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Pravin Paudel CHEM 742 Dr. Dona Chen Department of Chemistry and Biochemistry University of South Carolina
and various application of this technique. quadruple. These emitted secondary ions are then analyzed by mass spectrometry.Introduction: Secondary ion mass spectrometry (SIMS) is a common technique used in surface science in which solid surface is bombarded by energetic primary ions. The three different basic mass analyzers: sector field. The particles are emitted from the layer close to the area of impact. The quadrupole mass analyzer uses combination of direct current and electric field to separate ions . study of ion chemistry. particles like Aun +. The emphasis has been given to the mechanism involved in the ion sputtering and secondary ion formation. Static and dynamic operational mode of the SIMS has been explained. neutrons or photons. and time of flight have been reviewed.Abstract: This paper talks about a Secondary Ion Mass Spectrometry (SIMS). the energy of the primary particles is transferred to the atoms of the solid by collision. electrons. However. and their various uses of those modes have been explored. When highly energetic primary particles are bombarded to the surface. The secondary particles emitted by the surface are positive ions. Magnetic sector uses the radius of parabolic path followed by the ions in presence of magnetic field to separate the particles. and about 95% of the emitted particles are from the first two layer of surface (book). negative ions or neutral particles. This collision of atoms results in the emission of the secondary particles from the surface. and detail chemical analysis of the solid surface. and different experiments have different demands of mass analyzer. alkali metal ions. Ga+. ion imaging. only the ionized particles emitted by surface are analyzed by mass analyzer in most of the cases (2). Bin +. SIMS is a common surface technique that is used for depth profiling. The three different mass analyzers are magnetic sector. and various other applications has been reported throughout. Some of the traditionally used primary ions are Ar+. 1. and secondary ions emitted from the surface are analyzed by mass spectrometry. analysis of trace elements in solid. Application of SIMS in dynamic analysis of trace amount of elements in solid materials. SF5 + and C60 + are commonly used as primary beams because they are less destructive to surface and they have higher secondary ion yields. Different modes of SIMS. when the sample is bombarded with high energy primary ions. Nowadays. quadrupole mass analyzer and time of flight mass analyzer. a technique that performs the mass spectroscopy of secondary ions emitted by the sample.
and Imaging SIMS is used t generate the image of analyte using secondary ions emitted. and secondary ions are emitted. General Concept 2.1 SIMS Formula: SIMS deals with the secondary ions emitted by the analyte. Static SIMS is commonly used to study the chemistry of surface layer. Collision cascade model has been most successful to explain quantitatively how the primary ion beams interacts with the atoms of . is ionization probability of ions. is fractional concentration of the species in surface layer. particles with higher masses moves slowly than the particles with lower masses. There are various models that explain how the primary ions interact with the sample surface. 2. However. Time of flight mass analyzer uses the concept that at same kinetic energy. Dynamic SIMS uses higher particle flux and is commonly used to generate sample depth profiles. Y is total sputter yield. The advances in time of flight mass analyzer have opened the door of SIMS to various applications. 2. Based on the primary particle flux density. and are no longer limited to the atomic analysis of surfaces. It was one of the most used mass analyzer technique in early work because of its small size that made it easy to use in ultrahigh Vacuum system (book). there are three analysis modes of SIMS: static or molecular SIMS.according to their mass to charge ratio. Imaging SIMS and Dynamic SIMS. Time of flight mass analyzer is the most used mass analyzer these days because of its very high transmission. Ip is a primary ion current.2 Sputtering Effects: When the energetic primary particles are bombarded to the surface of analyte. the exchange of energy takes place by series of collision. Static SIMS and Imaging SIMS uses lower primary flux particles and chemical damage of the surface is significantly low. and is a mass spectrometer transmission. The basic SIMS formula is given as: Is = IpY Where Is is secondary ion current of a particular species.
