• Bulletin of the Korean Chemical Society
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• 제32권2호
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• pp.389-398
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• 2011

Although the currently available surface spectroscopic techniques provide powerful means of studying atoms and simple molecules on surfaces, the identification of complex molecules and functional groups is a major concern in surface analysis. This article describes a recently developed method of surface molecular analysis based on reactive ion scattering (RIS) of low energy (< 100 eV) $Cs^+$ beams. The RIS method can detect surface molecules via a mechanism in which a $Cs^+$ projectile picks up an adsorbate from the surface during the scattering process. The basic principles of the method are reviewed and its applications are discussed by showing several examples from studies of molecules and their reactions on surfaces.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2010년도 제39회 하계학술대회 초록집
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• pp.64-64
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• 2010

Ice film surfaces were examined by using the reactive ion scattering (RIS) of low energy (<35 eV) cesium ion beams. Neutral molecules (X) on the surface were detected in the form of cesium-molecule ion clusters (CsX+). Ionic species on the surface were desorbed from the surface via a low energy sputtering (LES) process below the threshold energy of secondary ion emission. The RIS and LES methods allowed us to study the H/D exchange reactions between H2O and D2O molecules on the surface and the associated proton transfer mechanisms. Specifically, H/D exchange kinetics was examined for D2O ice films (~10 BL) covered with a small amount of H2O (<0.5 BL), in the presence or absence of HCl adsorbates which provided excess protons on the surface.

• Journal of Korean Vacuum Science & Technology
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• 제6권1호
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• pp.30-35
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• 2002

We show that a combined technique of Cs$^{+}$ reactive ion scattering (Cs$^{+}$ RIS) and low-energy secondary ion mass spectrometry (LESIMS) provides a powerful means for probing molecular films and their surface reactions. Simple molecules, including HCI, NH$_3$, D$_2$O, and their mixtures, were deposited into a thin film of several monolayer thickness on Ru(001) at low temperature in vacuum, and the surface was characterized by Cs$^{+}$ RIS and LESIMS. On pure films, D$_2$O, HCI, and NH$_3$ existed in the corresponding molecular states. When HCI and NH$_3$ were co-deposited, ammonium ion(NH$_4$$^{+}$) was readily formed by proton transfer from HCI to NH$_3$. In the presence of water molecules, HCI ionized first to hydronium ion(H$_3$O$^{+}$), which subsequently transferred proton to NH$_3$ to form NH$_4$$^{+}$. The proton transfer, however, did not occur to a completion on ice, in contrast to the complete reaction in aqueous solutions.s solutions.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2000년도 제18회 학술발표회 논문개요집
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• pp.155-155
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• 2000

Adsorption of alkali metals on a silicon surface has attracted much attention due to its importance in metal-semiconductor interface technology, In particular, the bonding nature of alkali metal to silicon substrate has been a focus of fundamental research efforts. We examined the adsorbed layer of Cs on a Si(111)-(7$\times$) surface by reactive ion scattering (RIS) of hyperthermal Cs+ beams. RIS from a Cs-adsorbed surface gives rise to Cs, representing pickup of surface Cs by Cs projectile. The Cs intensity is proportional to surface coverage of Cs at a high substrate temperature (473 K), while it varies anomalously with Cs coverage at low temperatures (130-170 K). This observation indicates that RIS selectively detects metallic Cs on surface, but discriminates ionic Cs. Transition from ionic to metallic Cs adlayer is driven by thermal diffusion of Cs and their clustering process.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2009년도 제38회 동계학술대회 초록집
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• pp.395-395
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• 2010

RIS(Reactive Ion Scattering)은 저 에너지 이온 빔을 쏘아 표면을 분석하는 방법이다. 분자 동력학 계산(MD simulation) 결과에 따르면 $Cs^+$이온은 두꺼운 얼음 표면에서 산란이 거의 일어나지 않는다. 본 연구에서는 이와 달리 Pt(111)과 Ru(0001) 표면에 생성시킨 두꺼운 얼음 표면에서 $Cs^+$이온 산란 실험이 가능함을 보였다. 한편, RIS signal은 얼음 층이 쌓인 구조나 두께에 따라 영향을 받는데, Ru(0001)과 Pt(111)의 표면에 생성시킨 crystalline water ice에서 시간과 water ice film의 두께가 RIS signal에 어떠한 영향을 미치는지도 조사하였다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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• pp.280-280
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• 2012

We examined ammonia diffusion on the surface of amorphous ice film through the measurement of decreasing residual quantity of $NH_3$ molecules compared to $H_2O$. The populations of $NH_3$ molecules on the surface of amorphous ice were monitored by using the techniques of temperature programmed reactive ion scattering (TPRIS) method. The ratio of intensity between ammonia and water was examined as a function of time at controlled temperature. When ammonia molecules were externally added onto an ice film at a temperature of 80 K, ammonia coverage with regard to ice was 0.12-0.16 ML. The intensity of ammonia molecules on the surface of ice decreased as time increased and the extent of decreased intensity of ammonia increased as controlled temperature increased. Moreover, energy barrier was estimated to be $51kJmol^{-1}$ on amorphous ice film. The results of the experiment indicate that ammonia molecules have a property of vertical diffusion into amorphous ice and the energy barrier of ammonia diffusion into bulk of ice is higher than that of hydrogen bonding.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제40회 동계학술대회 초록집
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• pp.338-338
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• 2011

