JPS60114753A - Quantitative analysis method of constituent and device thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates generally to sensitive analytical techniques, and more particularly to the quantitative analysis of the concentration of specific constituent elements in a sample. This is sufficient sensitivity to isolate a single atom of a specific constituent element of the phase material.

Several methods are known in the art for determining the concentration of specific elements in Zanfur with relatively high sensitivity. One such method is known as resonance ionization spectroscopy, commonly abbreviated as RS. This method is described, for example, in U.S. Pat. It is also used as a reference here. The RIS method and its improvements have also been described in several publications, including an article titled ``Atomic Measurement'' in the September 1980 magazine ``Modern Physics.'' included. This paper is also referenced here.

Almost all atoms in the periodic table can be analyzed using 1(iS), but the sample must be in a gaseous state. It has the ability to define one atom.

As another highly sensitive and selective analysis method, secondary ion mass spectrometry, usually abbreviated as SIMS, is known. This method is described, for example, in Special Publication No. 4 of the National Bureau of Standards, published by the US Department of Commerce in October 1975.
It is described in No. 27. This is a newsletter that prints the work related to the S-Engineering MB and the ion microprobe mass spectrometer, and was edited by K.F.G./.Inrich and D.E. Newbury. Generally speaking, the SIMEI method bombards a sample with relatively high energy ions and then measures the secondary ions emitted from the sample. To increase selectivity, these secondary ions are subjected to Slil fractionation to define ions of a specific mass corresponding to the desired atom. Although such methods are mass selective, they are not elementally selective, eg, isobaric nuclei cannot be distinguished.

Another recognized problem with the 61MS method is that relatively few groups of secondary ions are generated during bombardment with Zanfur. Therefore, it is relatively difficult to define extremely small numbers of atoms of the desired nuclide. Furthermore, the 611MS method is difficult to perform quantitative analysis and may be unreliable due to chemical and physical matrix effects that greatly affect the secondary ion field. moreover,
Since various gaseous atmospheres are often used to assist in the generation of secondary ions, the 61MS method is also not applicable when measuring atoms with additional atmospheres.

Therefore, it would be desirable to provide an analytical method that is both sensitive and selective, and that is suitable for a larger number of samples than these prior art methods.

Therefore, it is an object of the present invention to scatter material from the surface of a sample and then ionize specific constituent elements of interest from the resulting scattered material by RIB to detect selected constituent elements in the sample. The object of the present invention is to provide a method for detecting these ions in order to measure the concentration of the element.

Another object of the invention is to prevent interference by secondary ions generated during scattering of lunar particles from the surface of the sample;
The objective is to detect ions generated by ionization of only neutral particles by RIB.

It is also an object of the present invention to scatter material from a homogeneous sample by means of an ion beam, to successfully define both compositional and geometrical dimensions, and then use RIB to determine the constituent elements of analytical interest. The aim is to uniquely ionize the resulting neutral particles and to detect these ions in order to determine the concentration of their constituent elements.

Another object of the invention is to provide a device for carrying out the above-mentioned method.

Furthermore, it is an object of the present invention to directly detect the ions produced by the RIB. Alternatively, these ions may be subjected to time-of-flight analysis (with or without an energy filter), quadrupole filter mass spectrometry, mass spectrometry, and/or other magnetic mass spectrometry or spectrophotographic analysis. An object of the present invention is to provide a device for detecting ions of.

In terms of the present invention, an apparatus and method of operating the apparatus are provided for sensitive and selective analysis of specific constituent elements in a sample. The sample is bombarded with energetic particles, such as ions, thereby creating a cloud containing neutral particles and secondary ions of the constituent elements within the sample. The secondary ions can be separated from the neutral particles, and the remaining neutral particles are ionized from a laser device with an appropriate wavelength to selectively ionize the neutral particles of the desired elemental nuclide. receive photons. Alternatively, all scattered material is ionized by RIS. Ions produced from selected nuclides can be processed in several ways to determine the concentration of constituent elements in a sample. These processing methods include direct measurements, time-of-flight mass spectrometry, rf quadrupole mass spectrometry, and magnetic mass spectrometry.