when incident ion beams hit the target. they pass the energy to the sample atom through a series of binary collisions.3 Matrix Effect: Very small fraction of the particles emitted from the surface are in the ionized state. electronic interaction cannot be ignored. . According to this model. When the surface is bombarded with oxygen. the yield of positive ions is higher. secondary particles are emitted. the yield of negative ion is higher. Fig 3 shows the general picture of mechanism involved in sputtering. The probability of the particles to be emitted as ion depends on the chemical and electronic properties of the matrix of the material to be studied that is formed by collision. When these collided particles are returned to the surface. However. Thus formed energetic target atoms colloide with other atoms. when the particle flux is lower as in Static SIMS. Fig. The capability of sputtering particle to gain or lose electron determines the ionization of the particles. and primary ion beams. and form collision cascade. interaction between primary ions and target atom is lower and can be neglected. 2. and if the surface is bombarded with the cesium. When the particle flux is high as in Dynamic SIMS.3 and 4 shows the variation of ion yield with electron affinity with respect to ionization potential and electron affinity. Fig.3: Cascade model for ion sputtering. and this effect is termed as matrix effect. Therefore. The graph shows that variation of ion yield with ionization potential and electron affinity is not regular. This probability of particle to be ionized also greatly depends on the composition of neighboring environment. This cascade model disregards the sputtering by electronic excitation.analyte. the secondary ion yields mainly depend on ionization potential for positive ion and electron affinity for negative ions. There should be a transfer of electrons or protons during sputtering to form an ion. and only considers the Knock on sputtering (book) as explained above.
Quadrupole mass analyzer consists of 4 parallel rods in which fixed DC and alternating radio frequency (RF) potential is applied.3: Variation of ion yield with ionization potential Fig. Resolution of this analyzer is determined by diameter and length of the rod. The specific combination of DC potential and radiofrequency electric field will result in some ions to follow stable path through quadrupole and hit to the detector. and is the angular frequency. However. other ions with m/Z will follow unstable path and are not detected by detectors.4: Variation of ion yield with Electron affinity 3.Fig. 3.1 Quadrupole mass analyzer This mass analyzer is also called mass filter because ions of single ion to mass ratio can pass through the apparatus. The secondary ions emitted are passed along the middle of quadrupole. Mass Analyzers: Different modes of SIMS have different requirements of mass analyzers. Two opposite parallel rods are applied a potential of +(U+Vcos t) and two others rod have potential of (U+Vcos t). V is the amplitude of applied RF. . where U is a fixed DC potential.
The ions with mass to charge ratio will pass through the flight tube that has equal centrifugal and centripetal force. From the definition of kinetic energy. Therefore. secondary ions are extracted by using applied voltage with a kinetic energy ZV. by changing either voltage or magnetic field. 3. to pass through the flight tube = (2) Where. where Z is the charge of ion and V is the applied voltage. all secondary ions emitted by the analyte are accelerated in field free space so that all particles have same kinetic energy. Fig.3. v is the velocity of secondary ion. m/Z of the ions that reaches the detector can be varied. we know particles with higher mass has .3 Time of Flight mass analyzer Time of Flight (TOF) mass analyzer is the simplest and most widely used mass analyzer.1: Schematic diagram of magnetic sector mass analyzer (0). These ions enter the flight tube where they encounter magnetic field B. r is the radius of circular path and m is the mass of secondary ion. 1 gives the basic instrumentation of the magnetic sector mass analyzer and indicates the pathway followed by the ions.2 magnetic sector mass analyzer In magnetic sector mass analyzer. In this analyzer. Equation two can be written as: = Thus. Fig. When these ions experience field force they follow a circular path.
Te secondary ions emitted may not have same energy distribution. Therefore. and that may create problem in the mass resolution. Combining eqn (2). Imaging SIMS . v= L/T Where L is the length travelled by particle and T is the time of flight of particle. Static SIMS 5. to compensate the degradation of mass resolution. the particles with mass m and charge Z can be separated by mass analyzer. T = (5) (4) (3) (2) Therefore. The particles are also accelerated before they reach the detector by applying the voltage so that all the particles reach the detector in given amount of time. 4. then KE = zV We also know.lower velocity and particle with lower mass has higher velocity at same kinetic energy(KE). (3). then KE is given as: KE = If the particle with mass m and charge Z is accelerated with potential V. Dynamic SIMS 6. If v is the velocity of particle with mass m. by looking at the time of flight. and (4) we get. the energy analyzer is used in flight tube.
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