The behavior of hydroxide ions on water-ice films was studied by using $Cs^+$ reactive ion scattering (RIS), low energy sputtering (LES) and temperature-programmed desorption (TPD). A $Cs^+$ beam of a low kinetic energy (<100 eV) from $Cs^+$ ion gun was scattered at the film surface, and then $Cs^+$ projectiles pick up the neutral molecules on the surface as $Cs^+$-molecule clusters form (RIS process). In LES process, the preexisting ions on the surface are desorbed by the $Cs^+$ beam impact. The water-ice films made of a thick (>50 BL) $H_2$O layer and a thin $D_2O$ overlayer were controlled in temperatures 90~140K. We prepared hydroxide ions by using Na atoms which proceeded hydrolysis reaction either on the ice film surface or at the interface of the $H_2O$ and $D_2O$ layers.[1] The migration of hydroxide ions from the $H_2O/D_2O$ interface to the top of the film was examined as afunction of time. From this experiment, we show that hydroxide ions tend to reside at the water-ice surface. We also investigated the H/D exchange reactions of $H_2O$ and $D_2O$ molecules mediated by hydroxide ions to reveal the mechanism of migration of hydroxide to the ice surface.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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• pp.279-279
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• 2012

In order to estimate the average migration lengths of $H_3O^+$ ions in amorphous ice, we conducted experiments of reactive ion scattering (RIS), low energy sputtering (LES), and reflection absorption IR spectroscopy (RAIRS) with an ultra-high vacuum (UHV) chamber. Dopped water-ice films were grown on the clean surface of Ru single crystal and analyzed with RIS, LES and RAIRS methods. The population changes of probe molecules, which were buried at a controlled distance from the surface, were monitored by those methods so that we can mesure the migration efficiencies. From the measured efficiencies, we evaluated the average migration lengths. This result is expected to give the information about the dynamics of proton in water-ice film.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제40회 동계학술대회 초록집
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• pp.333-333
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• 2011

We studied the H/D exchange kinetics of pure and acid dopped water-ice film by using the techniques of reactive ions scattering (RIS) and low energy sputtering (LES) with low kinetic energy cesium ion beam (<35 eV). From RIS, neutral water isotopomers were detected in the form of cesium-molecule ion clusters, $CsX^+$ (X= $H_2O$, HDO, $D_2O$). Ionic species, like $H_3O^+$, $DH_2O^+$, $D_2HO^+$, $D_3O^+$, adsorbed on the surface were ejected via LES process. Those techniques allowed us to trace the isotopomeric populations of water-ice film. To show the catalytic effect of excess proton in the H/D exchange reaction, our study was conducted with two types of water-ice films. In film 1, about 0.5 BL of $H_2O$ was adsorbed on HCl (0.1 ML) dopped $D_2O$ (8 BL) film. In film 2, similar amount of $H_2O$ used in film 1 was adsorbed on pure $D_2O$ film. Kinetic data were obtained from each film type for 90-110 K (film 1) and 110-130 K (film 2) and fitted with numerically integrated lines. Through the Arrhenius plot of kinetic coefficient deduced from fitting of the H/D exchange reaction, the activation energy of film 1 and 2 were estimated to be $10{\pm}3kJmol^{-1}$ and $17{\pm}4kJmol^{-1}$. This activation barrier difference could be understood from detailed pictures of H/D exchange. In film 2, both the formation of ion pair, $H_3O^+$ and OH. and proton transfer were needed for the H/D exchange. However, in film 1, only proton transfer was necessary but ion pair formation was not, so this might reduce the activation energy.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
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• pp.192-192
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• 2011

Hyperthermal ion scattering experiments were conducted with low kinetic energy (<35 eV) cesium ion beams to analyze the UV-photolyzed water-ice films. Neutral molecules (X) on the surface were detected as cesium-molecule ion clusters ($CsX^+$) which were formed through a Reactive Ion Scattering (RIS) process. Ionic species on the surface were desorbed from the surface via a low energy sputtering (LES) process, and were analyzed [1]. Using these methods, the thermal stability of hydronium ion ($H_3O^+$) that was produced by UV light was examined. As the thermal stability of $H_3O^+$ is related with the reaction, $H_3O^+$ + OH + $e^-$ (or $OH^-$) ${\rightarrow}$ $2H_2O$, which is similar or same with the reverse reaction of the auto-ionization of water, the result from this work would be helpful to understand the auto-ionization of $H_2O$ in water-ice that has not been well-understood yet. However, as $H_3O^+$ was not detected through a LES method, the titration experiment of $H_3O^+$ with methylamine ($CH_3NH_2$, MA), MA + $H_3O^+\;{\rightarrow}\;MAH^+$ + $H_2O$, was conducted. In this case, the presence of $MAH^+$ indicates that of $H_3O^+$ in the ice. Thus the pristine ice was photolyzed with UV light for a few minutes and this photolyzed ice was remained at the certain temperature for minutes without UV light. Then MA was adsorbed on that surface so that the population of $H_3O^+$ was found. From the calibration experiments, the relation of $MAH^+$ and $H_3O^+$ was found, so that the thermal stability of $H_3O^+$ can be investigated [2].