If desired, even the isotopic species of the constituent elements can be sorted out by the following six processing methods for final analysis.

Referring to FIG. 1, a periodic table of elements is shown. Within each compartment are shown the element symbol, the first excited state energy, the second excited state energy (if used), and the ionization potential for that element.

Additionally, in the center of each compartment is shown the specific resonance ionization spectroscopy scheme used to ionize that element.

These specific resonance ionization spectroscopy schemes (hereinafter referred to as R-S schemes) are shown above the periodic table. In Scheme 1, using potassium as an example, photons of selected wavelengths are used to excite electrons in the atom from the ground state to the first excited state. A secondary photon of the same wavelength ionizes the atom. Similarly for Scheme 3, a photon of the first wavelength excites the atom from its ground state to the first excited state. A photon of the secondary wavelength further excites the atom to a secondary excited state, and another photon of another wavelength completes the ionization process. This scheme 3 is used, for example, to generate zirconium ions. All elements on the periodic table except helium and neon are
By using commercially available lasers, it can be analyzed by one of five RS schemes.

FIG. 2 shows the basic principle of the invention.

According to the invention, a sample, whether solid or liquid, is bombarded with energetic particles. The energetic particles may be, for example, ions (including electrons) or neutral particles. If the particles have significant energy, a cloud of scattered material will form near the surface of the sample. This cloud will contain charged and neutral particles of nearly all constituent elements of the sample. The cloud is then passed through one or more laser beams, which emit wavelengths of light corresponding to those required to RIB ionize specific constituent elements of the cloud. It has been adjusted. In this way, R-S ions corresponding to the 414 elements in the sample to be analyzed are generated,
The amount of this ion is related to the concentration of the constituent elements in the sample.

Referring to FIG. 3, the basic components and principles necessary to practice the present invention are illustrated.

Sample 10 of the material to be investigated is in vacuum container 1
It is installed properly in 2. The specific pressure (degree of vacuum) required to carry out the present invention will be detailed later. Sample 10 is bombarded with an ion beam 14 emitted from ion source 16 in this example. Since the ion source also produces ions of other materials than those desired for beam 14, a magnetic mass filter can be used as an element of beam conditioning device 18 to remove these extra ions. The ion beam 1
4 bombards the sample 10, causing the release of a cloud of secondary ions and neutral atoms from the sample, for example. Although not shown in this figure, a device is provided to suppress the secondary ions and leave behind neutral particles, which can be used in the subsequent analysis step if this suppression is desired. It will be done. After suppressing these secondary ions, a laser beam 20 emitted from an R/S laser source 22 is passed through the neutral particles, where material corresponding to the RI8 photon wavelength is ionized. Ru. These R-S generated ions are shown in the drawing as an ion beam 24, which is applied to a suitable ion counter 26 and connected to a conductor 28.
Give an electrical signal to the top. Also, although not shown here (and not shown in Figures 4 to 7), a device may be provided to accelerate and/or converge the ions produced by the RS toward the detector. It is being

Although RS ionizes atoms of a particular element or molecule by selecting the laser wavelength, in certain special applications, different ions with different masses may be produced.

These are small amounts of ions of the element we are trying to detect, as well as other elements that are present in the gas. Industrial lasers can be used to discriminate isotopes of a given element, but only in certain special cases. On the other hand, it is often desired to select ions with a particular mass from among various actually produced ions. Therefore, the present invention includes the use of various mass spectrometers.

One of the simplest ways to obtain information about the mass of an ion is by using a time-of-flight TI mass spectrometer. This is shown in FIG. As in FIG. 6, an ion beam 24 containing mainly ions of a single element is produced by using the R process on the neutral particles generated from the sample 10.

These ions are then passed through a time-of-flight mass spectrometer (TOF) 30 before hitting a detector 26. Determining the time between the creation of the ion and the time it reaches the detector determines the specific gravity of the ion(s) providing the signal on conductor 28, which in turn determines the RIS process l
The influence of foreign ionization at c can be reduced. Furthermore, to select 2 (atomic number) of the atom, RI
By using B and using a mass spectrometer to select A (atomic mass) of the atom, it is possible to select 2 and A for the same atom. For example, by this method it is possible to separate isobaric nuclei with the same A and different z.

