (GCIB) irradiation with acetic acid vapor was studied. GCIB irradiation realizes surface smoothing and surface reaction enhancement without severe damage. Therefore, it is promising for SAB. In this study, acetic acid vapor was introduced during Ar-GCIB irradiation to assist the removal of surface oxides on the Cu surface. XPS results showed that Cu(OH)₂ was effectively removed by reaction with adsorbed acetic acid, and there was no residue by acetic acid adsorption. In addition, surface roughness decreased by Ar-GCIB irradiation with acetic acid because of the preferential removal of protrusion. Preliminary bonding experiments showed an increase of Cu–Cu bond strength by Ar-GCIB irradiation with acetic acid vapor.

A silane coupling-based procedure for decoration of an insulator surface containing abundant hydroxy groups by constructing redox-active self-assembled monolayers (SAMs) is described. A newly synthesized ferrocene (Fc) derivative containing a triethoxysilyl group designated FcSi was immobilized on SiO2/Si by a simple operation that involved immersing the substrate in a toluene solution of the Fc silane coupling reagent and then rinsing the resulting substrate. X-ray photoelectron spectroscopy (XPS) measurements confirmed that the Fc group was immobilized on SiO2/Si in the Fe(II) state. Cyclic voltammetry measurements showed that the Fc groups were electrically insulated from the Si electrode by the SiO2 layer. The FcSi on SiO2/Si structures were found to serve as a good scaffold for formation of organic semiconductor thin films by vacuum thermal evaporation of C8-BTBT (2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene), which is well-known as an organic field-effect transistor (OFET) material. The X-ray diffraction profile indicated that the conventional standing-up conformation of the C8-BTBT molecules perpendicular to the substrates was maintained in the thin films formed on FcSi@SiO2/Si. Further vacuum thermal evaporation of Au provided an FcSi-based OFET structure with good transfer characteristics. The FcSi-based OFET showed pronounced source-drain current hysteresis between the forward and backward scans. The degree of this hysteresis was varied reversibly via gate bias manipulation, which was presumably accompanied by trapping and detrapping of hole carriers at the Fc-decorated SiO2 surface. These findings provide new insights into application of redox-active SAMs to nonvolatile OFET memories while also creating new interfaces through junctions with functional thin films, in which the underlying redox-active SAMs play supporting roles.