Ions generated via RIB of scattered atoms can have a fairly wide energy range. Therefore, for all mass analysis, an energy filter 32 is inserted into the ion beam 24 before the mass spectrometer, in this case TOF3Q. Such an energy filter may also be utilized in a variety of possible cases, as shown in FIGS. 5, 6 and 7.

Another method for obtaining information such as regarding the mass of an ion is to use an r-f quadrupole mass spectrometer 34, as shown in FIG. This quadrupole mass spectrometer has certain advantages over TOF when it is desirable to keep the ion energy low and better mass selection is required.

FIG. 6 shows another mass spectrometer using a fan-shaped magnetic mass spectrometer 36 inserted into the ion beam in front of the detector 26. Magnetic analyzers are very efficient (high throughput) and have isotope detection sensitivities of 106 or I
There are advantages to having a high value of about L17. In this way, additional mass discrimination can be performed.

FIG. 7 shows a modified example of the mass spectrometer shown in FIG. A principle for significantly increasing isotope detection sensitivity is presented. The ions that have passed through the sector magnet 36 are
It is driven into the target 38. Additional ion acceleration must be performed to drive the ions into the target.

This is accomplished by an accelerating grid 40, which is supplied with suitable voltage(s) through conductors 44 from a voltage source 42. During this implant, a detector 26 measures the electrons emitted from the target.

Once a fraction of the constituent elements of interest in the sample have been removed, ionized, and implanted into the target, the target can be returned to the sample location. This nuclide of interest is re-ionized and the ions are passed through the magnetic mass spectrometer again. If the isotope extraction sensitivity of a mass spectrometer is 106, the degree of discrimination between adjacent mass numbers (e.g. isotopes) is 10 by passing twice.
12, and after n passes through the spectrometer, the degree of discrimination between adjacent masses will be i o'n.

Having thus far described the basic principles of the invention, FIG. 8 depicts an exemplary apparatus for carrying out the invention.

This is a top cross-sectional view of analysis vessel 46, which is provided with, for example, a plurality of flange holes 48-58, the purpose of which will be described below. Said hole 50.
58 are fitted with full/shiro 0.62, each having a radar beam penetrable window 64,66, which allows the radar beam 68 to pass from the source 7o into the vessel 46. I can do it. The laser source TO may, if desired, include a device for generating the laser beam in pulses. Mounted above the hole 52 is a flange 72 or other suitable support device, which provides a ground collimator leading into the container 46.
Hole 52 is also fitted with a franchise 6 or other suitable connector for a transport tube 78 emerging from charged particle source 8o. Source 8o passes charged particle beam 82 through transport tube 78 and collimating tube T4. Said transport tube γ8 and/or source 80 includes devices for converging and/or pulsing charged particle beam 82. (not shown) may be provided.

Sample 84 may be positioned close to the trajectory of laser beam 68 by any suitable mechanism. In this figure, a sample 84 is mounted on the end of a sample support 86, which may be attached to a suitable fastener 90.
It is attached from the rod 88 using. The rod 88 passes through an insulator 92 in a flange 94 attached to the hole 48, and the terminal 96 of the rod 88 has a
If desired, a voltage (E4) can be applied.

Also shown in FIG. 9, when the sample 84 is placed in the analysis position, it is placed in the bottom of the 7 Alladay shield 98 and the Faraday shield Halley beam 68.
It has opposing openings 100, 102 for passage of the material. The seven Alladay traces 98 can be supported from an insulator 104. Furthermore, the insulator is a group of electrodes 1
06-114, which are separated from each other by suitable insulators. The electrode 106 is provided with a grid 116 within its opening 118 to better contain the electric field generated by the electrode. A similar grid is placed on the electrodes 108, 110 for the same purpose. Electrodes 106-110 are each connected to a suitable voltage J via conductors 120-124.
Fi2°E3 is applied and the conductor passes through a suitable flange 126 attached to hole 56. In the illustrated embodiment, electrodes 112 and 114 are
It is operated with the same voltage E3 as .

The electrode 114 is attached to the inner end of a zero field drift tube 128. The tube 128 is located within a grounded support sleeve 130 that is attached to the bore 56 with a flange 132 or other suitable device. The outer end of the drift tube 128 passes through a conduit 134 that can be attached from a flange 136, for example. This drift tube is directed to a suitable ion handling device and/or recognition device M138, such as an F4 organ analyzer and/or detector.

In normal operation of the apparatus shown in FIG.
A beam of energetic particles, such as positive ions, is generated at source 80 and passed through collimator 74 to bombard sample 84 .

This beam produces a cloud of scattered material near the surface of the sample, containing both ions and neutral particles. As described above, as the appropriate laser beam(s) 68 pass through this cloud, the wavelength of the laser beam is selected corresponding to the element(s) selected for the RISiC. ions are generated. This R engineering S ion is applied to electrodes 106 to 114.
K is drawn into the drift tube 128 using an appropriate voltage applied thereto. If the ions produced during scattering are not analyzable, a repulsive electric field is created between electrode 106 and sample 84 (and shield 98); in this case,
Until the laser beam passes through the cloud, the electrode 106
sample) will also have a positive voltage.

The device shown in Figure 8 is designed primarily for pulse operation.
The various operating steps of the method are performed in a time sequence. For example, a typical time graph of this method is
It is shown in Figure 0. During an initial period of time, such as from time to to t2, target 84 is impacted. There is no flow of energetic particles. Then, between times t2 and t3, the beam of energetic particles 82 can impact the sample and scatter material therefrom. During approximately the same time interval or a slightly longer time interval, for example between tl and t4, the positive voltage E1.
E2 is applied to electrodes 106 and 108VC, respectively.

If desired, sample 84 and shield 98 also have a negative voltage I! You may also multiply by 84. If these voltages are present at electrode 106 and sample 84, any ions generated during scattering will be repelled towards the sample and the shield.

Immediately after this load particle pulse is completed, a radar pulse is generated at time t5. At or near this time, the voltage El 11!
: E2 will be reversed and will extract the R-S ions produced by the radar beam 6B. These voltages may last until time t6, for example, to ensure that the RS ions are drawn into the drift tube 128. Electrode 110 (and electrodes 112, 114) are held at a constant voltage E3 to aid in the extraction of R-S ions.

Alternatively, the shape of the electrodes can be changed to allow the laser beam to pass between the repulsion electrode 106 and the extraction electrode 108. In this case, repositioning and/or shaping of the repulsion electrode near the sunhole may be necessary.

The time sequence may also need to change, as is understood in the art.

Ion detectors, typically electron multiplier detectors, produce many spurious signals. It is therefore necessary to discriminate between these signals and the signals emanating from the ions of interest.

One way to do this is to use a detector that dates the pulses a little later than the radar pulses. During this pulse-keying interval, the desired output signal will occur with minimal interference.

The signal can represent either ions of an element or isotopes of that element. Referring to FIG. 11, for example, confirmation of the isotope of a specific element is shown. A graph of the count rate of a laser beam as a function of mass, as shown for a particular atomic number and a constant laser wavelength(s), is based on the atomic mass (i.e., the isotope) of the element. element), for example (
A).

(A+1) and (A+2) are shown.

Alternatively, the wavelength(s) of the laser beam can be varied with respect to constant (A) to discriminate between isobaric nuclei. In this case, the counting rate per laser pulse at each wavelength is a specific element, for example (211A1), even in the case of isobaric nuclei.

(Z2 + A1) will be confirmed. This is shown in the bar graph for the combination of (Z) and (A) for each phase in FIG. The above graph also shows a typical case, in which a certain nuclide (Z3
r A3 ) abundance ratio and other nuclides (Z4 + A4
), the wavelength (which defines (2)) and the magnetic field (which defines (A)) are programmed together.

To further illustrate the invention, the following examples provide analysis of the constituent elements of specific samples.

Aluminum impurity in silicon is one analysis that can be performed using the present invention.

A small silicon chip with dimensions of approximately 0°5 x 6 x 6' mm is placed on the support 86, which is spaced approximately 1.5 cIn from the extraction electrode 106 and is also spaced from the container 46.
is approximately 5 X I Ll” Torr (6,80X
The sample is then baked to a temperature of approximately 250°C to drive out any residual gas atoms or absorbed molecules from the previous atmospheric environment from the sample. Thereafter, The degree of vacuum is approximately iQ'-9 Torr
r (1°66×10-”kg/cIn”).

A positive argon ion beam is adjusted to produce a current of about 1 mA under an accelerating voltage of about 20 KV.

This ion beam has a frequency of 10H2 and 2×10
It is generated in pulses at a rate of one ion pulse hitting the target in -6 seconds. During this pulse generation, approximately 1.3 x IU'' of argon ions are focused to a 1-2 mm diameter point on the sample.

Both aluminum and silicon scattering generate approximately 2 neutral atoms per ion bombardment, and therefore approximately 2.5 x 1010 silicon neutral atoms and , 2-6 aluminum atoms are scattered. Atoms are ejected in each direction as indicated by the cosine distribution.

The atoms are also ejected with an average energy of about 10 eV. This scattered ion (silicon and aluminum) is located between the target and the electrode 106 at a distance of about -600 mm.
It is pulled back to the target by the bias voltage. The scattered neutral atoms of silicon and aluminum are
It is intersected by a 1u diameter laser beam centered 11i above the sample surface.

The laser Ikkou is typically the Quanta Ray model, D
OR-IA na:yAG and model PDL-1 die-cast. The wavelength of the laser light produced by the laser beam is 6096 angstroms (6096 angstroms), and excites the neutral atoms of aluminum from the ground state force to the excited state. This excited aluminum atom has a wavelength of 3093. is photoionized by absorption of secondary photons (see Scheme 1 in Figure 1, I1.).

Typically, the Quantarey model DOR-IAN
(1: YAG, model pDb-1 die race using DOM die supplied by Exciton Chemical Co., and 58° supplied by Quantarey) (DjP
A frequency doubling crystal emits 3093 A of light with an energy of 10 millijoules per p per ), 07 renu. This light energy is expressed in a beam of 1-diameter, which is about υ2 after the incidence of 2×1'08-m.
．． After a delay of 5 x 10' seconds, Jl/nu is reached. During this time both fast and slow neutral aluminum atoms can be moved into the laser beam.

In the case of aluminum, the laser beam will ionize about 1 percent of the atoms in the selected R&S process.
If all ions are sent through the system and 6000 laser pulses are used, then 1 in 1010 silicon atoms
Aluminum atoms can be measured with an error of 70 las minus 10%.

If additional sensitivity and/or dust is desired,
The number of laser pulses can be increased.

As mentioned above, the method described with respect to the apparatus of FIG. 8 is a Hapars mode method. 21ni 914's 7 mars, i.e., the ion beam bombarding the sample/clueless,
Laser beam pulses are used. In some types of analysis, it may be difficult to determine the composition of specific elements at the surface of a sample, and then to determine the composition at various locations within the sample. This means that
Using the apparatus described herein, analysis of the composition at a surface can be performed by first pulsing the ion beam and then using a pulsed plasma beam. The ion beam then bombards the sample over a longer time interval and/or at a higher frequency, which can scatter a portion of the surface. This allows the analysis of specific constituent elements to be repeated at depths below the surface, a technique called desozorofiling.

The apparatus and method of operation of what is considered to be the preferred embodiment of the invention has been described herein. It will be appreciated by those skilled in the art that various changes and modifications can be made without departing from the invention. Accordingly, the scope of the invention is to be determined solely by the appended claims and their equivalents.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the elements of the periodic table and various possible co-11β ionization spectroscopic schemes suitable for selective white ionization of these elements; FIG. 2 is a schematic diagram illustrating the principle of the invention; FIG. 6 is a schematic diagram illustrating the principle of the invention, namely RIEI starting by scattering by direct detection of ions produced by resonance ionization spectroscopy (RIB); FIG. Schematic diagram illustrating the principle of the present invention using a type mass spectrometer, FIG.
-f A schematic diagram showing the principle of the present invention using a quadrupole mass spectrometer, FIG. 6 is a schematic diagram showing the principle of RIB initiated by scattering using a sector magnetic mass spectrometer, and FIG. FIG. 8 is a schematic diagram illustrating the principles of the invention and the principle of enriching selected constituent elements, or isotopes thereof, in a sample to increase sensitivity; FIG. FIG. 9 is a partially enlarged view of the device shown in FIG. FIG. 12 is a graph showing a method for detecting isotopic nuclides of elements in a sample by changing the magnetic field of a sector-shaped magnetic mass spectrometer according to the invention; FIG. 1 is a graph showing a method for detecting a specific element in a sample by changing the magnetic field of the meter. In the figure, 10.84...Sample 14.82...Energy particle beam 16.80...
・Ion source 20.68...Laser-beam 22.70...Laser-beam source 26...Detector 30...Time-of-flight mass spectrometer 34...Quadrupole mass spectrometer 36... Fan-shaped magnetic mass spectrometer 38... Target 106... First electrode 108... Second electrode representative Year-711 Oblique Grass γ11 N1:,ni-”1/Circulation+t Continuation of page 1 @Inventor James E.P.Arks ■Inventor's Button Lud W. Ashmit Oak Ridge, Tennessee, United States of America, Oak Ridge, New Work Lane 103 Canterbury Road, Oak Ridge, Tennessee, United States of America 121 Procedural amendment (method) % formula % 1. Indication of the case Patent Application No. 221934 of 1983 3. Person making the amendment jI (Relationship with I'l) ,:'1 Applicant address 4, Agent 5, Daily j1ζ of amendment order (February 28, 2016 6, Number of inventions increased by amendment 7, Power of attorney subject to amendment, and 1 translation of ?) General

Claims (1)

[Scope of Claims] (1) In a quantitative analysis method having sufficient sensitivity to determine constituent elements in a sample as small as 11 atoms, a) bombarding the sample with energetic particles; and thereby producing a cloud of constituent elements in said sample. (1) In order to selectively ionize the constituent elements in the cloud corresponding to the constituent elements, resonance ionization spectroscopy using a laser beam is performed on the first cloud. c) Accurately and substantially simultaneously detecting pre-self ions resulting from resonance ionization spectroscopy by the laser in order to measure the amount of the constituent elements in the sample with high self-sensitivity. A method for quantitative analysis of constituent elements, characterized by comprising: (2. The method of claim 1, wherein the cloud includes ions and neutral particles, and the method further includes removing the ions from the cloud prior to the resonant ionization spectroscopy step with the laser. (3) A method for quantitative analysis of constituent elements, wherein the method according to claim 1, wherein the energetic particles include a beam of energetic ions. (4) A method for quantitative analysis of constituent elements, comprising: The method according to claim 1, further comprising subjecting the ions produced by resonance ionization spectroscopy using the laser to mass spectrometry before the detection step. (5) Quantitative analysis of constituent elements. The method according to claim 4, wherein the mass spectrometry comprises passing the ions through a time-of-flight mass spectrometer. (6) The method according to claim 4, Mass spectrometry involves passing the ions through an r-f quadrupole mass spectrometer. A method for quantitative analysis of constituent elements, comprising passing the ions through a fan-shaped magnetic mass spectrometry needle. A method for quantitative analysis of constituent elements, comprising: implanting a target into a target; and returning the target to the sample for repeating the analysis. (9) The method according to claim 6. In this method, the impacting ion beam includes a positive argon ion. (In the method described in claim 1, the impacting energetic particles are a repeatedly pulsed beam. Quantitative analysis method for constituent elements comprising: aη In the method according to claim 10, the laser beam for performing resonant ionization spectroscopy has a temporal relationship selected with respect to the frequency of the energetic particle beam. Q4. In the method of claim 2, removing the ions from the cloud involves applying a negative voltage across the sample to the A method for quantitative analysis of constituent elements, which is carried out by maintaining a voltage higher on the negative side than the voltage applied to the first electrode adjacent to the sample. (b) The method according to claim 4, further comprising: A method for quantitative analysis of constituent elements, comprising passing ions generated by resonance ionization spectroscopy using the laser beam through an energy filter before subjecting the ions to the mass spectrometry. α4 In the method according to claim 12, a voltage is further applied to a second electrode adjacent to the first electrode in order to accelerate the ions generated by resonance ionization spectroscopy by the laser. and removing more from the sample than from the first electrode. 0 Clause The method according to claim 14, wherein the ionization step by resonance ionization spectroscopy using radar is carried out between the first electrode and the sample. 15. The method according to claim 14, wherein the ionization step by resonance ionization spectroscopy using radar is performed between the first electrode and the second electrode. αη The method according to claim 1, wherein the detection of the ions of the specific element is performed by an electron multiplier detector. 0. Regarding the constituent elements in a sample, in a quantitative analyzer having sufficient sensitivity to determine small atomic species, a) a device for mounting the sample; a) a source of energetic particles having sufficient energy to scatter material from the sample to form a cloud of scattered constituent elements of the sample; c) an apparatus for directing the energetic particles onto the sample, thereby creating a scattering cloud of the constituent elements in the sample; 2) a laser beam source tuned to emit a beam of photons having selective wavelengths capable of producing ions by resonant ionization spectroscopy of selected constituent elements within the cloud; e) an apparatus for directing the selected photons from the laser source to intersect with the cloud, thereby selectively ionizing the selected constituent elements; f) a detection device for accurately and substantially simultaneously measuring the ions generated by the resonance ionization spectroscopy in order to measure the amount of the constituent elements with the sensitivity; A quantitative analysis device for constituent elements, characterized by comprising: (6) The apparatus according to claim 18, wherein the energetic particle source is an energetic ion beam source.翰 The apparatus according to claim 18, further comprising a device for separating ions produced by the energetic particles from the cloud. Qυ The apparatus of claim 20, wherein the apparatus for separating ions includes a first pole adjacent to the sample attachment device, the voltage at the first electrode being relative to the sample; An apparatus for quantitative analysis of constituent elements maintained at a voltage such that the ions are repelled towards the sample. The apparatus according to claim 21 further includes an accelerator adjacent to the first electrode, for accelerating the ions produced by the resonance ionization spectroscopy toward the detection device. A quantitative analysis device for constituent elements that removes more from one electrode than from the sample mounting device. (c) The apparatus according to claim 22, wherein the accelerator includes a second electrode maintained at a voltage sufficient for the acceleration. (c) In the apparatus according to claim 19, the ion source produces a beam of positive argon ions.
Quantitative analysis device for constituent elements. (c) The apparatus according to claim 24, further comprising a device for pulsing the ion beam from the source before directing the ions from the ion source onto the sample. Quantitative analysis device for constituent elements. (c) The apparatus according to claim 25, further comprising a device for converting the photon beam into a pulse having a frequency having a time relationship with the pulse of the ion beam. Quantitative analysis device. (2) The apparatus according to claim 18, wherein the detection device for the ions of the constituent elements in the sample includes an electron multiplier detector. (c) In the apparatus according to claim 18, the sample mounting device and the A quantitative analysis device for constituent elements that includes an energy filter inserted between the detection device and the detection device. 28) The apparatus according to claim 28, further comprising a mass spectrometer disposed on the output side of the energy filter for mass-discriminating the ions generated by the resonance ionization spectroscopy. Quantitative analysis device for constituent elements. (g) The apparatus according to claim 29, wherein the mass spectrometer is a time-of-flight mass spectrometer. 0me The apparatus according to claim 29, wherein the mass spectrometer is an RF quadrupole mass spectrometer. 0埠 The apparatus according to claim 29, wherein the mass spectrometer is a fan-shaped magnetic mass spectrometer.